Surface Site Density Research Articles

Strong Selective Adsorption of Polymers

A scaling theory is developed for of polymers induced by the strong binding between specific monomers and complementary surface By selective we mean specific attraction between a subset of all monomers, called sticky, and a subset of surface sites, called adsorption sites. We demonstrate that, in addition to the expected dependence on the polymer volume fraction ϕbulk in the bulk solution, strongly depends on the ratio between two characteristic length scales, the root-mean-square distance l between neighboring sticky monomers along the polymer, and the average distance d between neighboring surface The role of the ratio l/d arises from the fact that a polymer needs to deform to enable the spatial commensurability between its sticky monomers and the surface sites for adsorption. We study strong of both telechelic polymers with two end monomers being sticky and multisticker polymers with many sticky monomers between sticky ends. For telechelic polymers, we identify four regimes at l/d 1, we expect that the layer at exponentially low ϕbulk consists of separated unstretched loops, while as ϕbulk increases the layer crosses over to a brush of extended loops with a second layer of weakly overlapping tails. For multisticker chains, in the limit of exponentially low ϕbulk, adsorbed polymers are well separated from each other. As l/d increases, the conformation of an individual polymer changes from a single-end-adsorbed mushroom to a random walk of loops. For high ϕbulk, adsorbed polymers at small l/d are mushrooms that cover all the At sufficiently large l/d, adsorbed multisticker polymers strongly overlap. We anticipate the formation of a self-similar carpet and with increasing l/d a two-layer structure with a brush of loops covered by a self-similar carpet. As l/d exceeds the threshold determined by the energy, the brush of loops under the carpet reaches a saturated state, resulting in a l/d-independent brush-under-carpet structure, which can also be applied to describe adsorbed multisticker polymers in nonselective where a sticker can strongly bind to any place on the surface. We examine the adsorbed amount Γ of multisticker polymers in different regimes for adsorption. If the adsorbed multisticker polymers are nonoverlapping mushrooms, the adsorbed amount Γ increases linearly with the surface density of sites Σ ≈ 1/d2. In the self-similar carpet regime, Γ increases sublinearly as Σ0.15 in a good solvent, while only logarithmically in a theta solvent. Formation of a brush layer under the carpet contributes an additional adsorbed amount. This additional amount increases linearly with Σ and eventually dominates the overall adsorbed amount Γ before saturating at a plateau value controlled by the energy.

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of 17 ice nucleation measurement techniques

Abstract. Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, ns, to develop a representative ns(T) spectrum that spans a wide temperature range (−37 °C < T < −11 °C) and covers 9 orders of magnitude in ns. In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency expressed in ns of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns(T) spectra and identified a section with a steep slope between −20 and −27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below −27 °C. While the agreement between different instruments was reasonable below ~ −27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in ns was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about −27 and −18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above −18 °C. A possible explanation for the deviation between −27 and −18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based ns(T) and geometric surface area-based ns(T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.

Uranium transport in a crushed granodiorite: Experiments and reactive transport modeling

The primary objective of this study was to develop and demonstrate an experimental method to refine and better parameterize process models for reactive contaminant transport in aqueous subsurface environments and to reduce conservatism in such models without attempting to fully describe the geochemical system. Uranium was used as an example of a moderately adsorbing contaminant because of its relevance in geologic disposal of spent nuclear fuel. A fractured granodiorite from the Grimsel Test Site (GTS) in Switzerland was selected because this system has been studied extensively and field experiments have been conducted with radionuclides including uranium. We evaluated the role of pH, porous media size fraction, and flow interruptions on uranium transport. Rock cores drilled from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and optical microscopy, and used in uranium batch sorption and column breakthrough experiments. A synthetic water was prepared that represented the porewater that would be present after groundwater interacts with bentonite backfill material near a nuclear waste package. Uranium was conservatively transported at pH8.8. Significant adsorption and subsequent desorption was observed at pH ~7, with long desorption tails resulting after switching the column injection solution to uranium-free groundwater. Our experiments were designed to better interrogate this slow desorption behavior. A three-site model predicted sorption rate constants for a pH7.2 solution with a 75–150μm granodiorite fraction to be 3.5, 0.012, and 0.012mL/g-h for the forward reactions and 0.49, 0.0025, and 0.001h−1 for the reverse reactions. Surface site densities were 1.3, 0.042, and 0.042μmol/g for the first, second, and third sites, respectively. 10-year simulations show that including a slow binding site increases the arrival time of a uranium pulse by ~70%.

