Adsorption at Nanoconfined Solid-Water Interfaces.

Reactions at solid-water interfaces play a foundational role in water treatment systems, catalysis, and chemical separations, and in predicting chemical fate and transport in the environment. Over the last century, experimental measurements and computational models have made tremendous progress in capturing reactions at solid surfaces. The interfacial reactivity of a solid surface, however, can change dramatically and unexpectedly when it is confined to the nanoscale. Nanoconfinement can arise in different geometries such as pores/cages (3D confinement), channels (2D confinement), and slits (1D confinement). Therefore, measurements on unconfined surfaces, and molecular models parameterized based on these measurements, fail to capture chemical behaviors under nanoconfinement. This review evaluates recent experimental and theoretical advances, with a focus on adsorption at solid-water interfaces. We review how nanoconfinement alters the physico-chemical properties of water, and how the structure and dynamics of nanoconfined water dictate energetics, pathways, and products of adsorption in nanopores. Finally, the implications of these findings and future research directions are discussed.

Impact of Variable Water Chemistry on PFOS-Goethite Interactions: Experimental Evidence and Surface Complexation Modeling.

Perfluorooctanesulfonate (PFOS) has become a major concern due to its widespread occurrence in the environment and severe toxic effects. In this study, we investigate PFOS sorption on goethite surfaces under different water chemistry conditions to understand the impact of variable groundwater chemistry. Our investigation is based on multiple lines of evidence, including (i) a series of sorption experiments with varying pH, ionic strength, and PFOS initial concentration, (ii) IR spectroscopy analysis, and (iii) surface complexation modeling. PFOS was found to bind to goethite through a strong hydrogen-bonded (HB) complex and a weaker outer-sphere complex involving Na+ coadsorption (OS-Na+). The pH and ionic strength of the solution had a nontrivial impact on the speciation and coexistence of these surface complexes. Acidic conditions and low ionic strength promoted hydrogen bonding between the sulfonate headgroup and protonated hydroxo surface sites. Higher electrolyte concentrations and pH values hindered the formation of strong hydrogen bonds upon the formation of a ternary PFOS-Na+-goethite outer-sphere complex. The findings of this study illuminate the key control of variable solution chemistry on PFOS adsorption to mineral surfaces and the importance to develop surface complexation models integrating mechanistic insights for the accurate prediction of PFOS mobility and environmental fate.

Multicomponent and Surface Charge Effects on PFOS Sorption and Transport in Goethite-Coated Porous Media under Variable Hydrochemical Conditions.

Perfluorooctanesulfonate (PFOS), a toxic anionic perfluorinated surfactant, exhibits variable electrostatic adsorption mechanisms on charge-regulated minerals depending on solution hydrochemistry. This work explores the interplay of multicomponent interactions and surface charge effects on PFOS adsorption to goethite surfaces under flow-through conditions. We conducted a series of column experiments in saturated goethite-coated porous media subjected to dynamic hydrochemical conditions triggered by step changes in the electrolyte concentration of the injected solutions. Measurements of pH and PFOS breakthrough curves at the outlet allowed tracking the propagation of multicomponent reactive fronts. We performed process-based reactive transport simulations incorporating a mechanistic network of surface complexation reactions to quantitatively interpret the geochemical processes. The experimental and modeling outcomes reveal that the coupled spatio-temporal evolution of pH and electrolyte fronts, driven by the electrostatic properties of the mineral, exerts a key control on PFOS mobility by determining its adsorption and speciation reactions on goethite surfaces. These results illuminate the important influence of multicomponent transport processes and surface charge effects on PFOS mobility, emphasizing the need for mechanistic adsorption models in reactive transport simulations of ionizable PFAS compounds to determine their environmental fate and to perform accurate risk assessment.

Eu(III) and Am(III) adsorption on aluminum (hydr)oxide minerals: surface complexation modeling.

Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals-corundum (α-Al2O3), γ-alumina (γ-Al2O3) and gibbsite (γ-Al(OH)3)-and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al2O3) and γ-alumina (γ-Al2O3) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals.

Acid-Base Properties of Cis-Vacant Montmorillonite Edge Surfaces: A Combined First-Principles Molecular Dynamics and Surface Complexation Modeling Approach.

Montmorillonite layer edge surfaces have pH-dependent properties, which arises from the acid-base reactivity of their surface functional groups. Edge surface acidity (with intrinsic reaction equilibrium constant, pKa) is a chemical property that is affected by crystal structure. While a cis-vacant structure predominates in natural montmorillonites, prior molecular-level studies assume a centrosymmetric trans-vacant configuration, which potentially leads to an incorrect prediction of montmorillonite acid-base surface properties. We computed intrinsic acidity constants of the surface sites of a montmorillonite layer with a cis-vacant structure using the first-principles molecular dynamics-based vertical energy gap method. We evaluated pKa values for both non-substituted and Mg-substituted layers on common edge surfaces (i.e., surfaces perpendicular to [010], [01̅0], [110], and [1̅1̅0] crystallographic directions). The functional groups ≡Si(OH), ≡Al(OH2)2/≡Al(OH)(OH2), and ≡SiO(OH)Al sites on surfaces perpendicular to [010] and [01̅0] and ≡Si(OH)U, ≡Si(OH)L, ≡Al(OH2), and ≡Al(OH2)2 on surfaces perpendicular to [110] and [1̅1̅0] determine the proton reactivity of non-substituted cis-vacant edge surfaces. Moreover, the structural OH sites on edge surfaces had extremely high pKa values, which do not show reactivity at a common pH. Meanwhile, Mg2+ substitution results in an increase in pKa values at local or adjacent sites, in which the effect is limited by the distance between the sites. A surface complexation model was built with predicted pKa values, which enabled us to predict surface properties as a function of pH and ionic strength. Edge surface charge of both trans- and cis-vacant models has little dependence on Mg2+ substitutions, but the dependence on the crystal plane orientation is strong. In particular, at pH below 7, edge surfaces are positively or negatively charged depending on their orientation. Implications of these findings on contaminant adsorption by smectites are discussed.

The role of organic and inorganic substituents of roxarsone determines its binding behavior and mechanisms onto nano-ferrihydrite colloidal particles.

The retention and fate of Roxarsone (ROX) onto typical reactive soil minerals were crucial for evaluating its potential environmental risk. However, the behavior and molecular-level reaction mechanism of ROX and its substituents with iron (hydr)oxides remains unclear. Herein, the binding behavior of ROX on ferrihydrite (Fh) was investigated through batch experiments and in-situ ATR-FTIR techniques. Our results demonstrated that Fh is an effective geo-sorbent for the retention of ROX. The pseudo-second-order kinetic and the Langmuir model successfully described the sorption process. The driving force for the binding of ROX on Fh was ascribed to the chemical adsorption, and the rate-limiting step is simultaneously dominated by intraparticle and film diffusion. Isotherms results revealed that the sorption of ROX onto Fh appeared in uniformly distributed monolayer adsorption sites. The two-dimensional correlation spectroscopy and XPS results implied that the nitro, hydroxyl, and arsenate moiety of ROX molecules have participated in binding ROX onto Fh, signifying that the predominated mechanisms were attributed to the hydrogen bonding and surface complexation. Our results can help to better understand the ROX-mineral interactions at the molecular level and lay the foundation for exploring the degradation, transformation, and remediation technologies of ROX and structural analog pollutants in the environment.

Enhanced adsorption and colorimetric detection of tetracycline antibiotics by using functional phosphate/carbonate composite with nanoporous network coverage.

