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.     

Compositional variation in three Cascade stratovolcanoes: Jefferson,Rainier, and Shasta

Detailed major and trace element studies of volcanic rocks from Jefferson, Rainier, and Shasta stratovolcanoes in the Cascade Range indicate that each volcano has distinct geochemical distribution patterns. Silica variation diagrams are not smooth nor, in general, continuous for any volcano. Portions of stratigraphic sections within the volcanoes exhibit compositional coherency and are interpreted as eruptive groups which were extruded over time intervals which are short compared to the lifetimes of the volcanoes. The results of this investigation indicate the leasibility of geochemically mapping eruptive groups within stratovolcanoes. Systematic compositional trends are not observed within thick (500–1000 m) eruptive groups but may occur over thicknesses of <200 m. Compositional variations within eruptive groups are commonly non-systematic and show ranges similar to the ranges observed in individual flows. Correlations between the amounts or kinds of phenocryst phases present and intra-group compositional variation is not observed. Inter-group compositional differences are sometimes accompanied by mineralogical differences. Late andesites and dacites at Rainier and Shasta are characterized by decreases in K and Rb while at Jefferson increases in these elements and other compositional changes occur in the late eruptives. Progressive fractional crystallization models do not seem capable of explaining the element distributions observed in the three volcanoes. Existing data are consistent with a model involving varying degrees of melting of some combination of amphibolite, eclogite or peridotite in or above a subduction zone with varying water contents. Segregation and sequential eruption of small batches of magma may produce the eruptive groups characterizing the volcanoes. Late mafic magmas erupted at satellite vents appear to be produced in different (deeper?) mantle source areas.     

Geometric constraints on composition of sediment derived from erosional landscapes

Although unroofing sequences are well known in the stratigraphic record, there is no general theory for estimating relevant basic quantities such as the time history of sediment production from a particular unit or the degree of mixing between successive units. Here we investigate the production of sediment from layered source rocks that are milled off by steady-state erosional topography. The shape of the sediment-production function for milling off a thin horizontal layer is given by the derivative of the hypsometric function, in the form of area contained within contours as a function of contour altitude. The time-scale for the production function, the ‘topographic mixing time’, is set by the topographic relief divided by the uplift rate. The production function for a sharp transition from one unit to another is given directly by the hypsometric function. The effects of stratal dip parallel to the mean slope of the erosional topography and finite layer thickness can be accounted for to a first approximation by simple geometric corrections to the mixing time. Finite layer thickness also has the effect of smoothing the production function although most natural hypsometric functions are smooth enough that this effect is relatively weak. The quality of an unroofing sequence can be measured in terms of the ‘sharpness’ of separation of successive peaks in sediment production produced by milling off a sequence of geometrically similar layers. This peak sharpness can be parameterized by a ratio of the interval between successive peaks in sediment production to topographic mixing time. By this measure, the quality of unroofing sequences is controlled by two parameters: the ratio of layer thickness to topographic relief, and the dip angle. The dip angle in concert with topographic mixing exerts a strong control on the degree of signal segregation; in particular, production of cleanly segregated signals for dip angles greater than about 15° requires very high ratios of layer thickness to relief. Hence identification of distinct unroofing sequences may place significant and useful constraints on the attitude and/or thickness of units in the eroding stratigraphy.     

The Euro-Atlantic Circulation Response to the Madden-Julian Oscillation Cycle of Tropical Heating: Coupled GCM Intervention Experiments

Abstract

Intervention experiments using the Coupled Forecast System model, version 2 (CFSv2), have been performed in which various Madden-Julian Oscillation (MJO) evolutions were added to the model’s internally generated heating: Slow Repeated Cycles, Slow Single Cycle, Fast Repeated Cycles, and Fast Single Cycle. In each experiment, one of these specified MJO evolutions of tropical diabatic heating was added in multiple ensemble reforecasts of boreal winter (1 November to 31 March for 31 winters: 1980–2010). Since in each experiment, multiple re-forecasts were made with the identical heating evolution added, predictable component analysis is used to identify modes with the highest signal-to-noise ratio. Traditional MJO-phase analysis of total model heating (dominated by internally generated heating) shows that the MJO-related heating structure compares well with heating estimated from observed fast and slow episodes; however, the model heating is larger by a factor of two. The evolution of Euro-Atlantic circulation regimes indicates a clear response due to the added heating, with a robust increase in the frequency of occurrence of the negative phase of the North Atlantic Oscillation (NAO?) after the heating crosses into the Pacific and a somewhat less robust increase in the positive phase of the NAO (NAO+) following Indian Ocean heating. In the Fast Cycle experiments, the model response is somewhat muted compared with the Slow Cycle experiments. The Scandinavian Blocking regime becomes more frequent prior to the NAO? regime. The two leading modes in the predictable component analysis of 300?hPa height (Z300), synoptic scale feedback (DZ300), and planetary wave diabatic heating in all experiments form an oscillatory pair with high statistical significance. The oscillatory pair represents the cyclic response to the particular MJO signal (Fast or Slow, Single, or Repeated Cycles) in each case. The period is about 64 days for the Slow Cycle and 36 days for the Fast Cycle, consistent with the imposed periods. The time series of one of the leading modes of Z300 is highly anti-correlated with the frequency of occurrence of the NAO– in the Repeated Cycle experiments. A clear cycle involving the Z300 and DZ300 leading modes is identified.     

