© 2018 Académie des sciences This article gives an overview of the preparation, applications, and limits of organoclay materials in the environment field. Organoclays are obtained by the combination of clay minerals and surfactants (quaternary alkyl ammonium salts and others) and are appropriate candidates for the adsorption of organic contaminants such as pesticides, herbicides, and pharmaceuticals that are more and more found in the water resource despite wastewater treatments. This review article focuses on novel organoclay preparation methods based on the use of nonconventional nonionic surfactants and the interest and limits of these hybrid materials for the adsorption of organic compounds at both batch equilibrium and dynamical percolation experimental conditions.

© 2018 by the authors. The present study demonstrates the effectiveness of hydroxyapatite nanopowders in the adsorption of zinc in aqueous solutions. The synthesized hydroxyapatites before (HAp) and after the adsorption of zinc (at a concentration of 50 mg/L) in solution (HApD) were characterized using X-ray diffraction (XRD), and scanning and transmission electron microscopy (SEM and TEM, respectively). The effectiveness of hydroxyapatite nanopowders in the adsorption of zinc in aqueous solutions was stressed out through ultrasonic measurements. Both Langmuir and Freundlich models properly fitted on a wide range of concentration the equilibrium adsorption isotherms, allowing us to precisely quantify the affinity of zinc to hydroxyapatite nanopowders and to probe the efficacy of hydroxyapatite in removal of zinc ions from aqueous solutions in ultrasonic conditions.

© 2018 Author(s). Nowadays, the advances in materials science have created the possibility of using nanomaterials as adsorbents in environmental technologies. This study is focused on the evaluation of C-HAp powders capacity in lead ions removal from contaminated solutions. The C-HAp powders after removal of lead (Pb2+) ions from contaminated water were characterized by X-Ray Photoelectron Spectroscopy (XPS) and Energy Dispersive X-ray analysis (EDX). The presence of lead in the hydroxyapatite powders after removal experiments was observed in the XPS general spectrum and also in the EDX spectra. In addition, the AAS studies revealed that the C-HAp powders possess a high affinity towards lead ions with an effective removal rate of 80% for an initial lead concentration of 20 mg·L-1.

© 2017 Elsevier B.V. The design of French VFCWs leads to the formation of a sludge layer at the surface of the first filters due to the retention of suspended solids from the percolation of unsettled wastewater. This layer plays a major role in the system but still little is known on its characteristics and evolutions. In this study, suspended solids and sludge deposits sampled from two French VFCW plants were analyzed by different methods in the objective to assess the evolution of particulate organic matter (POM) along the treatment chain and within the sludge layer, and identify relevant analytical indicators of these phenomena. The treatment chain included an aerobic trickling filter followed by FeCl3injection and two successive stages of filters. Thermal analyses showed that OM contents of suspended solids decreased along the treatment chain. POM in inflow suspended solids was predominantly composed of reactive, biodegradable compounds which were partly hydrolyzed and mineralized notably at the trickling filter stage. 3D fluorescence spectra collected from aqueous POM extracts confirmed the evolution of organic matter from low-molecular reactive compounds to more complex and stable structures such as humic-like substances. FTIR confirmed the mineralization of POM's reactive constituents along the treatment chain by the decrease in the intensities of the characteristics bands of aliphatic compounds or proteins, and its humification in the sludge deposits through the relative increase of the bands at 1634 cm− 1(vC = O) and 1238 cm− 1(δC = Oand/or δOH). Isotopic ratios δ2H/1H and δ15N/14N were found to be good indicators of POM evolutions. The higher values of δ2H/1H and δ15N/14N ratios measured in sludge deposits as compared to inflow suspended solids were related to POM humification and to microbial processes of POM hydrolysis and mineralization, respectively.

The research conducted in this study presented for the first time results of physico-chemical properties and in vitro antimicrobial activity of hydroxyapatite plant essential oil against Gram-positive bacteria (methicillin-resistant Staphylococcus aureus (MRSA) and S. aureus 0364) and Gram-negative bacteria (Escherichia coli ATCC 25922). The samples were studied by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy to determine the morphology and structure of the nanocomposites of hydroxyapatite coated with basil (HAp-B) and lavender (HAp-L) essential oils (EOs). The values of the BET specific surface area (SBET), total pore volume (VP) and pore size (DP) were determined. The results for the physico-chemical properties of HAp-L and HAp-B revealed that lavender EOs were well adsorbed on the surface of hydroxyapatite, whereas basil EOs showed a poor adsorption on the surface of hydroxyapatite. We found that the lavender EOs hydroxyapatite (HAp-L) exhibited a very good inhibitory growth activity. The value of the minimum inhibitory concentration (MIC) related to growth bacteria was 0.039 mg/mL for MRSA, 0.02 mg/mL for S. aureus and 0.039 mg/mL E. coli ATCC 25922. The basil EO hydroxyapatite (HAp-B) showed poor inhibition of bacterial cell growth. The MIC value was 0.625 mg/mL for the HAp-B sample in the presence of the MRSA bacteria, 0.313 mg/mL in the presence of S. aureus and 0.078 mg/mL for E. coli ATCC 25922.

© 2018 Author(s). The progress of nanotechnology made possible the use of nanomaterials as adsorbents and magnetic iron oxides represents one of the first generations of nanoscale materials used in environment technologies [1]. A systematic characterization of commercial magnetite (Fe3O4) is presented in this research. The commercial (Fe3O4) magnetic adsorbents were characterized by various characterizations methods such as X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray analysis (EDX). This study was also focused on the study of adsorption isotherms and the kinetics evaluation. X-ray studies indicated that As3+and Cu2+removed by Fe3O4did not seem to alter the structure of Fe3O4but they were highlighted in the EDX analysis. In addition, the SEM studies were consistent with the XRD results. The rate of adsorption of contaminants, in contaminated solutions decreases when the amount of contaminant increases in all experiments performed. The results revealed that Fe3O4nanoparticles are promising candidates which could be used as sorbents for the removal of arsenic from the marine environment, for site remediation and groundwater treatment.

