Extraterrestrial 3He estimation across the Paleocene-Eocene thermal maximum at ODP Site 208-1266

In the deep-sea, the Paleocene-Eocene Thermal Maximum (PETM) is often marked by clay-rich condensed intervals caused by dissolution of carbonate sediments, capped by a carbonate-rich interval. Constraining the duration of both the dissolution and subsequent cap-carbonate intervals is essential to computing marine carbon fluxes and thus testing hypotheses for the origin of this event. To this end, we provide new high-resolution helium isotope records spanning the Paleocene-Eocene boundary at ODP Site 1266 in the South Atlantic. The extraterrestrial 3He, 3HeET, concentrations replicate trends observed at ODP Site 690 by Farley and Eltgroth (2003, doi:10.1016/S0012-821X(03)00017-7). By assuming a constant flux of 3HeET we constrain relative changes in accumulation rates of sediment across the PETM and construct a new age model for the event. In this new chronology the zero carbonate layer represents 35 kyr, some of which reflects clay produced by dissolution of Paleocene (pre-PETM) sediments. Above this layer, carbonate concentrations increase for ~165 kyr and remain higher than in the latest Paleocene until 234 +48/-34 kyr above the base of the clay. The new chronology indicates that minimum d13C values persisted for a maximum of 134 +27/-19 kyr and the inflection point previously chosen to designate the end of the CIE recovery occurs at 217 +44/-31 kyr. This allocation of time differs from that of the cycle-based age model of Röhl et al. (2007, doi:10.1029/2007GC001784) in that it assigns more time to the clay layer followed by a more gradual recovery of carbonate-rich sedimentation. The new model also suggests a longer sustained d13C excursion followed by a more rapid recovery to pre-PETM d13C values. These differences have important implications for constraining the source(s) of carbon and mechanisms for its subsequent sequestration, favoring models that include a sustained release

Gas distribution in shallow packed beds

Packed beds have many industrial applications and are increasingly used in the process industries due to their low pressure drop. With the introduction of more efficient packings, novel packing materials (i.e. adsorbents) and new applications (i.e. flue gas desulphurisation); the aspect ratio (height to diameter) of such beds is decreasing. Obtaining uniform gas distribution in such beds is of crucial importance in minimising operating costs and optimising plant performance. Since to some extent a packed bed acts as its own distributor the importance of obtaining uniform gas distribution has increased as aspect ratios (bed height to diameter) decrease. There is no rigorous design method for distributors due to a limited understanding of the fluid flow phenomena and in particular of the effect of the bed base / free fluid interface. This study is based on a combined theoretical and modelling approach. The starting point is the Ergun Equation which is used to determine the pressure drop over a bed where the flow is uni-directional. This equation has been applied in a vectorial form so it can be applied to maldistributed and multi-directional flows and has been realised in the Computational Fluid Dynamics code PHOENICS. The use of this equation and its application has been verified by modelling experimental measurements of maldistributed gas flows, where there is no free fluid / bed base interface. A novel, two-dimensional experiment has been designed to investigate the fluid mechanics of maldistributed gas flows in shallow packed beds. The flow through the outlet of the duct below the bed can be controlled, permitting a rigorous investigation. The results from this apparatus provide useful insights into the fluid mechanics of flow in and around a shallow packed bed and show the critical effect of the bed base. The PHOENICS/vectorial Ergun Equation model has been adapted to model this situation. The model has been improved by the inclusion of spatial voidage variations in the bed and the prescription of a novel bed base boundary condition. This boundary condition is based on the logarithmic law for velocities near walls without restricting the velocity at the bed base to zero and is applied within a turbulence model. The flow in a curved bed section, which is three-dimensional in nature, is examined experimentally. The effect of the walls and the changes in gas direction on the gas flow are shown to be particularly significant. As before, the relative amounts of gas flowing through the bed and duct outlet can be controlled. The model and improved understanding of the underlying physical phenomena form the basis for the development of new distributors and rigorous design methods for them.

Bearing capacity of circular footing on geocell-sand mattress overlying clay bed with void

The potential benefits of providing geocell reinforced sand mattress over clay subgrade with void have been investigated through a series of laboratory scale model tests. The parameters varied in the test programme include, thickness of unreinforced sand layer above clay bed, width and height of geocell mattress, relative density of the sand fill in the geocells, and influence of an additional layer of planar geogrid placed at the base of the geocell mattress. The test results indicate that substantial improvement in performance can be obtained with the provision of geocell mattress, of adequate size, over the clay subgrade with void. In order to have beneficial effect, the geocell mattress must spread beyond the void at least a distance equal to the diameter of the void. The influence of the void over the performance of the footing reduces for height of geocell mattress greater than 1.8 times the diameter of the footing. Better improvement in performance is obtained for geocells filled with dense soil. (C) 2008 Elsevier Ltd. All rights reserved.