This work presents efficient tetracycline (TC) antibiotics adsorption using a functional porous phosphate/carbonate composite (PCC). The PCC was fabricated by anion-exchange of phosphate on the surface of vaterite-phase calcium carbonate particle scaffolds. The PCC, having dense nanoporous network coverage with large surface area and pore volume, exhibited excellent TC adsorption in solution. Its adsorption isotherm fitted well to the Freundlich model, with a maximum adsorption capacity of 118.72 mg/g. The adsorption process was spontaneous, endothermic, and followed pseudo-second-order kinetics. From the XPS analysis, the hydrogen bonding and surface complexation were the key interactions in the process. In addition, a colorimetric TC detection method was developed considering its complexation with phosphate ions, originating from PCC dissolution, during adsorption. The method was used to detect TC in mg/L concentrations in water samples. Thus, the multifunctional PCC exhibited potential for use in TC removal and environmental remediation.

Community Data Mining Approach for Surface Complexation Database Development.

This paper presents a comprehensive data-to-model workflow, including a findable, accessible, interoperable, reusable (FAIR) community sorption database (newly developed LLNL Surface Complexation/Ion Exchange (L-SCIE) database) along with a data fitting workflow to efficiently optimize surface complexation reaction constants with multiple surface complexation model (SCM) constructs. This workflow serves as a universal framework to mine, compile, and analyze large numbers of published sorption data as well as to estimate reaction constants for parameterizing reactive transport models. The framework includes (1) data digitization from published papers, (2) data unification including unit conversions, and (3) data-model integration and reaction constant estimation using geochemical software PHREEQC coupled with the universal parameter estimation code PEST. We demonstrate our approach using an analysis of U(VI) sorption to quartz based on a first L-SCIE implementation, concluding that a multisite SCM construct with carbonate surface species yielded the best fit to community data. Surface complexation reaction constants extracted from this approach captured all available sorption data available in the literature and provided insight into previously published reaction constants and surface complexation model constructs. The L-SCIE sorption database presented herein allows for automating this approach across a wide range of metals and minerals and implementing novel machine learning approaches to reactive transport in the future.

Reduction of U(VI) on Chemically Reduced Montmorillonite and Surface Complexation Modeling of Adsorbed U(IV).

Adsorption and subsequent reduction of U(VI) on Fe(II)-bearing clay minerals can control the mobility of uranium in subsurface environments. Clays such as montmorillonite provide substantial amounts of the reactive surface area in many subsurface environments, and montmorillonite-containing materials are used in the storage of spent nuclear fuel. We investigated the extent of reduction of U(VI) by Fe(II)-bearing montmorillonite at different pH values and sodium concentrations using X-ray absorption spectroscopy and chemical extractions. Nearly complete reduction of U(VI) to U(IV) occurred at a low sodium concentration at both pH 3 and 6. At pH 6 and a high sodium concentration, which inhibits U(VI) binding at cation-exchange sites, the extent of U(VI) reduction was only 70%. Surface-bound U(VI) on unreduced montmorillonite was more easily extracted into solution with bicarbonate than surface-bound U(IV) generated by reduction of U(VI) on Fe(II)-bearing montmorillonite. We developed a nonelectrostatic surface complexation model to interpret the equilibrium adsorption of U(IV) on Fe(II)-bearing montmorillonite as a function of pH and sodium concentration. These findings establish the potential importance of structural Fe(II) in low iron content smectites in controlling uranium mobility in subsurface environments.

Interaction between Organic Compounds and Catalyst Steers the Oxidation Pathway and Mechanism in the Iron Oxide-Based Heterogeneous Fenton System.