The aggregation of surfactants on solid surfaces as they are adsorbed from solution is the basis of numerous technological applications such as colloidal stabilization, ore flotation, and floor cleaning. The understanding of both the structure and the dynamics of surfactant aggregates applies to the development of alternative ways of preparing hybrid layered materials. For this purpose, we study the adsorption of the triethylene glycol mono n-decyl ether (C10E3) nonionic surfactant onto a synthetic montmorillonite (Mt), an aluminosilicate clay mineral for organoclay preparation with important applications in materials sciences, catalysis, wastewater treatment, or as drug delivery. The aggregation mechanisms follow those observed in an analogous natural Mt, with the condensation of C10E3 in a bilayer arrangement once the surfactant self-assembles in a lamellar phase beyond the critical micelle concentration, underlining the importance of the surfactant state in solution. Solid-state H-1 nuclear magnetic resonance (NMR) at fast magic-angle spinning (MAS) and high magnetic field combined with(1)H-C-13 correlation experiments and different types of C-13 NMR experiments selectively probes mobile or rigid moieties of C10E3 in three different aggregate organizations: (0 a lateral monolayer, (ii) a lateral bilayer, and (iii) a normal bilayer. High-resolution H-1{Al-27} CP-H-1-H-1 spin diffusion experiments shed light on the-proximities and dynamics of the different fragments and fractions of the intercalated surfactant molecules with respect to the Mt surface. Na-23 and H-1 NMR measurements combined with complementary NMR data, at both molecular and nanometer scales, precisely pointed out the location of the C10E3 ethylene oxide hydrophilic group in close contact with the Mt surface interacting through ion dipole or van der Waals interactions.

The artificial mineralization of a polyresistant bacterial strain isolated from an acidic, oligotrophic lake was carried out to better understand microbial (i) early mineralization and (ii) potential for further fossilisation. Mineralization was conducted in mineral matrixes commonly found on Mars and Early-Earth, silica and gypsum, for 6 months. Samples were analyzed using microbiological (survival rates), morphological (electron microscopy), biochemical (GC-MS, Microarray immunoassay, Rock-Eval) and spectroscopic (EDX, FTIR, RAMAN spectroscopy) methods. We also investigated the impact of physiological status on mineralization and long-term fossilisation by exposing cells or not to Mars-related stresses (desiccation and radiation). Bacterial populations remained viable after 6 months although the kinetics of mineralization and cell-mineral interactions depended on the nature of minerals. Detection of biosignatures strongly depended on analytical methods, successful with FTIR and EDX but not with RAMAN and immunoassays. Neither influence of stress exposure, nor qualitative and quantitative changes of detected molecules were observed as a function of mineralization time and matrix. Rock-Eval analysis suggests that potential for preservation on geological times may be possible only with moderate diagenetic and metamorphic conditions. The implications of our results for microfossil preservation in the geological record of Earth as well as on Mars are discussed.

Investigation of organic matter (OM) preservation mechanisms is crucial for understanding organic accumulation in sedimentary environments. We focus here on the contribution of organo-clay interaction in such preservation. Most studies addressing this issue deal with organo-mineral complexes which have settled, omitting consideration of early aggregation within the water column. We therefore investigated the sorption of OM on montmorillonite (Na MMt) and kaolinite (Kaol) immersed in a permanently stratified water column (Lake Pavin, France). The two types of clay samples were kept immersed for different lengths of time and characterized via analytical methods suited for the organic phase [pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), GC-MS, Fourier transform infrared spectroscopy (FTIR) and dissolved organic carbon (DOC) analysis], as well as for the mineral phase [X ray diffraction (XRD) and microprobe elementary cartography]. Results suggest that strong organo-clay interaction occurred within the water column to a varying extent depending on water physicochemical conditions and the mineral phase typology. A higher concentration of DOC was observed in the proximal environment of the clay traps, suggesting an attractive effect induced by the clay minerals. Lipid compounds sorbed during the immersion were essentially fatty acids and aromatic compounds. Their distributions were closer to a phytoplankton signature than allochtonous pedogenetic OM.
The sorption was particularly efficient in the O-2 transition zone, with a greater amount of OM on Na-MMt than Kaol. This was principally due to the high specific surface area and cationic exchange capacity (CEC) of the 2/1 clay mineral. Besides, XRD characterization revealed an increase in Na MMt interlayer spacing, which did not necessarily correspond to organic intercalation.
The study confirms that the sorption of dissolved OM cannot alone explain the preservation of hydrocarbon-rich OM in such a lacustrine environment. Indeed, the sorbed OC was very low compared with the amount proposed by several authors as an expression of the monolayer equivalent principle. (C) 2017 Elsevier Ltd. All rights reserved.

Among pharmaceutical products (PPs) recalcitrant to water treatments, diclofenac shows a high toxicity and remains at high concentration in natural aquatic environments. The aim of this study concerns the understanding of the adsorption mechanism of this anionic PP onto two organoclays prepared with two long-alkyl chains cationic surfactants showing different chemical-nature for various experimental pH and temperature conditions. The experimental data obtained by a set of complementary techniques (X-ray diffraction, elemental analyses, gas chromatography coupled with mass spectrometry, and Fourier transform infrared spectroscopy) and the use of Langmuir, Freundlich and Dubinin-Radushkevish equation models, reveal that organoclays show a good affinity to diclofenac which is enhanced as the temperature is under 35 degrees C and for pH above 4.5 (i.e. >pKa of diclofenac) while the chemical nature of surfactant appears to play a minor role. The thermodynamic parameters derived from the fitting procedure point out the strong electrostatic interaction with organic cations adsorbed within the interlayer space in the organoclays for the adsorption of diclofenac. This study stress out the application of organoclays for the adsorption of a recalcitrant PPs in numerous aquatic compartments that can be used as a complement with activated carbon for waste water treatment. (C) 2016 Elsevier B.V. All rights reserved.

The aim of this study consisted to develop novel synthetic magnetite nanoparticles (nFe(3)O(4)) with preferential reactivity to trace elements (TE) for possible environmental applications as adsorbents. The synthetic magnetite materials obtained through the co-precipitation of both Fe3+ and Fe2+ ions (Fe2+ / Fe3+ = 0.5) were characterized by a set of complementary techniques: X-ray diffraction, transmission and scanning electron microscopy, Fourier transform infrared and Raman spectroscopy, and BET adsorption method. The resulting nFe(3)O(4) displayed a wide specific surface area (100 m(2) g(-1)) with particles reaching a size of about 10 nm, smaller than those of the well-crystallized commercial ones (cFe(3)O(4)) estimated at 80 nm while showing a BET surface area of 6.8 m(2) The adsorption properties of the synthetic nFe(3)O(4) magnetite nanoparticles were characterized and compared to the commercial analogous with the adsorption of both As and Cu. The equilibrium adsorption isotherms were properly fitted with Langmuir and Freundlich equation models and suggested that the developed iron oxides nanoparticles display a certain potential for removal and/or immobilization of TE from contaminated waters and/or soils, with an increase of 69.5% of the adsorbed amount compared to that of the commercial ones. (C) 2016 Elsevier B.V. All rights reserved.