Evidence for a Frozen Bed, Byrd Glacier, Antarctica

Ice thickness, computed within the fjord region of Byrd Glacier on the assumptions that Byrd Glacier is in mass-balance equilibrium and that ice velocity is entirely due to basal sliding, are on average 400 m less than measured ice thicknesses along a radio-echo profile. We consider four explanations for these differences: (1) active glacier ice is separated from a zone of stagnant ice near the base of the glacier by a shear zone at depth; (2) basal melting rates are some 8 m/yr; (3) internal shear occurs with no basal sliding in much of the region above the grounding zone; or (4) internal creep and basal sliding contribute to the flow velocity in varying proportions above the grounding zone. Large gradients of surface strain rate seem to invalidate the first explanation. Computed values of basal shear stress (140 to 200 kPa) provide insufficient frictional heat to melt the ice demanded by the second explanation. Both the third and fourth explanations were examined by making simplifying assumptions that prevented a truly quantitative evaluation of their merit. Nevertheless, there is no escaping the qualitative conclusion that internal shear contributes strongly to surface velocities measured on Byrd Glacier, as is postulated in both these explanations.

Influence of drying conditions on the moisture diffusion during single stage and two stage fluidized bed drying of bovine intestine for pet food

Bovine intestine samples were heat pump fluidized bed dried at atmospheric pressure and at temperatures below and above the material freezing points equipped with a continuous monitoring system. The investigation of the drying characteristics has been conducted in the temperature range -10~25oC and the airflow in the range 1.5~2.5 m/s. Some experiments were conducted as a single temperature drying experiments and others as two stage drying experiments employing two temperatures. An Arrhenius-type equation was used to interpret the influence of the drying air parameters on the effective diffusivity, calculated with the method of slopes in terms of energy activation, and this was found to be sensitivity of the temperature. The effective diffusion coefficient of moisture transfer was determined by Fickian method using uni-dimensional moisture movement in both moisture, removal by evaporation and combined sublimation and evaporation. Correlations expressing the effective moisture diffusivity and drying temperature are reported.

Influence of drying conditions on the moisture diffusion and fluidization quality during multi-stage fluidized bed drying of bovine intestine for pet food

In order to establish the influence of the drying air characteristics on the drying performance and fluidization quality of bovine intestine for pet food, several drying tests have been carried out in a laboratory scale heat pump assisted fluid bed dryer. Bovine intestine samples were heat pump fluidized bed dried at atmospheric pressure and at temperatures below and above the materials freezing points, equipped with a continuous monitoring system. The investigation of the drying characteristics have been conducted in the temperature range −10 to 25 ◦C and the airflow in the range 1.5–2.5 m/s. Some experiments were conducted as single temperature drying experiments and others as two stage drying experiments employing two temperatures. An Arrhenius-type equation was used to interpret the influence of the drying air temperature on the effective diffusivity, calculated with the method of slopes in terms of energy activation, and this was found to be sensitive to the temperature. The effective diffusion coefficient of moisture transfer was determined by the Fickian method using uni-dimensional moisture movement in both moisture, removal by evaporation and combined sublimation and evaporation. Correlations expressing the effective moisture diffusivity and drying temperature are reported. Bovine particles were characterized according to the Geldart classification and the minimum fluidization velocity was calculated using the Ergun Equation and generalized equation for all drying conditions at the beginning and end of the trials. Walli’s model was used to categorize stability of the fluidization at the beginning and end of the dryingv for each trial. The determined Walli’s values were positive at the beginning and end of all trials indicating stable fluidization at the beginning and end for each drying condition.

Habitat dynamics in the bed sediments of an intermittent upland stream

The effects of the hydrological regime on temporal changes to physical characteristics of substratum habitat, sediment texture of surface sediments (<10 cm), were investigated in a sub-tropical headwater stream over four years. Surface discharge was measured together with vertical hydraulic gradient and groundwater depth in order to explore features of sediment habitat that extend beyond the streambed surface. Whilst the typical discharge pattern was one of intermittent base flows and infrequent flow events associated with monsoonal rain patterns, the study period also encompassed a drought and a one-in-a-hundred-year flood. Rainfall and discharge did not necessarily reflect the actual conditions in the stream. Although surface waters were persistent long after discharge ceased, the streambed was completely dry on several occasions. Shallow groundwater was present at variable depths throughout the study period, being absent only at the height of the drought. The streambed sediments were mainly gravels, sand and clay. Finer sediment fractions showed a marked change in grain size over time, although bedload movement was limited to a single high discharge event. In response to a low discharge regimen (drought), sediments characteristically showed non-normal distributions and were dominated by finer materials. A high-energy discharge event produced a coarsening of sands and a diminished clay fraction in the streambed. Particulate organic matter from sediments showed trends of build-up and decline with the high and low discharge regimes, respectively. Within the surface sediment intersticies three potential categories of invertebrate habitat were recognised, each with dynamic spatial and temporal boundaries.