Effects of Calcination Temperature on Properties of Mg-Al Mixed Oxide Nanoparticle

The limited size and high density of surface sites that characterize nanoparticles result in unique chemical and physical properties. Magnesium aluminum mixed oxide was synthesized by co-precipitation method using Al2 (SO4)3.16H2O and MgSO4.7H2O precursors in 1:1 molar ratio. The calcination temperature was varied from 250, 300 and 700oC. Nanoparticles synthesized were characterized using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and TGA-DTA. At low temperature synthesized spherical particles are amorphous and they start to transform into spinel crystalline structure around 650°C. Generally particle size increased with increase in temperature.

2D nanosheet molybdenum disulphide (MoS2) modified electrodes explored towards the hydrogen evolution reaction.

We explore the use of two-dimensional (2D) MoS2 nanosheets as an electrocatalyst for the Hydrogen Evolution Reaction (HER). Using four commonly employed commercially available carbon based electrode support materials, namely edge plane pyrolytic graphite (EPPG), glassy carbon (GC), boron-doped diamond (BDD) and screen-printed graphite electrodes (SPE), we critically evaluate the reported electrocatalytic performance of unmodified and MoS2 modified electrodes towards the HER. Surprisingly, current literature focuses almost exclusively on the use of GC as an underlying support electrode upon which HER materials are immobilised. 2D MoS2 nanosheet modified electrodes are found to exhibit a coverage dependant electrocatalytic effect towards the HER. Modification of the supporting electrode surface with an optimal mass of 2D MoS2 nanosheets results in a lowering of the HER onset potential by ca. 0.33, 0.57, 0.29 and 0.31 V at EPPG, GC, SPE and BDD electrodes compared to their unmodified counterparts respectively. The lowering of the HER onset potential is associated with each supporting electrode's individual electron transfer kinetics/properties and is thus distinct. The effect of MoS2 coverage is also explored. We reveal that its ability to catalyse the HER is dependent on the mass deposited until a critical mass of 2D MoS2 nanosheets is achieved, after which its electrocatalytic benefits and/or surface stability curtail. The active surface site density and turn over frequency for the 2D MoS2 nanosheets is determined, characterised and found to be dependent on both the coverage of 2D MoS2 nanosheets and the underlying/supporting substrate. This work is essential for those designing, fabricating and consequently electrochemically testing 2D nanosheet materials for the HER.

A comprehensive parameterization of heterogeneous ice nucleation of dust surrogate: laboratory study with hematite particles and its application to atmospheric models

Abstract. A new heterogeneous ice nucleation parameterization that covers a wide temperature range (−36 to −78 °C) is presented. Developing and testing such an ice nucleation parameterization, which is constrained through identical experimental conditions, is important to accurately simulate the ice nucleation processes in cirrus clouds. The ice nucleation active surface-site density (ns) of hematite particles, used as a proxy for atmospheric dust particles, were derived from AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud chamber measurements under water subsaturated conditions. These conditions were achieved by continuously changing the temperature (T) and relative humidity with respect to ice (RHice) in the chamber. Our measurements showed several different pathways to nucleate ice depending on T and RHice conditions. For instance, almost T-independent freezing was observed at −60 °C < T < −50 °C, where RHice explicitly controlled ice nucleation efficiency, while both T and RHice played roles in other two T regimes: −78 °C < T < −60 °C and −50 °C < T < −36 °C. More specifically, observations at T lower than −60 °C revealed that higher RHice was necessary to maintain a constant ns, whereas T may have played a significant role in ice nucleation at T higher than −50 °C. We implemented the new hematite-derived ns parameterization, which agrees well with previous AIDA measurements of desert dust, into two conceptual cloud models to investigate their sensitivity to the new parameterization in comparison to existing ice nucleation schemes for simulating cirrus cloud properties. Our results show that the new AIDA-based parameterization leads to an order of magnitude higher ice crystal concentrations and to an inhibition of homogeneous nucleation in lower-temperature regions. Our cloud simulation results suggest that atmospheric dust particles that form ice nuclei at lower temperatures, below −36 °C, can potentially have a stronger influence on cloud properties, such as cloud longevity and initiation, compared to previous parameterizations.

