Permanent Structural Charge Research Articles

Fate of pathological prion (PrPsc92–138) in soil and water: prion-clay nanoparticle molecular dynamics

Pathogenic prion protein scrapie (PrPsc) may contaminate soils for decades and remain in water in colloidal suspension, providing infection pathways for animals through the inhalation of ingested dust and soil particles, and drinking water. We used molecular dynamics simulations to understand the strong binding mechanism of this pathogenic peptide with clay mineral surfaces and compared our results to experimental works. We restricted our model to the moiety PrP(92–138), which is a portion of the whole PrPsc molecule responsible for infectivity and modeled it using explicit solvating water molecules in contact with a pyrophyllite cleavage plane. Pyrophyllite is taken as a model for common soil clay, but it has no permanent structural charge. However, partial residual negative charges occur on the cleavage plane slab surface due to a slab charge unbalance. The charge is isotropic in 2D and it was balanced with K+ ions. After partially removing potassium ions, the peptide anchors to the clay surface via up to 10 hydrogen bonds, between protonated lysine or histidine residues and the oxygen atoms of the siloxane cavities. Our results provide insight to the mechanism responsible for the strong association between the PrPsc peptide and clay nanoparticles and the associations present in contaminated soil and water which may lead to the infection of animals.

Nano Dimensional Hybrid Organo-clay Langmuir-Blodgett Films

Clay mineral particles are interesting nanosized building blocks due to their high aspect ratio and the chemical properties. The main interest in this nanosized building blocks results essentially from the colloidal size and the permanent structural charge of the particles. Smectites or swelling clay minerals are naturally occurring nanomaterials that can be fully delaminated to elementary clay mineral platelets in dilute aqueous dispersion. This dilute aqueous smectite suspensions are well suited to convert into functional nanofilms. The functionalization is performed by ion exchange reaction with amphiphilic molecules carrying the desired functionality, such as chirality, two photon absorption, energy transfer, optical nonlinearity and magnetism, which are due to the nature of the amphiphilic cations and to the organization of both the amphiphilic molecules and the elementary clay mineral platelets. Controlling the structure of materials at the nanometre scale is of fundamental importance for tailoring such materials properties. Langmuir Blodgett films are known for a high degree of organization of organic molecules. Fundamental research into the organization of molecules at clay mineral platelets is necessary to optimize the materials for specific applications. This paper gives an overview of organo-clay hybrid Langmuir-Blodgett nano films. Keywords: Langmuir-Blodgett, J-aggregate, Fluorescence resonance Energy Transfer (FRET), Oragano-clay.

Structure and dynamics of the water films confined between edges of pyrophyllite: A first principle study

Edge sites of clay minerals play a key role for pH dependent sorption of ions from solutions of electrolytes. Pyrophyllite, Al 2[Si 4O 10](OH) 2, is an important structural prototype for a variety of 2:1 dioctahedral phyllosilicates but in contrast to the other clays has no permanent structural charge. The structure of thin water films confined between most common edges of 1Tc pyrophyllite: (0 1 0), (1 1 0) and (1 0 0), was analyzed by means of ab initio molecular dynamic simulations. The system setup allowed for a full flexibility of the interfaces and a proton exchange between the edges of pyrophyllite and water molecules in solution. The structure of hydrated surfaces is compared with the recent predictions of static geometry optimizations for edge-vacuum interfaces. All surfaces studied reveal a strong hydrophilic character of edge similar to the hydrated silica surface and the facets of simple layered hydroxides. Spontaneous proton transfer between different surface sites were observed in molecular dynamics simulations of the (0 1 0) interface. The proton bound to the Si OH site was found to exchange with the Al OH group by the mechanism Si OH + Al OH ↔ Si O - + Al OH 2 + . The direction of the proton transfer agrees with the scale of relative proton affinities for surface sites obtained from the static calculations. Alternatively, the proton attached to the Al OH 2 site exchanges with the Al OH group. In both reactions, the protons are transferred through the chains of hydrogen bonds formed between water molecules in the solution and the surface sites. The observed mechanisms might be one of the basic schemes for the surface proton diffusion in compacted clays. Kinetics of the proton transfer at edge sites is limited by the rate of rearrangements of the water molecules near interface.