Schiff Base Complexes and their Assemblies on Surfaces

Schiff bases and their transition metal complexes are of significant current interest even though they have been prepared for decades. They have been used in various applications such as catalysis, corrosion protection, and molecular sensors. In this study, N-aryl Schiff base ketimine ligands as well as numerous new, differently substituted salen and salophen-type ligands and their cobalt(II), copper(II), iron(II), manganese(II), and nickel(II) complexes were synthesised. New solid state structures of the above compounds and the dioxygen coordination properties of cobalt(II) complexes and catalytic properties of three synthesised binuclear complexes were examined. The prepared complexes were applied in the formation of self-assembled layers on a polycrystalline gold surface and liquid-graphite interface. The effect of metal ion and ligand structure on the as-formed patterns was studied. When studying gold surfaces, a unique thiol-assisted dissolution of elemental gold was observed and a new thin gold foil preparation method was introduced. In the summary, synthesis, structures, and properties of Schiff base ligands and their transition metal complexes are described in detail and the applications of these reviewed. Assemblies of other complexes on a liquid-graphite interface and on a gold surface are also presented, and the surface characterisation methods and surfaces employed are described.

An ab-initio study of the proton affinity of conjugated schiff-base and related nitrogen compounds: an analysis of the triggering site of bacteriorhodopsin

The chemical groups which take part in the proton transfer reaction in bacteriorhodopsin have been studied by ab initio quantum chemical methods. The various factors such as conjugation with a linear system, electron delocalization of the guanidine type, cis-trans isomerism, geometry distortion and hydrogen bonding with charged groups can influence the properties of a given chemical group. Several systems are studied at 4-31G and STO-3G levels. Some of the Schiff-base analogues and guanidine type molecules are characterized by their molecular orbital diagrams, energy levels and the nature of charge distribution. Also, the effects of the above-mentioned factors on proton affinity are studied. It is hoped that the values thus obtained can be helpful in evaluating various structural models for proton transfer.

Effect of base dissipation on the granular flow down an inclined plane

The effect of base dissipation on the granular flow down an inclined plane is examined by altering the coefficient of restitution between the moving and base particles in discrete element (DE) simulations. The interaction laws between two moving particles are kept fixed, and the coefficient of restitution (damping constant in the DE simulations) between the base and moving particles are altered to reduce dissipation, and inject energy from the base. The energy injection does result in an increase in the strain rate by up to an order of magnitude, and the temperature by up to two orders of magnitude at the base. However, the volume fraction, strain rate and temperature profiles in the bulk (above about 15 particle diameters from the base) are altered very little by the energy injection at the base. We also examine the variation of h(stop), the minimum height at the cessation of flow, with energy injection from the base. It is found that at a fixed angle of inclination, h(stop) decreases as the energy dissipation at the base decreases.

Dielectric relaxations above room temperature in DMPU derived polyaniline film

Dielectric measurements carried out on drop casted from solution of emeraldine base form of polyaniline films in the temperature range 30-300 degrees C revealed occurrence of two maxima in the loss tangent as a function of temperature. The activation energies corresponding to these two relaxation processes were found to be similar to 0.5 eV and similar to 1.5 eV. The occurrence of one relaxation peak in the dispersion curve of the imaginary part of the electric modulus suggests the absence of microphase separation in the film. Thermogravimetric analysis and infrared spectroscopic measurements showed that the films retained its integrity up to 300 degrees C. The dielectric relaxation at higher temperatures with large activation energy of 1.5 eV is attributed to increase in the barrier potential due to decrease in the polymer conjugation as a result of wide amplitude motion of the chain segments well above the glass transition temperature. (c) 2012 Elsevier B.V. All rights reserved.