Surface Heterogeneity of SiO2 Polymorphs: An XPS Investigation of α-Quartz and α-Cristobalite

Silica minerals, one of the most abundant mineral species on the earth, play important roles in geochemistry and environment processes. The diversity of the SiO4 tetrahedron polymerization style might result in the heterogeneity of the surface microstructures and properties of SiO2 polymorphs. The surface properties of two common crystalline SiO2 polymorphs, i.e., α-quartz and α-cristobalite, have been investigated by the surface site density measurement, batch methylene blue (MB) adsorption, and X-ray photoelectron spectroscopy (XPS). The Langmuir adsorption isotherms suggest the formation of monolayer MB on both α-quartz and α-cristobalite surfaces. The adsorption capacity of α-quartz toward MB is larger than that of α-cristobalite, which positively correlates with the density of surface site. XPS spectra reveal that the adsorption takes place between the nitrogen atom of the dimethylamino groups in MB and silanols on α-quartz and α-cristobalite surfaces. The O/Si atom ratio related with adsorption of α...

Sensing and pH-imaging properties of niobium oxide prepared by rapid thermal annealing for electrolyte–insulator–semiconductor structure and light-addressable potentiometric sensor

A niobium oxide (NbOx) layer is firstly investigated as a pH sensing membrane in single-layer light-addressable potentiometric sensor (LAPS) in this study. To confirm basic sensing performances, NbOx layer directly deposited on silicon substrate was prepared by reactive rf sputtering and following with post-deposition rapid thermal anneal (RTA) for electrolyte insulator semiconductor (EIS) structure first. RTA processed at 500 to 700°C can be used to make the increases of calculated pH sensitivity and linearity, especially performed in O2 ambience. Increases of pH sensitivity can result from the surface site density increases causing by the re-crystallization in RTA, which be supported by the larger grain size and surface roughness in AFM analysis. In this single-layer structure, desified layer with slightly higher atom concentration by RTA and partial Si out-diffusion to surface shown in SIMS analysis could be another factor for better pH sensing performance. 30nm-thick NbOx layer is suggested to have a lower drift coefficient after RTA in O2 ambience compare to 5nm-thick NbOx layer. An acceptable pH sensing performance including a pH sensitivity of 57–60mV/pH and a drift of −3mV/h is achieved in the 30nm-thick NbOx-EIS structure with RTA in O2 ambience at 500 to 700°C, which could be a candidate of pH sensing membrane. This developed process of NbOx sensing membrane is also applied to LAPS to collect a hydrogen-ion image for area defined by photolithography and buffer solution with red laser scanning controlled by X–Y stage.

Application of surface complexation models to anion adsorption by natural materials

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical.

Transient numerical modeling of catalytic channels using a quasi-steady gas phase