Structural model for the biogenic Mn oxide produced by Pseudomonas putida

X-ray diffraction (XRD) and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to elaborate a structural model for phyllomanganates (layer-type Mn oxides) lacking 3D ordering (turbostratic stacking). These techniques were applied to a sample produced by a common soil and freshwater bacterium (Pseudomonas putida), and to two synthetic analogs, δ-MnO2 and acid birnessite, obtained by the reduction of potassium permanganate with MnCl2 and HCl, respectively. To interpret the diffraction and spectroscopic data, we applied an XRD simulation technique utilized previously for well-crystallized birnessite varieties, complementing this approach with single-scattering-path simulations of the Mn K-edge EXAFS spectra. Our structural analyses revealed that all three Mn oxides have an hexagonal layer symmetry with layers comprising edgesharing Mn4+O6 octahedra and cation vacancies, but no layer Mn3+O6 octahedra. The proportion of cation vacancies in the layers ranged from 6 to 17%, these vacancies being charge-compensated in the interlayer by protons, alkali metals, and Mn atoms, in amounts that vary with the phyllomanganate species and synthesis medium. Both vacancies and interlayer Mn were most abundant in the biogenic oxide. The diffracting crystallites contained three to six randomly stacked layers and have coherent scattering domains of 19.42 Å in the c* direction, and of 60.85 Å in the a-b plane. Thus, the Mn oxides investigated here are nanoparticles that bear significant permanent structural charge resulting from cation layer vacancies and variable surface charge from unsaturated O atoms at layer edges.

Ab Initio Study of Sorption on Pyrophyllite: Structure and Acidity of the Edge Sites

Pyrophyllite, Al2[Si4O10](OH)2, is the simplest structural prototype for 2:1 dioctahedral phyllosilicates. Since it does not possess permanent structural charge as other clay minerals do, it is used to investigate sorption properties of the clay surfaces not related to the permanent structural charge. The bulk structure and surface geometries of pyrophyllite have been modeled using an orthorhombic constrained supercell. The results of the calculations are in excellent agreement with available experimental data and earlier ab initio simulations. It is shown that the symmetry-constrained model is able to accurately reproduce the basic structural characteristic of pyrophyllite. The electrostatic potential near the (001) surface was used to analyze a possible scenario for the water sorption on the basal plane of pyrophyllite. The calculations predict a slightly hydrophobic behavior of the basal plane. The hydronium ion was found to form a strongly bonded conformation in the siloxane cavity. The relative stability and composition of lateral facets of pyrophyllite have been studied using the supercell approach. The crystals of pyrophyllite are predicted to have a prismatic habit dominated by (110) and (-110) edge facets and basal plane. On the basis of the Fukui functions and the relative protonation/deprotonation enthalpies, the relative acidity and density of the reactive surface sites have been predicted. The triple bond Al-O-Si triple bond sites have the highest proton affinity on the (100), (110), and (130) facets and three line sign Al-OH groups on the (010) edges. The deprotonation of the triple bond Al-OH2 sites is followed by triple bond Al-OH and triple bond Si-OH groups. The calculations suggest a new scale for acidities of edge sites in pyrophyllite that should facilitate the thermodynamic modeling of the sorption processes in compacted clays.