The aim of this study was to prepare and characterize a hybrid layered material (organoclay) with a Na-montmorillonite and the triethylene glycol mono-n-decyl ether (C10E3) nonionic surfactant which forms a lamellar phase at room temperature. The synthesized organoclay was characterized by complementary techniques (Fourier transform infrared spectroscopy and X-ray diffraction). Experiments in conjunction with electron density analysis showed that a bilayer or membrane of C10E3 was intercalated within the interlayer space of a naturally exchanged Na-montmorillonite. The intercalation of a bilayer of C10E3 in a clay mineral offers new perspectives for the manufacturing of nanomaterials. While showing a hydrophobic surface and a large interlayer space value, the resulting organoclay preserves the compensating cations within the interlayer space allowing one to perform ion exchanges, making easier the intercalation of further organic molecules of important size with functional properties or for environmental purposes.

A Na-smectite clay mineral (Na-Mt) was exchanged with various amounts of benzyldimethyltetradecyl ammonium chloride cationic surfactant (BDTAC) up to four times the cation exchange capacity (CEC). The adsorption properties of these organoclays as well as a coupled micelle/organoclay process were evaluated to remove an anionic pharmaceutical product, the diclofenac (DCF), recognized as a recalcitrant compound for conventional water treatments and to be poorly adsorbed onto untreated clay mineral. The DCF affinity appears to depend on the lipophilic character of organoclays in correlation to the density of intercalated BDTA and is particularly enhanced for sorbent systems with free surfactant or micelle in solution. The combination of both organclay and BDTA in excess or micelle as a one pot adsorption system appears to be the most efficient material for the sequestration of DCF and other pharmaceutical products (PPs) with a K-F Freundlich constant of 1.7 L g(-1) and no restriction of the adsorbed DCF amount as the linear adsorption isotherm shows. A BDTA hydrophobic core micelle coupled with a positive electric charge forms an organic complex with DCF that is properly intercalated within the interlayer space of BDTA-Mt organoclays as both Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data supported.

The nature and the origin of zinc clays are poorly understood. With the example of the Bou Arhous Zn-Pb ore deposit in the Moroccan High Atlas, this study presents new data for the mineralogical and chemical characterization of barren and zinc clays associated with non-sulfide zinc ores. In the field, white to ocher granular clays are associated with willemite (Zn2SiO4), while red clays fill karst-related cavities cutting across the non-sulfide ore bodies. Red clays (kaolinite, chlorite, illite, and smectite) present evidence of stratification that reflects internal sedimentation processes during the karst evolution. White clays contain 7- clay mineral/smectite irregular interstratified minerals with less than 20 % of smectite layers. Willemite is partially dissolved and is surrounded by authigenic zinc clay minerals. Together with XRD results, WDS analyses on newly formed clay aggregates suggest that this interstratified mineral is composed of fraipontite and sauconite. CEC measurements support that zinc is only located within the octahedral sheets. These new results support the following process: (i) dissolution of willemite, leading to release of Si and Zn, (ii) interaction between Zn-Si-rich solutions and residual-detrital clays, and (iii) dissolution of kaolinite and formation of interstratified zinc clay minerals that grew over detrital micas.

Natural Organic Matter (OM) preservation and sedimentary burial mechanisms are still poorly understood despite their importance in oil source rock characterization and carbon cycle issues. It is now recognized that mineral sorption contributes significantly to OM preservation by conferring steric protection and preventing enzymatic access. Most of the studies dealing with OM preservation have focused on settled OM, omitting aggregation in the water column. For the first time, we have tested the complexation of natural OM on 3 types of clays in seawater in-situ conditions. Samples of Na exchanged montmorillonite (Na MMt), synthetic montmorillonite (S Na MMt) and natural kaolinite (Kaol) were immersed in an upwelling zone (Antofagasta bay, Chile). Three depths were studied: 15 m (photic zone), 40 m (oxygen transition zone) and 80 m (anoxic zone). The clayey samples were kept immersed for different durations and analyzed after removal, via GC/MS, Py-GC/MS, flash elementary pyrolysis, DOC analyzer and XRD. The main results are: (1) for the shortest immersion times, DOC analyzes performed on clays' proximal water indicated excessive DOC concentrations compared to seawater values. This attraction effect was however temporary, as values tended to rebalance with seawater concentrations for the longest immersion times. (2) Molecular analyses performed on seawater organic extracts indicated that fatty acids, alkanes, alkyl benzenes and methoxy-benzenes were the main dissolved lipid groups. (3) These lipids were also the main sorbed compounds identified on immersed clays, with a predominance of fatty acids. This is due to the higher availability and better affinity of fatty acids with the clayey samples. (4) Because of its higher specific area and CEC, Na MMt exhibited the best sorption rates compared to Kaol and SNa MMt. X ray analyses performed on Na MMt indicated d(001)spacing growths, but these growths are not attributed to OM intercalation. Sorbed OM is probably located on the external surfaces leaf edges of clays. (C) 2016 Elsevier B.V. All rights reserved.

The removal of a Pharmaceutically Active Compound (PhAC) pool using a well referenced clay mineral from Wyoming (SWy-2) as a geosorbent was studied for a better understanding of the environmental fate. As expected, the selected material shows its particular adsorption properties to PhAC under different experimental conditions with two main features depending on the chemical nature of the emerging micro-pollutants. Cationic PhACs, for which the driving force for their adsorption results from electrostatic interaction via the exchange with the inorganic cations of the clay mineral, are almost completely removed for all studied experimental conditions where it appears that the S/L ratio plays a minor role and the only one limitation for their removal is the cation exchange capacity of the adsorbent. In contrast, anionic and neutral PhACs are adsorbed to the clay mineral surface (silanol groups on the sheet edges, inorganic cations.) through other interactional mechanisms involving ion-dipole, van der Waals interaction, leading to a competition of all organic molecules where their chemical nature (electric charge, hydrophobicity) may also play a role in their adsorption. While the adsorption of ketoprofen, naproxen, diclofenac and salicylic acid anionic PhACs slightly increases with the increase of the S/L ratio, the removal of the neutral and the other anionic PhACs (gemfibrozil and ibuprofen) seems to be independent of that ratio and is particularly enhanced. The efficiency of the removal for a global pool of PhACs even in low S/L ratio stresses the control of the selected natural minerals on the dynamics of PhACs in the environment.