This paper presents a transient model of internal catalytic combustion suitable for isolated channels and monolith reactors. Due to time-scales in the problem, the model considers a quasi-steady gas phase with a transient solid. The gas is described by axially varying bulk temperature and species. The gas includes lateral diffusion via transfer coefficients and the specification of a gas-phase species concentration at the wall; axial diffusion is neglected. The solid phase is a thermally thin shell with axially varying temperature, surface species, and surface species concentrations. The solid includes axial heat conduction and external heat loss by convection and radiation. The combustion process utilizes detailed gas and surface reaction models. The gas-phase model becomes a system of stiff ordinary differential equations with respect to axial position; the upstream (inlet) boundary conditions are specified and the axially varying solid properties are parameters in integration. The solid phase discretizes into a system of stiff ordinary differential-algebraic equations with respect to time. The time evolution of the system comes from alternating integrations of the quasi-steady gas phase and transient solid.The model is compared to two experimental cases using CO fuel: (1) steady-state conversion in an isothermal platinum tube and (2) transient propagation of a catalytic reaction inside a small platinum tube and includes external tube temperature measurements. This work presents sensitivity studies on important parameters including internal transfer coefficients, catalytic surface site density, external heat-loss, and others. Under mass-transfer limited conditions, global transfer coefficients are adequate to predict fuel conversion. Near light-off, the model predictions improve for the first case after adjusting the surface kinetics such that the net rate of CO adsorption increases compared to O2. For the second case, predictions of transient propagation speeds are good for equivalence ratios near unity and greater but require adjustment of external heat loss or kinetics to match under lean conditions.

Modeling immersion freezing with aerosol‐dependent prognostic ice nuclei in Arctic mixed‐phase clouds

AbstractWhile recent laboratory experiments have thoroughly quantified the ice nucleation efficiency of different aerosol species, the resulting ice nucleation parameterizations have not yet been extensively evaluated in models on different scales. Here the implementation of an immersion freezing parameterization based on laboratory measurements of the ice nucleation active surface site density of mineral dust and ice nucleation active bacteria, accounting for nucleation scavenging of ice nuclei, into a cloud‐resolving model with two‐moment cloud microphysics is presented. We simulated an Arctic mixed‐phase stratocumulus cloud observed during Flight 31 of the Indirect and Semi‐Direct Aerosol Campaign near Barrow, Alaska. Through different feedback cycles, the persistence of the cloud strongly depends on the ice number concentration. It is attempted to bring the observed cloud properties, assumptions on aerosol concentration, and composition and ice formation parameterized as a function of these aerosol properties into agreement. Depending on the aerosol concentration and on the ice crystal properties, the simulated clouds are classified as growing, dissipating, and quasi‐stable. In comparison to the default ice nucleation scheme, the new scheme requires higher aerosol concentrations to maintain a quasi‐stable cloud. The simulations suggest that in the temperature range of this specific case, mineral dust can only contribute to a minor part of the ice formation. The importance of ice nucleation active bacteria and possibly other ice formation modes than immersion freezing remains poorly constrained in the considered case, since knowledge on local variations in the emissions of ice nucleation active organic aerosols in the Arctic is scarce.

Physicochemical properties of WOx/ZrO2 catalysts for palmitic acid esterification

A series of WOx/ZrO2 with various tungsten loadings was prepared via incipient-wetness impregnation of zirconium hydroxide. The resulting thermally processed materials were characterised by XRD, XPS, porosimetry, NH3-TPD and pyridine FTIR spectroscopy to elucidate their composition, morphology and acidity, and subsequently tested in the esterification of palmitic acid with methanol. Catalytic performance was strongly dependent upon calcination temperature and W surface density. Esterification activity increased with increasing surface W density, reaching a maximum at 8.9Wnm−2 corresponding to near monolayer coverage. Subsequent growth of crystalline WO3 lowered activity, consistent with a decrease in the density of active surface sites. Calcination temperatures as high as 800°C increased surface acidity and hence catalytic activity. The formation of polymeric tungstate species on zirconia is necessary to generate the Brönsted acid sites responsible for palmitic acid esterification under mild conditions.

Characterization of surface charge and zeta potential of colloidal silica prepared by various methods

Colloidal silica is prepared by hydrolysis of TEOS, direct oxidation of Si powder, condensation of silicic acid, etc. There are differences in surface reactivity of silica particle due to the preparation routes. Therefore, it is useful to evaluate surface properties accurately in order to understand the physiochemical properties of the products. The surface charge density, site density and zeta potential with respect to three types of colloidal silica were estimated and discussed. The surface charge density was different depending on preparation method. It is decreasing in the order of direct oxidation, ion exchange, TEOS hydrolysis. The zeta potential is decreasing in the order of ion exchange, TEOS hydrolysis, direct oxidation. The order in surface charge density is different from that in zeta potential because of the difference in stability depending on the particle size and surface charge density.