Stabilization and Structural Alteration of the G-Quadruplex DNA Made from the Human Telomeric Repeat Mediated by Troger's Base Based Novel Benzimidazole Derivatives

Ligand-induced stabilization of the G-quadruplex DNA structure derived from the single-stranded 3'-overhang of the telomeric DNA is an attractive strategy for the inhibition of the telomerase activity. The agents that can induce/stabilize a DNA sequence into a G-quadruplex structure are therefore potential anticancer drugs. Herein we present the first report of the interactions of two novel bisbenzimidazoles (TBBz1 and TBBz2) based on Troger's base skeleton with the G-quadruplex DNA (G4DNA). These Troger's base molecules stabilize the G4DNA derived from a human telomeric sequence. Evidence of their strong interaction with the G4DNA has been obtained from CD spectroscopy, thermal denaturation, and UV-vis titration studies. These ligands also possess significantly higher affinity toward the G4DNA over the duplex DNA. The above results obtained are in excellent agreement with the biological activity, measured in vitro using a modified TRAP assay. Furthermore, the ligands are selectively more cytotoxic toward the cancerous cells than the corresponding noncancerous cells. Computational studies suggested that the adaptive scaffold might allow these ligands to occupy not only the G-quartet planes but also the grooves of the G4DNA.

Universal flame propagation behavior in packed bed of biomass

This article aims at seeking the universal behavior of propagation rate variation with air superficial velocity (V-s) in a packed bed of a range of biomass particles in reverse downdraft mode while also resolving the differing and conflicting explanations in the literature. Toward this, measurements are made of exit gas composition, gas phase and condensed phase surface temperature (T-g and T-s), and reaction zone thickness for a number of biomass with a range of properties. Based on these data, two regimes are identified: gasificationvolatile oxidation accompanied by char reduction reactions up to 16 +/- 1cm/s of V-s and above this, and char oxidationsimultaneous char oxidation and gas phase combustion. In the gasification regime, the measured T-s is less than T-g; a surface heat balance incorporating a diffusion controlled model for flaming combustion gives and matches with the experimental results to within 5%. In the char oxidation regime, T-g and T-s are nearly equal and match with the equilibrium temperature at that equivalence ratio. Drawing from a recent study of the authors, the ash layer over the oxidizing char particle is shown to play a critical role in regulating the radiation heat transfer to fresh biomass in this regime and is shown to be crucial in explaining the observed propagation behavior. A simple model based on radiation-convection balance that tracks the temperature-time evolution of a fresh biomass particle is shown to support the universal behavior of the experimental data on reaction front propagation rate from earlier literature and the present work for biomass with ash content up to 10% and moisture fraction up to 10%. Upstream radiant heat transfer from the ash-laden hot char modulated by the air flow is shown to be the dominant feature of this model.

The effect of base roughness on the development of a dense granular flow down an inclined plane

The development of the flow of a granular material down an inclined plane starting from rest is studied as a function of the base roughness. In the simulations, the particles are rough frictional spheres interacting via the Hertz contact law. The rough base is made of a random configuration of fixed spheres with diameter different from the flowing particles, and the base roughness is decreased by decreasing the diameter of the base particles. The transition from an ordered to a disordered flowing state at a critical value of the base particle diameter, first reported by Kumaran and Maheshwari Phys. Fluids 24, 053302 (2012)] for particles with the linear contact model, is observed for the Hertzian contact model as well. The flow development for the ordered and disordered flows is very different. During the development of the disordered flow for the rougher base, there is shearing throughout the height. During the development of the ordered flow for the smoother base, there is a shear layer at the bottom and a plug region with no internal shearing above. In the shear layer, the particles are layered and hexagonally ordered in the plane parallel to the base, and the velocity profile is well approximated by Bagnold law. The flow develops in two phases. In the first phase, the thickness of the shear layer and the maximum velocity increase linearly in time till the shear front reaches the top. In the second phase, after the shear layer encompasses the entire flow, there is a much slower increase in the maximum velocity until the steady state is reached. (C) 2013 AIP Publishing LLC.

Seismic structure above and below the core-mantle boundary

Seismic structure above and below the core-mantle boundary (CMB) has been studied through use of travel time and waveform analyses of several different seismic wave groups. Anomalous systematic trends in observables document mantle heterogeneity on both large and small scales. Analog and digital data has been utilized, and in many cases the analog data has been optically scanned and digitized prior to analysis.