The aim of the current research work was to study the physicochemical and biological properties of synthesized zinc doped hydroxyapatite (ZnHAp) nanoparticles with Zn concentrations x(Zn) = 0 (HAp), x(Zn) = 0.07 (7ZnHAp), and x(Zn) = 0.1 (10ZnHAp) for potential use in biological applications. The morphology, size, compositions, and incorporation of zinc into hydroxyapatite were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Raman scattering, and X-Ray Photoelectron Spectroscopy (XPS). In addition, the cytotoxicity of ZnHAp nanoparticles was tested on both E. coli bacteria and human hepatocarcinoma cell line HepG2. The results showed that ZnHAp nanoparticles (HAp, 7ZnHAp, and 10ZnHAp) have slightly elongated morphologies with average diameters between 25 nm and 18 nm. On the other hand, a uniform and homogeneous distribution of the constituent elements (calcium, phosphorus, zinc, and oxygen) in the ZnHAp powder was noticed. Besides, FTIR and Raman analyses confirmed the proper hydroxyapatite structure of the synthesized ZnHAp nanoparticles with the signature of phosphate, carbonate, and hydroxyl groups. Moreover, it can be concluded that Zn doping at the tested concentrations is not inducing a specific prokaryote or eukaryote toxicity in HAp compounds.

An alternative and simple coprecipitation method was developed to obtain carbon nanotube-hydroxyapatite (CNTs:HAp) based nanocomposites. The incorporation of CNTs (in a concentration of 5% and 10% of total weight of the nanocomposite) and their impact on both structural and biological properties were studied by using a set of standard complementary biological, microscopic, and spectroscopic techniques. The characteristic peaks of carbon structure in CNTs were not observed in the CNTs-HAp composites by X-ray diffraction analysis. Moreover, FTIR and Raman spectroscopies confirmed the presence of HAp as the main phase of the synthesized CNTs: HAp nanocomposites. The addition of CNTs considerably affected the nanocomposite morphology by increasing the average crystallite size from 18.7 nm (for raw HAp) to 28.6 nm (for CNTs:HAp-10), confirming their proper incorporation. The biocompatibility evaluation of CNTs:HAp-5 and CNTs:HAp-10 nanocomposites included the assessment of several parameters, such as cell viability, antioxidant response, and lipid peroxidation, on human G-292 osteoblast cell line. Our findings revealed good biocompatibility properties for CNTs: HAp nanocomposites prepared by the coprecipitation method supporting their potential uses in orthopedics and prosthetics.

The objective of the study was to evaluate the sorption of a pool of pharmaceutically active compounds (PhACs) onto a clay-sand filter in a dynamic sorption experiment. The chosen adsorbent should have suitable chemical properties for the removal of the targeted PhACs and also a consistent hydrodynamic behavior regarding field application. In this aim, the impact of interfoliar cations (Ca2+ or Na+) intercalated into natural montmorillonite (Swy2) was tested by using different clay-sand ratios (from 0% to 100% of clay minerals). Only Ca-Swy2 showed a consistent hydraulic conductivity for field application with a value of 4.78 x 10(-8) m s(-1) for a 5%/95% clay-sand ratio. The sorption of PhACs onto this filter was investigated using oedometer cells by varying two parameters: the solution matrix (ultra-pure water or natural effluent) and the injection pressure (0.1 MPa and 0.2 MPa). The PhACs were effectively adsorbed onto the filter for each experiment at different levels. The drop in injection pressure was a favorable factor for sorption whatever the matrix was, with median global removal of similar to 45% at 0.2 MPa and similar to 75% at 0.1 MPa. The effect of the matrix exhibited two different trends as a function of the molecular charge of each PhAC. While cationic compounds were more effectively sorbed in the ultra-pure water matrix than in the effluent matrix, the sorption of anionic PhACs was more effective in the effluent matrix than in ultra-pure water. This indicates that the charge of the pollutant is a key parameter in controlling the efficiency of the adsorbent. Despite these removal variations, the filter exhibited a significant sorption capacity especially at 0.1 MPa. It can therefore be an efficient solution for the removal of PhACs by tertiary filtration.

While retaining its lamellar liquid crystal phase, K4Nb6O17 nanosheets were used as a template to sandwich and stabilize an alkylpoly(ethylene oxide) nonionic surfactant-water system showing monodomain (lamella) formation within the inorganic niobate sheets that appears to be not dependent on the surfactant liquid crystalline state in solution but more its concentration.

A sodium exchanged smectite clay mineral (Mt) was used as geo-sorbent for the adsorption of tramadol and doxepin: two pharmaceutical products (PPs) defined as emerging pollutants due to their presence at significant concentration in numerous water compartments. The adsorption isotherms for both the temperatures of 20 and 40 degrees C and the derived data determined through the fitting procedure by using Langmuir, Freundlich and Dubinin-Radushkevich equation models explicitly pointed out that the sorption of both tramadol and doxepin is mainly driven by electrostatic interaction. The studied PPs are intercalated in a monolayer arrangement within the interlayer space through a cation exchange in stoichiometric proportion with the Na+ cations leading to adsorbed PPs amounts that match the cation exchange capacity (CEC) of Mt. Due to their hydrophobic character, additional doxepin molecules could be adsorbed by weak molecular interaction driving to an increase of the adsorbed amount beyond the CEC at low temperature (20 degrees C). The confinement of PPs within the interlayer space of Mt confirms the use of clay minerals as potential material for the wastewater treatment as well as it drives to an amorphous or glassy state, which can find echo in biopharmaceutical applications for a controlled release of PPs. (C) 2015 Elsevier Inc. All rights reserved.

The goal of this study was to obtain at low temperature a functional nano-composite with characteristics similar to the natural bone by using a cost effective method. The structure and morphology of collagen coated zinc doped hydroxyapatite bio-composites (Zn:HAp-CBc) were examined by X-Ray diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD analysis revealed that the unique hexagonal Ca-10(PO4)(6)(OH)(2) in P-63m space group was observed in the obtained nanocomposites Zn: HAp-CBc. The cytotoxicity of the Zn: HAp-CBc was studied on HeLa cell lines. Cell cycle distribution after treatment was examined by flow cytometry analysis. Our preliminary in vitro studies revealed that the obtained composites based on Zn doped HAp embedded in collagen matrix have excellent biocompatibility and support their further characterization by in vivo approaches and development as a biomaterial used in bone regeneration.

