The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

GIS Spatial-Temporal Modeling of Water Systems in Greater Toronto Area, Canada

Modeling landscape with high-resolution digital elevation model (DEM) in a geographic information system can provide essential morphological and structural information for modeling surface processes such as geomorphologic process and water systems. This paper introduces several DEM-based spatial analysis processes applied to characterize spatial distribution and their interactions of ground and surface water systems in the Greater Toronto Area (GTA), Canada. The stream networks and drainage basin systems were derived from the DEM with 30 m resolution and the regularities of the surface stream and drainage patterns were modeled from a statistical/multifractal point of view. Together with the elevation and slope of topography, other attributes defmed from modeling the stream system, and drainage networks were used to associate geological, hydrological and topographical features to water flow in river systems and the spatial locations of artesian aquifers in the study area. Stream flow data derived from daily flow measurements recorded at river gauging stations for multi-year period were decomposed into “drainage-area dependent“ and “drainage-area independent“ flow components by two-step “frequency“ and “spatial“ analysis processes. The latter component was further demonstrated to relate most likely to the ground water discharge. An independent analysis was conducted to model the distribution of aquifers with information derived from the records of water wells. The focus was given on quantification of the likelihood of ground water discharge to river and ponds through flowing wells, springs and seepages. It has been shown that the Oak Ridges Moraine (ORM) is a unique glacial deposit that serves as a recharge layer and that the aquifers in the ORM underlain by Hilton Tills and later deposits exposed near the steep slope zone of the ridges of ORM provide significant discharge to the surface water systems (river flow and ponds) through flowing wells, springs and seepages. Various statistics (cross- and auto-correlation coefficients, fractal R/S exponent) were used in conjunction with GIS to demonstrate the influence of land types, topography and geometry of drainage basins on short- and long-term persistence of river flows as well as responding time to precipitation events. The current study has provided not only insight in understanding the interaction of water systems in the GTA, but also a base for further establishment of an on-line GIS system for predicting spatial-temporal changes of river flow and groundwater level in the GTA.     

Drying effects on sorption capacity of coastal sediment: The importance of architecture and polarity of organic matter

Investigations on how desiccation changes sorption of organic compounds by salt marsh sediments provide insight into the physical and chemical properties of these wide-spread coastal sediments. We measured sorption of compounds with different polarities (lysine, tyrosine, naphthalene and aniline) onto natural sediments and sediments that were dried and rewetted. Sorption of lysine by marsh sediment decreased significantly when the sediment was dried using a freeze-drier, oven, or desiccator, and sorption capacity was not restored when sediments were rewetted. In contrast to lysine, the sorption capacity of more hydrophobic compounds (tyrosine, aniline and naphthalene) increased significantly after salt marsh sediment was dried. These results suggest that drying greatly increased sediment hydrophobicity. Consistently, water drop penetration time, an index of hydrophobicity, was significantly lower for combusted sediments than for those that were simply dried. Sediments treated with EDTA, or boiled in seawater, exhibited a similar or even greater reduction in lysine sorption capacity compared with sediments that were dried. Water retention capacity of salt marsh sediment decreased 50% after sediment was dried. The effects of pH and salinity on lysine sorption in wet and dry sediments suggest that carboxyl groups play a major role in lysine sorption through cation ion exchange, and drying may reduce access to carboxyl groups. We hypothesize that the three-dimensional (3D) structure of organic matter, originating mainly from Spartina alterniflora, is an important factor controlling sorption capacity in salt marsh sediment. The drying process makes sedimentary organic matter change conformation, shrink in volume, and expose hydrophobic groups, thus becoming more hydrophobic. In environments with wet and dry cycles, the distribution of hydrophobic or hydrophilic compounds between solution and particulate phases could thus be influenced by the 3D structure and polarity of organic matter.     