In the past decades, extensive efforts have been devoted to the mechanistic understanding of various heterogeneous Fenton reactions. Nevertheless, controversy still remains on the oxidation mechanism/pathway toward different organic compounds in the classical iron oxide-based Fenton reaction, largely because the role of the interaction between the organic compounds and the catalyst has been scarcely considered. Here, we revisited the classic heterogeneous ferrihydrite (Fhy)/H2O2 system toward different organic compounds on the basis of a series of degradation experiments, alcohol quenching experiments, theoretical modeling, and intermediate analysis. The Fhy/H2O2 system exhibited highly selective oxidation toward the group of compounds that bear carboxyl groups, which tend to complex with the surface ≡Fe(III) sites of the Fhy catalyst. Such interaction results in a nonradical inner sphere electron transfer process, which seizes one electron from the target compound and features negligible inhibition by the radical quencher. In contrast, for the oxidation of organic compounds that could not complex with the catalyst, the traditional HO· process makes the main contribution, which proceeds via hydroxyl addition reaction and could be readily suppressed by the radical quencher. This study implies that the interaction between the organic compounds and the catalyst plays a decisive role in the oxidation pathway and mechanism of the target compounds and provides a holistic understanding on the iron oxide-based heterogeneous Fenton system.

Understanding Competitive Phosphate and Silicate Adsorption on Goethite by Connecting Batch Experiments with Density Functional Theory Calculations.

Despite the biogeochemical importance of phosphate fate and transport in aquatic environments, little is known about how competition with other common aqueous oxyanions affects its retention by mineral surfaces. Here, we examined the competitive uptake of phosphate and silicate on goethite over a wide pH range, using batch measurements supported by DFT calculations. The results show selective adsorption of phosphate at pH < 4 and silicate at pH > 10 with little to no competitive effect. However, between 4 < pH < 10, the total phosphate and silicate loading was found to be almost equal to that of silicate loading from single-component solution, revealing a proportionate competition for surface site types and a competitive effect controlling their mutual retention. DFT-calculated adsorption energies and charge density redistributions for various surface complexes on different charged (101) and (210) facets are consistent with the trends observed in batch measurements, suggesting that the observed behavior reflects the primary controlling influence of goethite surface chemistry at the molecular scale. An important implication is that at the circumneutral pH in most environmental systems, where iron oxyhydroxides comprise much of the reactive interfacial area, unbound phosphate concentrations may be strongly controlled by dissolved silicate concentration, and vice versa.

Predicting the electrokinetic properties on an outcrop and reservoir composite carbonate surfaces in modified salinity brines using extended surface complexation models.

Surface complexation models (SCM), based mainly on the diffuse double layer (DDL) theory, have been used to predict zeta potential at the crude oil-brine-rock (COBR) interface with limited success. However, DDL is inherently limited in accurately predicting zeta potential by the assumptions that all the brine ions interact with the rock surface at the same plane and by the double layer collapse at higher brine ionic strength (>1M). In this work, a TLM-based SCM captured zeta potential trends at the calcite-brine interface with ionic strength up to 3 M. An extended DDL and TLM-based SCMs were used to predict the electrokinetic properties of a composite carbonate rock showing a different mineralogical composition. The extended TLM-based SCM captured the zeta potential prediction trends and magnitude, highlighting the contribution of the inorganic minerals and organic impurities on the composite carbonate surface. In contrast, the extended DDL-based SCM captured the zeta potential trends but failed to capture the magnitude of the measured zeta potential. Interestingly, the TLM-based SCM predicted a positive SP for the rock-brine interface, which could explain the oil-wet nature of composite carbonate rocks due to electrostatic adsorption of negatively charged carboxylic acids. Conversely, the DDL-based SCM predicted a negative SP, leading to an inaccurate interpretation of the electrokinetic properties at the rock-brine interface. Thus, the use of extended TLM-based SCM was required to accurately predict the zeta potential and account for the adsorption of carboxylic acids on the reservoir composite carbonate surface.

Coprecipitation mechanisms of Zn by birnessite formation and its mineralogy under neutral pH conditions.