Acid–base properties and surface complexation modeling of phosphate anion adsorption by wasted low grade iron ore with high phosphorus

The adsorption phenomena and specific reaction processes of phosphate onto wasted low grade iron ore with high phosphorus (WLGIOWHP) were studied in this work. Zeta potential and Fourier transform infrared spectroscopy (FTIR) analyses were used to elucidate the interaction mechanism between WLGIOWHP and aqueous solution. The results implied that the main adsorption mechanism was the replacement of surface hydroxyl groups by phosphate via the formation of inner-sphere complex. The adsorption process was characterized by chemical adsorption onto WLGIOWHP. The non-electrostatic model (NEM) was used to simulate the surface adsorption of phosphate onto WLGIOWHP. The total surface site density and protonation constants for NEM (NT=1.6×10−4mol/g, Ka1=2.2×10−4, Ka2=6.82×10−9) were obtained by non-linear data fitting of acid–base titrations. In addition, the NEM was used to establish the surface adsorption complexation modeling of phosphate onto WLGIOWHP. The model successfully predicted the adsorption of phosphate onto WLGIOWHP from municipal wastewater.

Fischer–Tropsch Synthesis: Oxidation of a Fraction of Cobalt Crystallites in Research Catalysts at the Onset of FT at Partial Pressures Mimicking 50 % CO Conversion

Freshly H2-reduced catalyst samples and FTS catalyst samples (i.e., freshly reduced and immediately exposed to the onset of FTS conditions corresponding to 50 % CO conversion) were prepared. Each sample was coated in situ using molten polywax and solidified so that an air-protected sample was obtained, which was stored in inert gas. XAS was utilized to investigate the oxidation state of cobalt. A fraction of cobalt crystallites in the freshly reduced research catalysts having lower-than-commercial loading and smaller crystallites undergoes a degree of oxidation to CoO at the onset of FTS conditions simulating 50 % CO conversion (i.e., the H2O partial pressure is high enough to induce some oxidation). Therefore, by decreasing Co content with the aim of improving the dispersion of cobalt and Co efficiency, very small Co crystallites are obtained. Their reoxidation at the onset of FTS is an unintended consequence. Thus, catalysts should be designed to have an optimum narrow cluster size range—small enough to increase Co surface site densities, but large enough to avoid reoxidation, and the stability problems that arise from having unreduced Co in the working catalyst (e.g., a complex coalescence and reduction mechanism).

Laboratory studies of immersion and deposition mode ice nucleation of ozone aged mineral dust particles

Abstract. Ice nucleation in the atmosphere is central to the understanding the microphysical properties of mixed-phase and cirrus clouds. Ambient conditions such as temperature (T) and relative humidity (RH), as well as aerosol properties such as chemical composition and mixing state play an important role in predicting ice formation in the troposphere. Previous field studies have reported the absence of sulfate and organic compounds on mineral dust ice crystal residuals sampled at mountain top stations or aircraft based measurements despite the long-range transport mineral dust is subjected to. We present laboratory studies of ice nucleation for immersion and deposition mode on ozone aged mineral dust particles for 233 < T < 263 K. Heterogeneous ice nucleation of untreated kaolinite (Ka) and Arizona Test Dust (ATD) particles is compared to corresponding aged particles that are subjected to ozone concentrations of 0.4–4.3 ppmv in a stainless steel aerosol tank. The portable ice nucleation counter (PINC) and immersion chamber combined with the Zurich ice nucleation chamber (IMCA-ZINC) are used to conduct deposition and immersion mode measurements, respectively. Ice active fractions as well as ice active surface site densities (ns) are reported and observed to increase as a function of decreasing temperature. We present first results that demonstrate enhancement of the ice nucleation ability of aged mineral dust particles in both the deposition and immersion mode due to ageing. We also present the first results to show a suppression of heterogeneous ice nucleation activity without the condensation of a coating of (in)organic material. In immersion mode, low ozone exposed Ka particles showed enhanced ice activity requiring a median freezing temperature of 1.5 K warmer than that of untreated Ka, whereas high ozone exposed ATD particles showed suppressed ice nucleation requiring a median freezing temperature of 3 K colder than that of untreated ATD. In deposition mode, low exposure Ka had ice active fractions of an order of magnitude higher than untreated Ka, whereas high ozone exposed ATD had ice active fractions up to a factor of 4 lower than untreated ATD. From our results, we derive and present parameterizations in terms of ns(T) that can be used in models to predict ice nuclei concentrations based on available aerosol surface area.