In this study, a nanocomposite based on a biodegradable polymer poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) reinforced by triethylene glycol mono-n-decyl ether (C10E3) non-ionic organoclay (C10E3-Mt) was prepared. The morphology and the thermal and mechanical properties of PHBV/C10E3-Mt were compared with those of PHBV nanocomposites prepared using commercial organically modified montmorillonite Cloisite((R)) 30B (OMt) and raw montmorillonite (Mt). Nanocomposites with 3wt% nanoparticles were obtained by melt processing. The high level of dispersion with improved interfacial interactions between OMt and polymer led to an increase in the thermal stability and modulus of PHBV. However, this nanocomposite presented a lower strain before fracture, typical of brittle behavior. The transmission electron microscopy and wide angle X-ray diffraction results revealed a significant increase in the interlayer spacing of clay for the PHBV/C10E3-Mt nanocomposite, which was favored by the wide expansion of the platelets of the starting non-ionic organoclay. This characteristic of C10E3-Mt, together with its hydrophobic behavior, allowed its easy incorporation in the PHBV matrix, thus improving the processing and maintaining a high modulus with increased material toughness. (c) 2014 Society of Chemical Industry

A Na exchanged montmorillonite (Mt) was used as a starting layered material for the preparation of two organoclays synthesized with benzyl decyltrimethyl ammonium (BDTA) cationic surfactant and the triethylene glycol mono n-decyl ether(C10E3), a nonconventional nonionic surfactant. The adsorption of the surfactants was performed at an amount of 0.7 times the cation exchange capacity (CEC) for BDTA and below the critical micelle concentration (cmc) where C10E3 is in a monomer state, leading to the intercalation of a lateral monolayer surfactant arrangement within the interlayer space and about 5-7% organic carbon content in organoclays. The environmental properties of both nonionic (C10E3-Mt) and cationic (BDTA-Mt) organoclays were compared to those of the starting Mt clay with the sorption of three micro-pollutants: benzene, dimethyl-phthalate and paraquat. The adsorption isotherms and the derivative data determined through the fitting procedure by using Langmuir, Freundlich and Dubinin-Radushkevitch equation models explicitly highlighted the importance of the chemical nature of the micropollutants, which play on the adsorbents efficiency. The adsorption data combined with FTIR and XRD supplementary results suggest that C10E3-Mt nonionic organoclay, although being less efficient for the retention of the different micropollutants, turned out to be the most polyvalent adsorbent since such hybrid material could adsorb the entire studied organic compounds. (c) 2014 Elsevier Inc. All rights reserved.

This paper reports the systematic investigation of europium doped hydroxyapatite (Eu:HAp). A set of complementary techniques, namely Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and the Brunauer-Emmett-Teller (BET) technique were used towards attaining a detailed understanding of Eu:HAp. The XPS analysis confirmed the substitution of Ca ions by Eu ions in the Eu:HAp samples. Secondly, Eu:HAp and pure HAp present type IV isotherms with a hysteresis loop at a relative pressure (P/P-0) between 0.4 and 1.0, indicating the presence of mesopores. Finally, the in vitro biological effects of Eu:HAp nanoparticles were evaluated by focusing on the F-actin filament pattern and heat shock proteins (Hsp) expression in HEK293 human kidney cell line. Fluorescence microscopy studies of the actin protein revealed no changes of the immunolabelling profile in the renal cells cultured in the presence of Eu:HAp nanoparticles. Hsp60, Hsp70 and Hsp90 expressions measured by Western blot analysis were not affected after 24 and 48 hours exposure. Taken together, these results confirmed the lack of toxicity and the biocompatibility of the Eu:HAp nanoparticles. Consequently, the possibility of using these nanoparticles for medical purposes without affecting the renal function can be envisaged.

The efficiency of aided phytostabilization using organic amendments such as ramial chipped wood (RCW) and composted sewage sludge (CSS) was studied on contaminated techno-soils, on nine experimental plots. The objective was to characterize the role of fulvic (FA) and humic acids (HA) on the mobilization of trace elements, specifically As, Cu, Mo, Pb and Zn. Results showed that the addition of CSS increased the total organic carbon and nitrogen content more than with RCW and as a result, the C/N ratio in the CSS soil was higher than in the RCW and non-amended (NE) soil, reflecting the high decomposition of soil organic matter in the CSS soil compared with the other soils. The RCW and CSS amendments increased the hydrogen index (HI) values and the oxygen index (OI) values compared with the NE soil, especially for the soil treated with CSS which contained more aliphatic than aromatic compounds. The addition of CSS to the techno-soil significantly increased the percentage of C-org associated with the HA fractions compared with the RCW and NE soils. The soil amended with CSS showed the highest E-4/E-6 ratio and the lowest E-2/E-3 ratio of FA. Zn and As were more abundant in the FA fraction than in the HA fraction, whereas Pb, Cu and Mo were more associated to HA than to FA in the treated and untreated soils, which may explain the difference in their mobility and availability.

This study aims to investigate the influence of interlayer cation alkali metal series (Li+, Na+, K+, Rb+, Cs+) and alkali earth metal (Mg2+, Ca2+, Ba2+) on adsorption of model proteins (lysozyme and bovine serum albumin). The localizations of both proteins and their conformational modifications in the interlayer space of the natural clay mineral were studied by X-ray diffraction, transmission electronic microscopy and fluorescence experiments. Based on Langmuir model isotherms, a strong influence of interlayer cation on maximum adsorbed amount and adsorption equilibrium constant has been observed. However the usual kosmotrope/chaotrope classification cannot be used to describe protein adsorption. (C) 2014 Elsevier B.V. All rights reserved.

Peat is a mixture of compounds formed by the decomposition of plant residues and mineral materials that have accumulated at the bottom of ponds and flooded depressions in riverine areas. Due to their extreme heterogeneity and natural variety, the physical and chemical properties of peat can vary widely within or between deposits, and the characterization of isolated samples is still a challenging task that requires the combination of several chemical and spectroscopic methodologies. In this study, the structural characteristics of two Brazilian peat samples were evaluated using scanning electron microscopy (SEM), elemental (CHNS-O) and thermal (TGA) analysis, X-ray diffraction (XRD), and infrared (FT-IR) and solid-state C-13-nuclear magnetic resonance (C-13-NMR) spectroscopies. Although the samples originated from the same peatland, the data showed that the studied samples have distinct chemical properties and that the stage of decomposition played an important role in the differences observed.