A finite element model for the analysis of tailored pulse stimulation of boreholes

A constitutive model is described for the prediction of dynamic crack formation in geological media. The model includes a simple tensile failure criterion for crack formation and a soil plasticity model for both deviatoric and volumetric plasticity. Numerical results are presented which show that the model reproduces the observed dependence of fracture formation on loding rate for dynamic pressure loading of boreholes. The use of the model as a numerical tool for design is demonstrated through two example parameter studies.     

Salinity trends in Louisiana estuaries

If long-term trends in the character of the estuarine salinity field are contributing to land-loss in coastal Louisiana, then evidence of the presence of these trends may exist in historical salinity records. Nonparametric tests for the presence of a trend in the time series of various salinity statistics were performed. The results appear to be strongly influenced by climatological variations of decadal scale. Statistically significant trends were found at many stations. Both increasing and decreasing trends occurred with no apparent underlying spatial pattern. The observed changes during the time covered by the available records were generally too small to be lethal to the dominant marsh plants.     

Estimating geoid height change in North America: past, present and future

The forthcoming GRAV-D gravimetric geoid model over the United States is to be updated regularly to account for changes in geoid height. Its baseline precision is to be at the 10–20 mm level over non-mountainous regions. The aim of this study is to provide an estimate of the magnitude, time scale, and spatial footprint of geoid height change over North America, from mass redistribution processes of hydrologic, cryospheric and solid Earth nature. Geoid height changes from continental water storage changes over the past 50 years and predicted over the next century are evaluated and are highly dependent on the used model. Groundwater depletion from anthropogenic pumping in regional scale aquifers may lead to geoid changes of 10 mm magnitude every 50–100 years. The GRACE time varying gravity fields are used to (i) assess the errors in a glacial isostatic adjustment model, which, if used to correct the GRAV-D model, may induce errors at the 10 mm geoid height level after ~20 years, (ii), evaluate geoid height change over ice mass loss regions of North America, which, if they remain unchanged in the future, may lead to geoid height changes at the 10 mm level in under a decade and (iii), compute sea level rise and its effect on the geoid, which is found to be negligible. Coseismic gravitational changes from past North American earthquakes are evaluated, and lead to geoid change at the 10-mm level for only the largest thrust earthquakes. Finally, geoid change from volcanic processes are assessed and found to be significant with respect to the GRAV-D geoid model baseline precision for cataclysmic events, such as that of the 1980 Mt. St. Helens eruption. Recommendations on how to best monitor geoid change in the future are given.     

Comparative concentrations of metals in marine species from French Frigate Shoals, North Pacific Ocean.

Concentrations of arsenic, cadmium, chromium, copper, lead, mercury, selenium, and zinc were measured in coral, crab, eel, fish, lobster, and sediment samples collected from French Frigate Shoals, North Pacific Ocean. The sediments contained relatively high concentrations of selenium; moderate concentrations of arsenic, cadmium, copper and lead; and low concentrations of chromium and zinc. Metal concentrations were also determined in coral and crabs collected from the island of Oahu. Notably, a crab (Grapsus tenuicrustatus) and the undulated moray eel (Gymnothorax undulatus) exhibited high levels of copper and arsenic, respectively, relative to the other species studied. The concentrations of arsenic in the eel averaged 225 microg g(-1) dry wt, which was 3-12 times higher than that in all of the other species tested. The average concentration of copper in the crab was 343 microg g(-1) dry wt, 3-86 times greater than that in the other species studied. These data indicate background and comparative levels of the metals among the studied species. Lead levels in the coral (9-10 microg g(-1) dry wt) and crab (42-57 microg g(-1) dry wt) from Tern and Disappearing Islands were 23-283-fold greater than those from Oahu (0.4 and 0.2 microg g(-1) dry wt, respectively).