Differential travel times of S - SKS are shown to be an excellent diagnostic of anomalous lower mantle shear velocity (V s) structure. Wavepath geometries beneath the central Pacific exhibit large S- SKS travel time residuals (up to 10 sec), and are consistent with a large scale 0(1000 km) slower than average V_s region (≥3%). S - SKS times for paths traversing this region exhibit smaller scale patterns and trends 0(100 km) indicating V_s perturbations on many scale lengths. These times are compared to predictions of three tomographically derived aspherical models: MDLSH of Tanimoto [1990], model SH12_WM13 of Suet al. [1992], and model SH.10c.17 of Masters et al. [1992]. Qualitative agreement between the tomographic model predictions and observations is encouraging, varying from fair to good. However, inconsistencies are present and suggest anomalies in the lower mantle of scale length smaller than the present 2000+ km scale resolution of tomographic models. 2-D wave propagation experiments show the importance of inhomogeneous raypaths when considering lateral heterogeneities in the lowermost mantle.

A dataset of waveforms and differential travel times of S, ScS, and the arrival from the D" layer, Scd, provides evidence for a laterally varying V_s velocity discontinuity at the base of the mantle. Two different localized D" regions beneath the central Pacific have been investigated. Predictions from a model having a V_s discontinuity 180 km above the CMB agree well with observations for an eastern mid-Pacific CMB region. This thickness differs from V_s discontinuity thicknesses found in other regions, such as a localized region beneath the western Pacific, which average near 280 km. The "sharpness" of the V_s jump at the top of D", i.e., the depth range over which the V_s increase occurs, is not resolved by our data, and our data can in fact may be modeled equally well by a lower mantle with the increase in V_s at the top of D" occurring over a 100 krn depth range. It is difficult at present to correlate D" thicknesses from this study to overall lower mantle heterogeneity, due to uncertainties in the 3-D models, as well as poor coverage in maps of D" discontinuity thicknesses.

P-wave velocity structure (V_p) at the base of the mantle is explored using the seismic phases SKS and SPdKS. SPdKS is formed when SKS waves at distances around 107° are incident upon the CMB with a slowness that allows for coupling with diffracted P-waves at the base of the mantle. The P-wave diffraction occurs at both the SKS entrance and exit locations of the outer core. SP_dKS arrives slightly later in time than SKS, having a wave path through the mantle and core very close to SKS. The difference time between SKS and SP_dKS strongly depends on V_p at the base of the mantle near SK Score entrance and exit points. Observations from deep focus Fiji-Tonga events recorded by North American stations, and South American events recorded by European and Eurasian stations exhibit anomalously large SP_dKS - SKS difference times. SKS and the later arriving SP_dKS phase are separated by several seconds more than predictions made by 1-D reference models, such as the global average PREM [Dziewonski and Anderson, 1981] model. Models having a pronounced low-velocity zone (5%) in V_p in the bottom 50-100 km of the mantle predict the size of the observed SP_dK S-SKS anomalies. Raypath perturbations from lower mantle V_s structure may also be contributing to the observed anomalies.

Outer core structure is investigated using the family of SmKS (m=2,3,4) seismic waves. SmKS are waves that travel as S-waves in the mantle, P-waves in the core, and reflect (m-1) times on the underside of the CMB, and are well-suited for constraining outermost core V_p structure. This is due to closeness of the mantle paths and also the shallow depth range these waves travel in the outermost core. S3KS - S2KS and S4KS - S3KS differential travel times were measured using the cross-correlation method and compared to those from reflectivity synthetics created from core models of past studies. High quality recordings from a deep focus Java Sea event which sample the outer core beneath the northern Pacific, the Arctic, and northwestern North America (spanning 1/8th of the core's surface area), have SmKS wavepaths that traverse regions where lower mantle heterogeneity is pre- dieted small, and are well-modeled by the PREM core model, with possibly a small V_p decrease (1.5%) in the outermost 50 km of the core. Such a reduction implies chemical stratification in this 50 km zone, though this model feature is not uniquely resolved. Data having wave paths through areas of known D" heterogeneity (±2% and greater), such as the source-side of SmKS lower mantle paths from Fiji-Tonga to Eurasia and Africa, exhibit systematic SmKS differential time anomalies of up to several seconds. 2-D wave propagation experiments demonstrate how large scale lower mantle velocity perturbations can explain long wavelength behavior of such anomalous SmKS times. When improperly accounted for, lower mantle heterogeneity maps directly into core structure. Raypaths departing from homogeneity play an important role in producing SmKS anomalies. The existence of outermost core heterogeneity is difficult to resolve at present due to uncertainties in global lower mantle structure. Resolving a one-dimensional chemically stratified outermost core also remains difficult due to the same uncertainties. Restricting study to higher multiples of SmKS (m=2,3,4) can help reduce the affect of mantle heterogeneity due to the closeness of the mantle legs of the wavepaths. SmKS waves are ideal in providing additional information on the details of lower mantle heterogeneity.