A promising alternative for the treatment of effluents that contain pharmaceuticals concerns the adsorption processes that utilize agro-industrial wastes as adsorbents as a substitute for activated carbon. These processes have certain advantages from both economic and environmental points of view, such as availability, abundance, the renewable nature of the adsorbent material, and low cost. In the State of Rio Grande do Sul (Brazil), the grape bagasse is produced on a large scale. In most cases, the waste coming from wineries is disposed directly onto the soil of vineyards resulting in several environmental damages. Thus, the reuse of this biosorbent in adsorption processes can be a way to help manage solid wastes from wine industry. In view of these facts, the aim of the present work was to evaluate the adsorption capacity of the Isabel grape bagasse (Vitis labrusca x Vitis vinifera) in the removal of the DCF. In general way, it was observed that the adsorption process for DCF concentrations greater than 10.0 mg L-1 occurred in two stages. The pseudo-second-order kinetic model was more significant in the rate-controlling step in the first stage. In addition, the removal percentage (similar to 20%) was similar for all concentrations studied. For the second step, on the other hand, the intraparticle diffusion process showed the best fit to the experimental data and the removal percentage increased with increasing initial concentration of the drug (from 57 to 74%). Concerning to the equilibrium process, the Freundlich isotherm showed the best fit to the experimental results at 22 degrees C, and the adsorption of DCF onto grape bagasse presented a value of K-F and n equal to 1.72 g L-1 and 1.18, respectively. From the thermodynamic point of view, the process was exothermic, non-spontaneous, occurring with a decrease in the randomness of the system.

The adsorption of the tri-ethylene glycol mono-n-decyl ether (C10E3) nonionic surfactant, characterized by its self-assembled lamellar phase above the critical micelle concentration (cmc), in a wide range of concentration, onto a layered clay mineral (montmorillonite) has been studied. C10E3 exhibits a high affinity for the montmorillonite (Mt) surface with an adsorption isotherm that differs strictly from previous studies on the adsorption of nonionic surfactants onto clay minerals for which a maximum of adsorption was reached below cmc. The self-organization in a lamellar phase changes the interaction potential between C10E3 and Mt, a surface that favors the aggregation of normal bilayers which expands the interlayer space at wide values (>40 angstrom) while keeping the exchangeable Na+ cations conferring dual hydrophilic-hydrophobic behavior for the hybrid layered materials. Depending on the C10E3 phase state (in monomers or in a lamellar phase), the adsorption leads to four distinct surfactant arrangements (lateral layers to normal tilted bilayers) within the interlayer space of Mt. The hybrid layered materials show a thermal stability at 350 degrees C with a collapse of their interlayer space at 13 angstrom due to the degradation of the hydrocarbon chains of C10E3. FTIR during thermogravimetry analysis permits the identification of the portions of C10E3 corresponding to ethylene oxide groups in close interaction with the Mt surface.

The confinement of lysozyme in 3 layered materials based on montmorillonite and lamellar double hydroxides exhibiting different surface charges was studied. The protein structure and orientation in these materials were determined by X-ray diffraction, time resolved fluorescence and fluorescence anisotropy. For montmorillonite exchanged with sodium and modified with a non-ionic surfactant (tri-ethylene glycol mono n-decyl ether), the lysozyme was found to be located in the interlayer space with the "end-on" and "side-on" orientations, respectively. Conversely, no lysozyme intercalation was observed with a lamellar double hydroxide modified with an anionic surfactant (sodium octylsulfate), since the protein was adsorbed on the surface of the particles. Fourier transformed infrared spectroscopy analysis shows that lysozyme confinement in the interlayer space preserves its structure after dehydration, whereas some structural changes were observed for lysozyme adsorbed on the particle surface.

We present a detailed investigation of the molecular structure of montmorillonite, an aluminosilicate clay with important applications in materials sciences, such as for catalysis, drug delivery, or as a waste barrier. Solid-state Si-29, Al-27, Mg-25, and H-1 nuclear magnetic resonance (NMR) measurements combined with density functional theory (DFT) calculations provide a comprehensive picture of the local structure and composition of a synthetic clay and its naturally occurring analogue. A revised composition is proposed based on NMR results that allow the identification and quantification of the signatures of otherwise undetectable noncrystalline impurities, thus largely complementing the traditional elemental analyses. Solid-state H-1 NMR at fast magic-angle spinning (MAS) and high magnetic field provide quantitative information on intra- and interlayer local environments that are crucial for the determination of the amount of Mg/Al substitution within the octahedral layer. In combination with DFT calculations of energies, it suggests that pairs of adjacent Mg atoms are unfavorable, leading to a nonrandom cationic distribution within the layers.

The aim of the present work was to evaluate the morphologic and chemical characteristics of Isabel grape (Vitis labrusca x Vitis vinifera) bagasse and to describe the adsorption of diclofenac sodium (DCF) from aqueous solutions by this biomass. Grape bagasse constituted mainly of particles with heterogeneous shapes and sizes, and it exhibited a macroporous structure and a low specific surface area (similar to 2 m(2) g(-1)). The adsorbent material was also rich in oxygenated functional groups, especially -OH, and required an acidic pH to neutralize its surface. With respect to the adsorption of DCF, the percentage removal did not appear to depend on the initial concentration of the pharmaceutical. A pseudo-second-order kinetic model described the rate-controlling step, and the adsorption isotherms were well fitted by the Freundlich model. Concerning the thermodynamic data, the results showed that the adsorption of DCF onto grape bagasse occurred via an exothermic process accompanied by a decrease in the randomness at the solid/solution interface. Furthermore, the removal percentages of DCF ranged from 16.4% to 22.8%. (C) 2012 Elsevier B.V. All rights reserved.