Cargas elétricas estruturais e variáveis de solos tropicais altamente intemperizados

Os solos tropicais altamente intemperizados apresentam teor significativo de colóides com carga elétrica variável. Entretanto, são poucas as referências em relação à quantificação destas cargas, principalmente em solos ácricos, que representam o extremo na escala de intemperismo. Neste estudo, foram determinadas as cargas permanentes e as variáveis de dois Latossolos Vermelhos acriférricos, um Latossolo Amarelo ácrico e um Latossolo Amarelo acriférrico, que foram comparados a um Nitossolo Vermelho eutroférrico, com carga predominantemente permanente. As amostras foram investigadas pelo método da adsorção do íon césio (Cs+), que mede a carga estrutural permanente (sigmao) e baseia-se na preferência do Cs+ sobre o Li+ na superfície da siloxana de grupos de superfície ionizáveis de menor seletividade ao íon Cs+. A carga variável representou mais que 50 % da carga total dos solos estudados. Dois dos quatro Latossolos com propriedades ácricas exibiram quantidade significativa de carga permanente, provavelmente em razão da presença de vermiculita com hidróxi entrecamadas e clorita. A quantidade de carga permanente apresentada pelo Nitossolo foi até cinco vezes maior se comparada à dos Latossolos, o que pode ser atribuído à diferença na constituição mineralógica. O método da adsorção de Cs foi capaz de identificar teores significativos de carga permanente estrutural, mesmo em solos com baixo teor de minerais 2:1.

The titration of clay minerals: I. Discontinuous backtitration technique combined with CEC measurements

Previous experimental studies on clay potentiometric titration have been unable to distinguish inorganic cation exchange in the interlayer and on basal plane surfaces from specific pH-dependent sorption of cations and anions on the edges. In this study, we refined a titration technique, combining discontinuous backtitration and cation exchange capacity (CEC) measurements, and applied it to the potentiometric titration of Na- and Ca-conditioned montmorillonites. This technique can be used to accurately measure cation exchange, edge surface proton charge, dissolution of clay, and precipitation of new phases. Thus, a precise measurement of the variations of net proton surface charge is possible. This has important implications for clay surface modeling (see part II of this article) and for processes that depend on the clay surface charge, e.g., alteration, rheological processes, and contamination retention applications. In addition, this study confirms the adsorption of ionic pairs such as CaCl + in exchange site positions and shows that CaOH + could behave like CaCl +. This result, together with the evidence of precipitation of a CaSi phase over a short time-scale (1 week) at high pH and low temperature, can be used to model clay–concrete interactions more accurately. We confirmed and quantified the H +/Na + exchange reaction at low pH. Finally, we demonstrate that both the edge surface charge and the permanent structural charge are compensated for by the nonspecific sorption of cations from solution across the entire pH range from 4 to 11. Under these conditions, the surface potential is fully screened and does not need to be invoked in modeling sorption processes on clay particles in dilute suspensions.

Sorption of lanthanides on smectite and kaolinite

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3–9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO 3 or NaClO 4) under atmospheric conditions or N 2 flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO 2, but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient ( K D) above pH 5.5. At 0.025 M, the measured K D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K D. This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.

On the Applicability of DLVO Theory to the Prediction of Clay Colloids Stability

The stability behavior of Na–montmorillonite colloids has been studied by combining the analysis of their surface charge properties and time-resolved dynamic light scattering experiments. The chemical surface model for several types of clays, including montmorillonite, has to take into account the double surface charge contribution due to their permanent structural charge and to their pH-dependent charge, which is developed at the edge sites, therefore, these stability studies were carried out as a function of both ionic strength and pH. DLVO theory is largely applied for the prediction of the stability of many colloidal systems, including the natural ones. This work shows that the stability behavior of Na–montmorillonite colloids cannot be satisfactorily reproduced by DLVO theory, using the surface parameters experimentally obtained. Particularly, this theory is unable to explain their pH-dependent stability behavior caused by the small charge at the edge sites. Based on these results, a literature review of DLVO stability prediction of clay colloids was performed. It confirmed that this theory is not capable of taking into account the double contribution to the total surface charge and, at the same time, pointed out the main uncertainties related to the appropriate use of the input parameters for the calculation as, for example, the Hamaker constant or the surface potential.