Birnessite (δ-Mn(IV)O2) is a great manganese (Mn) adsorbent for dissolved divalent metals. In this study, we investigated the coprecipitation mechanism of δ-MnO2 in the presence of Zn(II) and an oxidizing agent (sodium hypochlorite) under two neutral pH values (6.0 and 7.5). The mineralogical characteristics and Zn-Mn mixed products were compared with simple surface complexation by adsorption modeling and structural analysis. Batch coprecipitation experiments at different Zn/Mn molar ratios showed a Langmuir-type isotherm at pH 6.0, which was similar to the result of adsorption experiments at pH 6.0 and 7.5. X-ray diffraction and X-ray absorption fine structure analysis revealed triple-corner-sharing inner-sphere complexation on the vacant sites was the dominant Zn sorption mechanism on δ-MnO2 under these experimental conditions. A coprecipitation experiment at pH 6.0 produced some hetaerolite (ZnMn(III)2O4) and manganite (γ-Mn(III)OOH), but only at low Zn/Mn molar ratios (< 1). These secondary precipitates disappeared because of crystal dissolution at higher Zn/Mn molar ratios because they were thermodynamically unstable. Woodruffite (ZnMn(IV)3O7•2H2O) was produced in the coprecipitation experiment at pH 7.5 with a high Zn/Mn molar ratio of 5. This resulted in a Brunauer-Emmett-Teller (BET)-type sorption isotherm, in which formation was explained by transformation of the crystalline structure of δ-MnO2 to a tunnel structure. Our experiments demonstrate that abiotic coprecipitation reactions can induce Zn-Mn compound formation on the δ-MnO2 surface, and that the pH is an important controlling factor for the crystalline structures and thermodynamic stabilities.

Intercomparison and Refinement of Surface Complexation Models for U(VI) Adsorption onto Goethite Based on a Metadata Analysis.

Adsorption of uranium onto goethite is an important partitioning process that controls uranium mobility in subsurface environments, for which many different surface complexation models (SCMs) have been developed. While individual models can fit the data for which they are parameterized, many perform poorly when compared with experimental data covering a broader range of conditions. There is an imperative need to quantitatively evaluate the variations in the models and to develop a more robust model that can be used with more confidence across the wide range of conditions. We conducted an intercomparison and refinement of the SCMs based on a metadata analysis. By seeking the globally best fit to a composite dataset with wide ranges of pH, solid/sorbate ratios, and carbonate concentrations, we developed a series of models with different levels of complexity following a systematic roadmap. The goethite-uranyl-carbonate ternary surface complexes were required in every model. For the spectroscopically informed models, a triple-plane model was found to provide the best fit, but the performance of the double-layer model with bidentate goethite-uranyl and goethite-uranyl-carbonate complexes was also comparable. Nevertheless, the models that ignore the bidentate feature of uranyl surface complexation consistently performed poorly. The goodness of fitting for the models that ignore adsorption of carbonate and the charge distributions was not significantly compromised compared with that of their counterparts that considered those. This approach of model development for a large and varied dataset improved our understanding of U(VI)-goethite surface reactions and can lead to a path for generating a single set of reactions and equilibrium constants for including U(VI) adsorption onto goethite in reactive transport models.

Heterogeneous Sorption of Radionuclides Predicted by Crystal Surface Nanoroughness.

Reactive transport modeling (RTM) is an essential tool for the prediction of contaminants' behavior in the bio- and geosphere. However, RTM of sorption reactions is constrained by the reactive surface site assessment. The reactive site density variability of the crystal surface nanotopography provides an "energetic landscape", responsible for heterogeneous sorption efficiency, not covered in current RTM approaches. Here, we study the spatially heterogeneous sorption behavior of Eu(III), as an analogue to trivalent actinides, on a polycrystalline nanotopographic calcite surface and quantify the sorption efficiency as a function of surface nanoroughness. Based on experimental data from micro-focus time-resolved laser-induced luminescence spectroscopy (µTRLFS), vertical scanning interferometry, and electron back-scattering diffraction (EBSD), we parameterize a surface complexation model (SCM) using surface nanotopography data. The validation of the quantitatively predicted spatial sorption heterogeneity suggests that retention reactions can be considerably influenced by nanotopographic surface features. Our study presents a way to implement heterogeneous surface reactivity into a SCM for enhanced prediction of radionuclide retention.