The change of the water structure in aqueous solutions of the tri-ethyleneglycol mono n-decyl ether (C(10)E(3)) was studied by micro Raman scattering. The results obtained on the O-H stretching band show that the behavior of the hydrogen bonding (H-bonds) water network can be used as a probe to follow the lamellar (L(alpha)) to sponge (L(3)) phase transition. In the lamellar phase, the stack of the surfactant molecules aggregated into a two-dimensional structure (membrane) acts as a soft confinement system for the H-bond water network of which the regular tetrahedral structure is perturbed. The change of the planar organization of the membranes to a highly disordered and infinite array of bilayers in the sponge phase amplifies the surface of contact between amphiphilic surfactant and water molecules which drives a strong disruption of the regular tetrahedral H-bonding water network. (C) 2011 Elsevier Inc. All rights reserved.

Changes in the structure of synthetic MgxAly(OH)(z) layered double hydroxides are studied during the sorption of organic compounds.

A nonionic surfactant, triethylene glycol mono-n-decyl ether (C10E3), characterized by its lamellar phase state, was introduced in the interlayer of a Na-montmorillonite clay at several concentrations. The synthesized organoclays were characterized by small-angle X-ray scattering in conjunction with Fourier transform infrared spectroscopy and adsorption isotherms. Experiments showed that a bilayer of C10E3 was intercalated into the interlayer space of the naturally exchanged Na-montmorillonite, resulting in the aggregation of the lyotropic liquid crystal state in the lamellar phase. This behavior strongly differs from previous observations of confinement of nonionic surfactants in clays where the expansion of the interlayer space was limited to two monolayers parallel to the silicate surface and cationic surfactants in clays where the intercalation of organic compounds is introduced into the clay galleries through ion exchange. The confinement of a bilayer of C10E3 nonionic surfactant in clays offers new perspectives for the realization of hybrid nanomaterials, since the synthesized organoclays preserve the electrostatic characteristics of the clays, thus allowing further ion exchange while presenting at the same time a hydrophobic surface and a maximum opening of the interlayer space for the adsorption of neutral organic molecules of important size with functional properties.

Humic substances (HS) perform a fundamental role in aquatic environments, exhibiting different levels of reactivity in retaining metal ions and organic pollutants Also, they control the primary production of these ecosystems and act in the carbon sequestering process. In order to improve our understanding vis-a-vis the structural and functional features of HS from aquatic systems, this study aimed to chemically and spectroscopically characterize humic acids (HA) isolated from bottom sediment samples of a stream in a Brazilian subtropical microbasin by elemental analysis, and infrared (FT-IR), ultraviolet and visible (UV-Vis) and solid-state C-13 nuclear magnetic resonance (CP-MAS C-13 NMR) spectroscopies, thermogravimetry (TG), and scanning electron microscopy (SEM) Although all samples originated from the same environment, the data showed that the HA have distinct chemical and spectroscopic properties, and that the location and characteristics of the sampling points from which the sediments were collected played an important role in the differences observed Furthermore, vascular plant matter is probably the main contributor to these samples (C) 2010 Elsevier B.V. All rights reserved

Leachates in waste landfills are characterized by the presence of ammonium ions in large excess. These ammonium ions can be exchanged with the interlayer cations in clay and modify the physical and chemical properties of clay geochemical barriers in waste landfills and drive to environmental problems. The purpose of this study was to understand the hydro-physical changes of a smectite in the presence of ammonium ions. An ammonium smectite was prepared by cation exchange from a natural montmorillonite (Wyoming). The samples were characterized and their properties were compared by the use of a set of complementary techniques (X-ray diffraction, infrared spectroscopy, N-2 adsorption desorption BET technique, thermal analysis, and percolation experiments). The main effect was a modification of the porosity and its network, and reduced crystalline swelling. These effects changed the hydraulic conductivity and macroscopic swelling of the clay. The oedometer experiments, which allow simulating the pressure on small amounts of samples, proved the strong increase of the permeability of NH4-smectite. This last point is of great importance in an environment point of view and raises questions on the impermeability behaviour on the long term of the clay geochemical barriers with the presence of ammonium ions in waste landfills. (C) 2010 Elsevier B.V. All rights reserved.

Latosols (Oxisols, Ferralsols) are characterized by a poor soil horizon differentiation, with a strong microgranular structure formed by microaggregates 50 to 300 mu m in size. This microgranular structure is generally considered to be very stable and the shrinkage properties of microaggregates as poor or absent. The objective of our study was to analyse the shrinkage properties of microaggregates in diagnostic Bw horizons collected in Latosols with various particle size distributions and mineralogical compositions depending on their location in a regional toposequence across the Brazilian central plateau. We measured the water retention properties at -300 and -1500 kPa with a centrifugation method. The morphology and size of elementary particles were examined by transmission electron microscopy; specific surface area (SSA) was determined by nitrogen adsorption. We also determined the pore size distribution of microaggregates by the combined use of mercury intrusion and the nitrogen desorption isotherm. Our results show that microaggregates of the Latosols studied were not rigid and shrank during drying. The pore volume of the -300 and -1500 kPa-treated samples, that of the dried microaggregates and the SSA were closely related to the clay content. The mineralogy of particles < 2 mu m played a secondary role in the properties studied. Our results show that microaggregate shrinkage at -300 kPa and -1500 kPa varied with the location of the Latosols in the landscape. Thus, microaggregates of Latosols located on the upper highland surface of Late Tertiary shrank less than those of the lowland surface of Late Quaternary, and this difference was attributed to their different hydric stress histories.

The transformation of clay minerals into organo-clays by surfactant intercalation is of great environmental and industrial importance because it causes the clay to attract hydrophobic contaminants and other non-polar organic compounds, but a better understanding is needed of the mechanisms by which different classes of surfactants are intercalated. The purpose of this study was to synthesize and characterize an organo-clay comprising triethylene glycol monodecyl ether (C(10)E(3)) non-ionic surfactant, which has a lamellar phase at room temperature, intercalated into Ca-montmorillonite from Wyoming (SWy-2). The C(10)E(3) non-ionic surfactant differed from previous non-ionic surfactants used in the formation of a lamellar phase in that it consisted of the stacking of molecules by hydrophobic interaction. C(10)E(3)-clay composites were characterized by complementary techniques (adsorption isotherms, X-ray diffraction, and infrared spectroscopy) and were compared to benzyldimethyltetradecyl ammonium chloride (BDTAC) cationic surfactant-clay composites for different loadings of the surfactant. For large loadings, the amount of C(10)E(3) adsorbed, which can be described by the Langmuir equation, seemed to reach a steady state close to that of the cationic surfactant. The adsorption processes of the two surfactants were different. For the cationic surfactant, the adsorption, as described in the literature, was due to ion exchange between organic cations and Ca(2+) counterions. The adsorption of C(10)E(3) did not depend on electrostatic interaction but rather was due to several interaction mechanisms (H-bonding, ion-dipole, and hydrophobic interaction). For both surfactants, the expansion was limited to two adsorbed monolayers parallel to the clay surface. The expansion of the basal spacing to 17 angstrom suggested a complete dissociation of the C(10)E(3) lamellar phase when adsorbed on the Ca-smectite. Organo-clays made using the non-ionic surfactant were stable, changing the chemical nature of clay to hydrophobic, and allowing for other cations to be exchanged, which has importance in the manufacture of new nanocomposites or geochemical barriers.