SURFACE IONIZATION AND SURFACE COMPLEXATION MODELS AT MINERAL/WATER INTERFACE

Surface complexation models(SCMs) have been widely used to study mineral surface adsorption and solution, especially for (hydr)oxide and phylloaluminosilicate minerals Surface functional groups are basic units of surface complexation reactions of minerals. (Hydr)oxide minerals possess surface hydroxyl groups only and phylloaluminosilicate minerals have ion bearing exchange sites in addition to surface hydroxyl groups. Surface charges on minerals consists of permanent structural charge, coordinative surface charge and dissociated surface charge. A variety of zero surface charge conditions could be presented with different types of points of zero charge. The constant capacitance model (CCM), the double layer model (DLM) and the triple layer model (TLM) are three most commonly used SCMs Among them, some differences existed in their electrical double layer structures, surface reactions (protolysis and surface complexation), surface charge and mass balance equations, and range of application.

Surface properties of natural aquatic sediments

Eleven geographically and hydrologically diverse sediment samples were collected from major rivers of China and determined for the surface properties. The results indicate the sediments have a large variation in surface area (6.9–16.0 m 2/g of SSA N2, 35.6–73.2 m 2/g of SSA CPB), surface site density (10.3–149.8 μmol/g) and surface acidity constants (1.56–2.50 of pK int 5,a1 and 3.75–5.58 of pK int 5,a2) but a small difference in PZSE (3.0–4.0). Within the pH range 3.0–9.0, all sediments present negative surface charges. Their surface charge distribution curves with pH extend between those of SiO 2, montmorillonite, kaolinite, α-MnO 2, calcite and γ-Al 2O 3. Correlation analysis reveals that surface area and surface site density of the sediments are correlated strongly with reactive and amorphous iron oxides, total aluminum, clay and total organic carbon, while surface acidity constants, PZSE and the permanent structural charge only show a weak correlation with total aluminum in the sediments.

Surface Charge Properties of Kaolinite

AbstractThe surface charge components of 2 Georgia kaolinites of differing degrees of crystallinity (KGa-1 and KGa-2) were determined using procedures based on charge balance concepts. Permanent structural charge density (σ0) was determined by measuring the surface excess of Cs, which is highly selective to permanent charge sites. The values of σ0 determined were -6.3 ± 0.1 and -13.6 ± 0.5 mmol kg−1 for kaolinites KGa-1 and KGa-2, respectively. The net proton surface charge density (σH) was determined as a function of pH by Potentiometrie titration in 0.01 mol dm-3 LiCl. Correction from apparent to absolute values of σH was made by accounting for Al release during dissolution, background ion adsorption and charge balance. Lithium and C1 adsorption accounted for the remainder of the surface charge components. Changes in surface charge properties with time were measured after mixing times of 1, 3 and 15 h, the latter representing “equilibrium”. Time-dependent behavior is believed to be caused by mineral dissolution followed by readsorption or precipitation of Al on the mineral surface. Both the point of zero net charge (p.z.n.c.) and the point of zero net proton charge (p.z.n.p.c.) changed with mixing time, generally increasing. The “equilibrium” p.z.n.c. values were approximately 3.6 for KGa-1 and 3.5 for KGa-2, whereas the corresponding p.z.n.p.c. values were about 5.0 and 5.4. The p.z.n.c. results were in good agreement with previous studies, but the values of p.z.n.p.c. were higher than most other values reported for specimen kaolinite.

Surface Charge Properties Of Kaolinite

AbstractThe surface charge components of two Georgia kaolinites of differing degree of crystallinity (KGa-1 and KGa-2) were measured using procedures based on charge balance concepts. Permanent structural charge density (Σ0) was determined by measuring the surface excess of Cs, which is highly selective to permanent charge sites. The values of Σ0 determined were -6.3 ± 0.1 and -13.6 ± 0.5 mmol kg-1 for kaolinites KGa-l and KGa-2, respectively. The net proton surface charge density (σH) was determined as a function of pH by potentiometric titration in 0.01 mol dm-3 LiC1. Correction from apparent to absolute values of ΣH was made by accounting for Al release during dissolution, background ion adsorption, and charge balance. Lithium and Cl adsorption accounted for the remainder of the surface charge components. Changes in surface charge properties with time were measured after mixing times of 1, 3, and 15 hours (the latter representing “equilibrium”). Time-dependent behavior is believed to be caused by mineral dissolution followed by readsorption or precipitation of Al on the mineral surface. Both the point of zero net charge (p.z.n.c.) and the point of zero net proton charge (p.z.n.p.c.) changed with mixing time, generally increasing. The “equilibrium” p.z.n.c. values were approximately 3.6 and 3.3 for KGa-1 and KGa-2, respectively, while the corresponding p.z.n.p.c. values were about 5.0 and 5.4. The p.z.n.c. results were in good agreement with previous studies, but the values of p.z.n.p.c. were higher than other values reported for specimen kaolinite.