Structure and Surface Complexation at the Calcite(104)-Water Interface.

Calcite is the most stable polymorph of calcium carbonate (CaCO3) under ambient conditions and is ubiquitous in natural systems. It plays a major role in controlling pH in environmental settings. Electrostatic phenomena at the calcite-water interface and the surface reactivity of calcite in general have important environmental implications. They may strongly impact nutrient and contaminant mobility in soils and other subsurface environments, they control oil recovery from limestone reservoirs, and they may impact the safety of nuclear waste disposal sites. Besides the environmental relevance, the topic is significant for industrial applications and cultural heritage preservation. In this study, the structure of the calcite(104)-water interface is investigated on the basis of a new extensive set of crystal truncation rod data. The results agree with recently reported structures and resolve previous ambiguities with respect to the coordination sphere of surface Ca ions. These structural features are introduced into an electrostatic three-plane surface complexation model, describing ion adsorption and charging at the calcite-water interface. Inner surface potential data for calcite, as measured with a calcite single-crystal electrode, are used as constraints for the model in addition to zeta potential data. Ion adsorption parameters are compared with molecular dynamics simulations. All model parameters, including protonation constants, ion-binding parameters, and Helmholtz capacitances, are within physically and chemically plausible ranges. A PhreeqC version of the model is presented, which we hope will foster application of the model in environmental studies.

Probing and understanding interaction of Eu(III) with γ- alumina in presenceof malonic acid.

Radionuclide migration in aquatic environment is influenced by its sorption onto colloids/mineral oxides and the presence of organic complexing anions. With a view to understand the sorption of trivalent actinides by mineral oxides in presence of organic acid, in the present study, Eu(III), malonic acid (MA) and γ-alumina are considered as representatives of trivalent actinides, low molecular weight natural occurring organic acid and aluminol sites, respectively. The influence of MA on sorption of Eu(III) by γ-alumina was elucidated by batch sorption, spectroscopic techniques and surface complexation modeling, for the first time. Attenuated Total Reflection-Fourier Transform Infrared spectroscopic studies of MA sorbed on γ-alumina revealed the presence of two inner-sphere surface complexes. Batch sorption for binary (alumina-Eu(III)) and ternary (alumina-Eu(III)-MA) systems were investigated as a function of pH, Eu(III) concentration and sequential addition of Eu(III)/MA. The pH edge for Eu(III) sorption shifts to higher pH with increasing Eu(III) concentration. In ternary systems, Eu(III) sorption is significantly enhanced at pH < 4.5. Eu(III) speciation on γ-alumina is independent of addition sequence of Eu(III)/MA. Time resolved fluorescence spectroscopy of Eu(III) sorbed on γ-alumina exhibited two surface species, XOEu2+ and (YO)2Eu+. The enhancement in I616/I592 and lifetime for ternary systems, as compared to binary system, at low pH, indicates the participation of Eu-MA complexes in the formation of surface species in ternary systems. The diffuse layer model has been employed to successfully model the experimental sorption profiles of binary and ternary systems, using code FITEQL 4.0, by considering the surface species identified by spectroscopic techniques.

Temperature effects on electrical double layer at solid-aqueous solution interface.

Despite the significant influence of solution temperature on the structure of electrical double layer, the lack of theoretical model intercepts us to explain and predict the interesting experimental observations. In this work, we study the structure of electrical double layer as a function of thermochemical properties of the solution by proposing a phenomenological temperature dependent surface complexation model. We found that by introducing a buffer layer between the diffuse layer and stern layer, one can explain the sensitivity of zeta potential to temperature for different bulk ion concentrations. Calculation of the electrical conductance as function of thermochemical properties of solution reveals the electrical conductance not only is a function of bulk ion concentration and channel height but also the solution temperature. The present work model can provide deep understanding of micro- and nanofluidic devices functionality at different temperatures.

Adsorptive performance of activated carbon reused from household drinking water filter for hexavalent chromium-contaminated water.