Regional variations in cleavage and fold development in North Wales

The arcuate pattern of the main Caledonian cleavage and associated fold axial plane traces in North Wales is due partly to NW-SE compression with tectonic transport to the southeast against the concealed crop of the Tan y grisiau Microgranite. Low-angle cleavage close to the microgranite is shown to be a local variant of the regional cleavage formed during the main deformation and not an earlier phase as previously supposed. Transcurrent movements along several major fault systems are also related to compression around the microgranite and the Harlech Dome block.     

Sampling the vertical particle flux in the upper water column using a large diameter free-drifting NetTrap adapted to an Indented Rotating Sphere sediment trap

Further development of the large, surface-tethered sediment trap (NetTrap) employed as part of the MedFlux program is described whereby the large collection capacity of the NetTrap is combined with an Indented Rotating Sphere/Sample Carousel (IRSC) sediment trap (IRSC–NT). This trap is capable of collecting particle flux either in a time series or settling velocity mode; settling velocity mode allows the collection of particles that fall within discrete settling velocity intervals. During short field deployments in the Mediterranean Sea the IRSC–NT configured in the settling velocity mode successfully collected unpoisoned samples for chemical and microbiological experiments. In addition to the development of the IRSC–NT, particle-settling behavior above and below the swimmer-excluding IRS valve was tested during on-deck experiments using a specially constructed water-tight trap. Chemical analyses of settling materials (published elsewhere) suggested that separation of particles by settling velocity was achieved. However, due to the motion of the ship, it was not possible to directly measure particle-settling velocities within the trap. Particle release from the IRS did not bias the apparent settling velocity spectrum. Rotation of the IRS did not engender turbulence at the surface of the sphere or within the skewed funnel below. Tests of different ball designs over the course of the MedFlux program showed that a “ridge and saddle” pattern was optimal for efficiently transferring particles under the IRS seal while still reducing swimmer entrance to the collection funnel. The large size of the IRSC–NT did not prevent it from drifting effectively with the current. Several modifications of the present design are proposed that should improve the accuracy of the settling velocity measurements.     

MedFlux: Investigations of particle flux in the Twilight Zone

The MedFlux project was devised to determine and model relationships between organic matter and mineral ballasts of sinking particulate matter in the ocean. Specifically we investigated the ballast ratio hypothesis, tested various commonly used sampling and modeling techniques, and developed new technologies that would allow better characterization of particle biogeochemistry. Here we describe the rationale for the project, the biogeochemical provenance of the DYFAMED site, the international support structure, and highlights from the papers published here. Additional MedFlux papers can be accessed at the MedFlux web site (http://msrc.sunysb.edu/MedFlux/).     

Investigating the effect of ballasting by CaCO3 in Emiliania huxleyi, II: Decomposition of particulate organic matter

The quantitative relationship between organic carbon and mineral contents of particles sinking below 1800 m in the ocean indicates that organisms with mineral shells such as coccolithophores are of special importance for transporting carbon into the deep sea. Several hypotheses about the mechanism behind this relationship between minerals and organic matter have been raised, such as mineral protection of organic matter or enhanced sinking rates through ballast addition. We examined organic matter decomposition of calcifying and non-calcifying Emiliania huxleyi cultures in an experiment that allowed aggregation and settling in rotating tanks. Biogenic components such as particulate carbon, particulate nitrogen, particulate volume, pigments, transparent exopolymer particles (TEP), and particulate amino acids in suspended particles and aggregates were followed over a period of 30 d. The overall pattern of decrease in organic matter, the amount of recalcitrant organic matter left after 30 d, and the compositional changes within particulate organic matter indicated that cells without a shell are more subject to loss than calcified cells. It is suggested that biogenic calcite helps in the preservation of particulate organic matter (POM) by offering structural support for organic molecules. Over the course of the experiment, half the particulate organic carbon in both calcifying and non-calcifying cultures was partitioned into aggregates and remained so until the end of the experiment. The partial protection of particulate organic matter from solubilization by biominerals and by aggregation that was observed in our experiment may help explain the robustness of the relationship between organic and mineral matter fluxes in the deep ocean.