Formation Mechanism of a Silane‐PVA/PVAc Complex Film on a Glass Fiber Surface

Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si-O-Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non-silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value Sa represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 μm(2) if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 μg mL(-1), respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (Ha ) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 μg mL(-1), respectively. The pH-dependent zeta-potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non-silanized glass fiber surface and the silane film have similar zeta potentials ranging from -64 to -12 mV at pH's of 10.5 and 3, respectively. The zeta potentials for the PVA/PVAc microspheres on the glass fiber surface and within the silane film significantly decrease and range from -25 to -5 mV. The shapes of the pH-dependent zeta potentials are different in the cases of silane groups over a pH range from 7 to 4. A triple-layer model is used to fit the non-silanized glass surface and the silane film. The value of the surface-site density for Γ(Xglass) and Γ(Xsilane), in which X denotes the Al-O-Si group, differs by a factor of 10(-4), which suggests an effective coupling of the silane film. A soft-layer model is used to fit the silane-PVA/PVAc complex film, which is approximated as four layers. Such a simplification and compensation of the microsphere shape gives an approximation of the relevant widths of the layers as the follows: 1) the layer of the silane groups makes up 10% of the total length (27 nm), 2) the layer of the first PVA shell contributes 30% to the total length (81 nm), 3) the layer of the PVAc core contributes 30% to the total length (81 nm), and finally 4) the layer of the second PVA shell provides 30% of the total length (81 nm). The coverage simulation resulted in a value of 0.4, which corresponds with the assumption of low-order coverage, and is supported by the AFM scans. Correlating the results of the AFM scans, and the zeta potentials sheds some light on the formation mechanism of the silane-PVA/PVAc complex film.

Zinc and nickel removal in limestone based treatment of acid mine drainage: The relative role of adsorption and co-precipitation

Mining influenced water may contain high metal and sulfate loads, and have low pH (acid mine drainage). Removal of these metals prior to environmental discharge is critical to maintain ecosystem vitality. Limestone based passive treatment systems are commonly used for pH neutralization. The same conditions that lead to pH neutralization may also remove a substantial amount of metals from solution, but the connection between treatment conditions and metal removal are not well understood. In this study, zinc and nickel removals are quantified in batch reactor simulated limestone treatment of acid mine drainage. The resulting solid phase is characterized with a sequential extraction procedure, and the removals are interpreted using surface complexation and surface precipitation models. Zinc and nickel removals are closely linked to the initial iron concentration in the mine water, but are also affected by pH, alkalinity, calcium and sulfate concentrations. The surface complexation model was based on literature descriptions of hydrous ferric oxide. In order to obtain a sufficient fit to the data, the surface site density was increased to an unrealistically high value. Uptake data was also fit to an existing surface precipitation model. The values used are similar to those found in previous studies. Both models indicate that adsorption is not the dominant removal process in the treatment system. Using adsorption only models will generally underpredict metal removals within limestone based treatment systems.