We analyze the molecular dynamics heterogeneity of the liquid crystal 4-n-octyl-4(')-cyanobiphenyl nanoconfined in porous silicon. We show that the temperature dependence of the dynamic correlation length xi(wall), which measures the distance over which a memory of the interfacial slowing down of the molecular dynamics persists, is closely related to the growth of the short-range static order arising from quenched random fields. More generally, this result may also shed some light on the connection between static and dynamic heterogeneities in a wide class of condensed and soft matter systems.

We present a neutron and X-rays scattering study of the phase transitions of 4-n-octyl-4' -cyanobiphenyl (8CB) confined in unidirectional nanopores of porous alumina and porous silicon (PSi) membranes with an average diameter of 30nm. Spatial confinement reveals a rich polymorphism, with at least four different low temperature phases in addition to the smectic A phase. The structural study as a function of thermal treatments and conditions of spatial confinement allows us to get insights into the formation of these phases and their relative stability. It gives the first description of the complete phase behavior of 8CB confined in PSi and provides a direct comparison with results obtained in bulk conditions and in similar geometric conditions of confinement but with reduced quenched disorder effects using alumina anopore membranes.

The remaining dynamical degrees of freedom of molecular fluids confined into capillaries of nano to sub-nanometre diameter are of fundamental relevance for future developments in the field of nanofluidics. These properties cannot be simply deduced from the bulk one since the derivation of macroscopic hydrodynamics most usually breaks down in nanoporous channels and additional effects have to be considered. In the present contribution, we review some general phenomena, which are expected to occur when manipulating fluids under confinement and ultraconfinement conditions.

We report incoherent quasielastic neutron scattering experiments on the thermotropic liquid crystal 4-n-octyl-40-cyanobiphenyl. The combination of time-of-flight and backscattering data allows analysis of the intermediate scattering function over about three decades of relaxation times. Translational diffusion and uniaxial molecular rotations are clearly identified as the major relaxation processes in, respectively, the nanosecond and picosecond time scales.

Confinement in the nanochannels of porous silicon strongly affects the phase behavior of the archetype liquid-crystal 4-n-octyl-4-cyanobiphenyl (8CB). A very striking phenomenon is the development of a short-range smectic order, which occurs on a very broad temperature range. It suggests in this case that quenched disorder effects add to usual finite size and surface interaction effects. We have monitored the temperature variation of the molecular dynamics of the confined fluid by incoherent quasielastic neutron scattering. A strongly reduced mobility is observed at the highest temperatures in the liquid phase, which suggests that the interfacial molecular dynamics is strongly hindered. A continuously increasing slowdown appears on cooling together with a progressive growth of the static correlation length.

4-n-octyl-4-cyanobiphenyl has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, the authors present the first investigation of the individual molecular dynamics of this system. A large reduction of the molecular dynamics is observed in the confined liquid phase, as a direct consequence of the boundary conditions imposed by the confinement. Temperature fixed window scans reveal a continuous glasslike reduction of the molecular dynamics of the confined liquid and SRS phases on cooling down to 250 K, where a solidlike behavior is finally reached by a two-step crystallization process. (c) 2007 American Institute of Physics.

Structural order parameters of a smectic liquid crystal confined into columnar form of porous silicon are studied using neutron scattering and optical spectroscopic techniques. It is shown that both the translational and orientational anisotropic properties of the confined phase strongly couple to the one-dimensional character of the porous silicon matrix. The influence of this confinement induced anisotropic local structure on the molecular reorientations occuring in the picosecond timescale is discussed.

We present a neutron scattering analysis of the structure of the smectic liquid crystal octylcyanobiphenyl (8CB) confined in one-dimensional nanopores of porous silicon films (PS). The smectic transition is completely suppressed, leading to the extension of a short-range ordered smectic phase aligned along the pore axis. It evolves reversibly over an extended temperature range, down to 50 K below the N-SmA transition in pure 8CB. This behavior strongly differs from previous observations of smectics in different one-dimensional porous materials. A coherent picture of this striking behavior requires that quenched disorder effects are invoked. The strongly disordered nature of the inner surface of PS acts as random fields coupling to the smectic order. The one-dimensionality of PS nanochannels offers perspectives on quenched disorder effects, of which observation has been restricted to homogeneous random porous materials so far.

Molecular computer simulation has been performed on liquid methanol confined into silica cylindrical pores with diameter D = 24 angstrom. It has been motivated by recent conclusions obtained from neutron scattering experiments in similar conditions of confinement. A central issue is the influence of H-bond interactions within the fluid and between the fluid and the pore surface on the local structure of the liquid. It relies on the use of a realistic atomic description of the porous silicate and the chemical nature of the surface. A description of the interfacial interactions and the spatial correlations has been achieved in terms of energy distribution functions and density radial distribution functions. It shows that surface silanols significantly affect the spatial arrangement of the interfacial methanol molecules, which occupy half the pore volume. In addition, the effects of the surface boundary conditions propagate into the entire volume through layering and orientation order. (C) 2005 Elsevier B.V. All rights reserved.

We present a neutron scattering analysis of the density and the static structure factor of confined methanol at various temperatures. Confinement is performed in the cylindrical pores of MCM-41 silicates with pore diameters D=24 and 35 Angstrom. A change of the thermal expansivity of confined methanol at low temperature is the signature of a glass transition, which occurs at higher temperature for the smallest pore. This is evidence of a surface induced slowing down of the dynamics of the fluid. The structure factor presents a systematic evolution with the pore diameter, which has been analyzed in terms of excluded volume effects and fluid-matrix cross correlation. Conversely to the case of Van der Waals fluids, it shows that stronger fluid-matrix correlations must be invoked most probably in relation with the H-bonding character of both methanol and silicate surface. (C) 2004 American Institute of Physics.