Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs(+ )formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs(+ )within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs(+ )for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs(+ )and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output

Toward a Comprehensive Approach to the Collection and Analysis of Pica Substances, with Emphasis on Geophagic Materials

Pica, the craving and subsequent consumption of non-food substances such as earth, charcoal, and raw starch, has been an enigma for more than 2000 years. Currently, there are little available data for testing major hypotheses about pica because of methodological limitations and lack of attention to the problem.In this paper we critically review procedures and guidelines for interviews and sample collection that are appropriate for a wide variety of pica substances. In addition, we outline methodologies for the physical, mineralogical, and chemical characterization of these substances, with particular focus on geophagic soils and clays. Many of these methods are standard procedures in anthropological, soil, or nutritional sciences, but have rarely or never been applied to the study of pica.Physical properties of geophagic materials including color, particle size distribution, consistency and dispersion/flocculation (coagulation) should be assessed by appropriate methods. Quantitative mineralogical analyses by X-ray diffraction should be made on bulk material as well as on separated clay fractions, and the various clay minerals should be characterized by a variety of supplementary tests. Concentrations of minerals should be determined using X-ray fluorescence for non-food substances and inductively coupled plasma-atomic emission spectroscopy for food-like substances. pH, salt content, cation exchange capacity, organic carbon content and labile forms of iron oxide should also be determined. Finally, analyses relating to biological interactions are recommended, including determination of the bioavailability of nutrients and other bioactive components from pica substances, as well as their detoxification capacities and parasitological profiles.This is the first review of appropriate methodologies for the study of human pica. The comprehensive and multi-disciplinary approach to the collection and analysis of pica substances detailed here is a necessary preliminary step to understanding the nutritional enigma of non-food consumption

Birth of biomolecules from the warm wet sheets of clays near spreading centers

The role of clay minerals in the abiotic synthesis of organic molecules near seafloor spreading centers was simulated experimentally. Clays are common hydrothermal alteration products of volcanic glass and due to their nano-scale crystal size, provide extensive and variably charged surfaces that interact with aqueous organic species. Volcanic gases H2 and CO2 have been shown to react on magnetite surfaces to form methanol, a primary organic molecule, under hydrothermal conditions. Therefore, our experiments simulated the temperature and pressure conditions (300°C, 100 MPa) that exist beneath hydrothermal vents, in stockwork fractures through which hydrothermal fluids interact with fresh basalt. We examined the products of reactions between aqueous methanol and three common clay minerals found in those environments (montmorillonite, saponite, illite). Montmorillonite reacted to ~60% illite over 6 weeks, while saponite and illite were mineralogically stable. Organic products extracted with dichloromethane from the two expandable smectite clays (montmorillonite, saponite) contained a variety of complex organic molecules including: alkanes, alkyl-benzenes, alkyl-naphthalenes, alkyl-phenols, alkyl-naphthols, alkyl-anthrols, methoxy and alkyl-methoxy-phenols, methoxy and alkyl-methoxy-naphthols, and long-chain methyl esters. Experiments with the non-expandable illite yielded only traces of alkanes and alkyl-benzene after 6 weeks. We infer that the interlayer surfaces of smectites provide crystallographic sites involved in the organic synthesis of polycyclic aromatic hydrocarbons. The largest variety and quantity of organic products was produced from montmorilloniteas the layer charge increased during conversion to illite