Surface charge characteristics of kaolinitic tropical soils

Surface charge properties of four representative kaolinitic soils from the humid tropics (Brazil) were investigated by a methodology involving independent measurements of net total permanent and variable charge components. Permanent structural charge was determined by Cs + adsorption, whereas variable charge was quantified by simultaneous proton titration and background electrolyte (LiCl) adsorption measurements. Data were obtained for homoionic soils suspended in LiCl solutions of ionic strength 1–10 mmol L −1 and pH value 2–6. Corrections were made in the titration data for proton consumption resulting from dissolution and aqueous-phase complexation reactions. Conjunctive use of proton titration and electrolyte adsorption data yielded independent assessments of proton surface charge densities and points of zero charge. The surface charge data were tested successfully for consistency with the law of surface charge balance. Three of the soils exhibited similar surface charge behavior, with no pronounced effect of differences in either organic C or Fe and aluminum oxide content. One soil containing significant manganese oxides showed points of zero charge well below those of the other three soils. The point of zero net charge (p.z.n.c) for the soils was ≤4, lower than values reported for specimen kaolinite. The point of zero net proton charge (p.z.n.p.c.) increased with decreasing ionic strength. In all cases, the presence of small quantities of structural charge in 2:1 clay minerals had a significant effect on surface charge properties; e.g., for all soils, p.z.n.c. < p.z.n.p.c. These characteristics of surface charge were shown to be consistent with the behavior of a mixture of kaolinite, organic matter, and a small quantity of 2:1 clay minerals. In conformity with the law of surface charge balance, ionic strength effects were found to be removed by plotting net adsorbed ion charge against net proton surface charge density.

Surface charge characteristics of kaolinitic tropical soils

Surface charge properties of four representative kaolinitic soils from the humid tropics (Brazil) were investigated by a methodology involving independent measurements of net total permanent and variable charge components. Permanent structural charge was determined by Cs+ adsorption, whereas variable charge was quantified by simultaneous proton titration and background electrolyte (LiCl) adsorption measurements. Data were obtained for homoionic soils suspended in LiCl solutions of ionic strength 1–10 mmol L−1 and pH value 2–6. Corrections were made in the titration data for proton consumption resulting from dissolution and aqueous-phase complexation reactions. Conjunctive use of proton titration and electrolyte adsorption data yielded independent assessments of proton surface charge densities and points of zero charge. The surface charge data were tested successfully for consistency with the law of surface charge balance. Three of the soils exhibited similar surface charge behavior, with no pronounced effect of differences in either organic C or Fe and aluminum oxide content. One soil containing significant manganese oxides showed points of zero charge well below those of the other three soils. The point of zero net charge (p.z.n.c) for the soils was ≤4, lower than values reported for specimen kaolinite. The point of zero net proton charge (p.z.n.p.c.) increased with decreasing ionic strength. In all cases, the presence of small quantities of structural charge in 2:1 clay minerals had a significant effect on surface charge properties; e.g., for all soils, p.z.n.c. < p.z.n.p.c. These characteristics of surface charge were shown to be consistent with the behavior of a mixture of kaolinite, organic matter, and a small quantity of 2:1 clay minerals. In conformity with the law of surface charge balance, ionic strength effects were found to be removed by plotting net adsorbed ion charge against net proton surface charge density.