Immersion freezing of ice nucleation active protein complexes

Abstract. Utilising the Leipzig Aerosol Cloud Interaction Simulator (LACIS), the immersion freezing behaviour of droplet ensembles containing monodisperse particles, generated from a Snomax™ solution/suspension, was investigated. Thereto ice fractions were measured in the temperature range between −5 °C to −38 °C. Snomax™ is an industrial product applied for artificial snow production and contains Pseudomonas syringae} bacteria which have long been used as model organism for atmospheric relevant ice nucleation active (INA) bacteria. The ice nucleation activity of such bacteria is controlled by INA protein complexes in their outer membrane. In our experiments, ice fractions increased steeply in the temperature range from about −6 °C to about −10 °C and then levelled off at ice fractions smaller than one. The plateau implies that not all examined droplets contained an INA protein complex. Assuming the INA protein complexes to be Poisson distributed over the investigated droplet populations, we developed the CHESS model (stoCHastic modEl of similar and poiSSon distributed ice nuclei) which allows for the calculation of ice fractions as function of temperature and time for a given nucleation rate. Matching calculated and measured ice fractions, we determined and parameterised the nucleation rate of INA protein complexes exhibiting class III ice nucleation behaviour. Utilising the CHESS model, together with the determined nucleation rate, we compared predictions from the model to experimental data from the literature and found good agreement. We found that (a) the heterogeneous ice nucleation rate expression quantifying the ice nucleation behaviour of the INA protein complex is capable of describing the ice nucleation behaviour observed in various experiments for both, Snomax™ and P. syringae bacteria, (b) the ice nucleation rate, and its temperature dependence, seem to be very similar regardless of whether the INA protein complexes inducing ice nucleation are attached to the outer membrane of intact bacteria or membrane fragments, (c) the temperature range in which heterogeneous droplet freezing occurs, and the fraction of droplets being able to freeze, both depend on the actual number of INA protein complexes present in the droplet ensemble, and (d) possible artifacts suspected to occur in connection with the drop freezing method, i.e., the method frequently used by biologist for quantifying ice nucleation behaviour, are of minor importance, at least for substances such as P. syringae, which induce freezing at comparably high temperatures. The last statement implies that for single ice nucleation entities such as INA protein complexes, it is the number of entities present in the droplet population, and the entities' nucleation rate, which control the freezing behaviour of the droplet population. Quantities such as ice active surface site density are not suitable in this context. The results obtained in this study allow a different perspective on the quantification of the immersion freezing behaviour of bacterial ice nucleation.

Heterogeneous ice nucleation ability of crystalline sodium chloride dihydrate particles

AbstractThe aerosol and cloud chamber AIDA (Aerosol Interactions and Dynamics in the Atmosphere) of the Karlsruhe Institute of Technology has been used to quantify the deposition mode ice nucleation ability of airborne crystalline sodium chloride dihydrate (NaCl ∙ 2H2O) particles with median diameters between 0.06 and 1.1 µm. For this purpose, expansion cooling experiments with starting temperatures from 235 to 216 K were conducted. Recently, supermicron‐sized NaCl ∙ 2H2O particles deposited onto a surface have been observed to be ice‐active in the deposition mode at temperatures below 238 K, requiring a median threshold ice saturation ratio of only 1.02 in the range from 238 to 221 K. In AIDA, heterogeneous ice nucleation by NaCl ∙ 2H2O was first detected at a temperature of 227.1 K with a concomitant threshold ice saturation ratio of 1.25. Above that temperature, the crystallized salt particles underwent a deliquescence transition to form aqueous NaCl solution droplets upon increasing relative humidity. At nucleation temperatures below 225 K, the inferred threshold ice saturation ratios varied between 1.15 and 1.20. The number concentration of the nucleated ice crystals was related to the surface area of the seed aerosol particles to deduce the ice nucleation active surface site (INAS) density of the aerosol population as a function of the ice supersaturation. Maximum INAS densities of about 6 ⋅ 1010 m−2 at an ice saturation ratio of 1.20 were found for temperatures below 225 K. These INAS densities are similar to those recently derived for deposition mode ice nucleation on mineral dust particles.