Powdered activated carbon blocks (PACBs) are waste products obtained from household drinking water purification systems. In this study, we demonstrate that they can be used as adsorbents for the cost-effective and environmentally benign removal of hexavalent chromium (Cr(VI)) from contaminated-water and rinse electroplating wastewater. To evaluate Cr(VI) sorption onto the PACB, studies on equilibrium, kinetics, and thermodynamics were performed using batch mode experiments. The experimental results indicated that Cr(VI) ions were efficiently adsorbed under acidic conditions (i.e., at initial pH below 3) and low initial Cr(VI) concentrations. The adsorptive behaviors of the PACB for Cr(VI) were well explained by the Langmuir isotherm, as well as pseudo-second-order kinetic models, suggesting that a Cr(VI) monolayer was adsorbed onto the PACB surface via chemisorption. The maximum adsorption capacity of Cr(VI) onto the PACB was determined to be 6.207 mg/g. The results of thermodynamic studies revealed that the adsorption process of Cr(VI) onto PACB was endothermic and non-spontaneous. Additionally, analysis of the PACB after Cr(VI) adsorption at an initial pH of 2 using scanning electron microscopy, energy dispersive spectrometry, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) revealed that the interaction between the surface oxygenic functional groups on the PACB and Cr(VI) was primarily responsible for Cr(VI) sorption via surface complexation and electrostatic interactions. Based on the result of XPS analysis, the presence of trivalent chromium on the PACB surfaces indicated that some synergistic redox reactions involving Cr(VI) could have occurred during the sorption process. Although a commercially available powdered activated carbon outperformed the PACB adsorbent with respect to Cr(VI) removal from wastewater, complete Cr(VI) adsorption could be achieved using relatively large quantities of the PACB. These findings indicate that the PACB adsorbent could be used as a cheap and efficient material for the removal of Cr(VI) from wastewater.

Direct Evidence of Salinity and pH Effects on the Interfacial Interactions of Asphaltene-Brine-Silica Systems.

The hydraulic fracturing technique remains essential to unlock fossil fuel from shale oil reservoirs. However, water imbibed by shale during hydraulic fracturing triggers environmental and technical challenges due to the low flowback water recovery. While it appears that the imbibition of fracturing fluid is a complex function of physico-chemical processes in particular capillary force which is associated with wettability of oil-brine-shale, the controlling factor(s) to govern the wettability is incomplete and the literature data in this context is missing. We thus measured the adsorption/desorption of asphaltenes on silica surface in the presence of brines using quartz crystal microbalance with dissipation (QCM-D). We detected zeta potential of asphaltene-brine and brine-silica systems and calculated the disjoining pressures of the asphaltene-brine-silica system in the case of different salinity. Moreover, we performed a geochemical study to quantify the variation of surface chemical species at asphaltene and silica surfaces with different pH values and used the chemical force microscope (CFM) method to quantify the effect of pH on intermolecular forces. Our results show that lowering salinity or raising pH reduced the adhesion force between asphaltene and silica surface. For example, at a pH value of 6.5, when the concentration of injected water is reduced from 1000 mM to 100 mM and 10 mM, the adhesion force decreased by approximately 58% and 66%, respectively. In addition, for the 100 mM NaCl solution, when the pH value increased from 4.5 to 6.5 and 9, the adhesion force decreased by approximately 56% and 87%, respectively. Decreased adhesion forces between asphaltene and the silica surface could promote the desorption of asphaltene from the silica surface, resulting in a negative zeta potential for both asphaltene-silica and brine-silica interfaces and a shift of wettability towards water-wet characteristic. During such a process, -NH+ number at asphaltene surfaces decreases and the bonds between -NH+ and >SiO- break down, to further interpret the formation of a thinner asphaltene adlayer on the rock surface. This study proposes a reliable theoretical basis for the application of hydraulic fracturing technology, and a facile and possible manipulation strategy to increase flowback water from unconventional reservoirs.