The Effect of Dissolved Humic Acids on Aluminosilicate Formation and Associated Carbon Sequestration

Allophane and imogolite neogenesis in soils may occur in the presence of organic matter. To understand this process under conditions relevant to soils, the influence of dissolved organic carbon (DOC) as humic acid (HA), on aluminosilicate formation was studied at 25◦C, pH 6, and low-DOC concentrations. For solutions with initial Al/Si ratios of 1–2.1, and 0–6mg/L DOC, precipitates recovered after 20h had Al/Si ratios of 2.2–2.7. The formation of allophane, imogolite-like material, and aluminosilicate gel was confirmed by XRD, FTIR, and NMR. The effect of DOC was to produce a small, but systematic increase in imogolite-like Si in the precipitate, and a decrease in the formation of aluminosilicate gel. Results suggest that the presence of DOC as HA slows the otherwise rapid polymerization of Al and Si at low temperature, and may also promote the formation of imogolite. The high C content of these precipitates indicates that this process may facilitate the sequestration of organic matter, slowing C cycling in soils

Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

<p>Abstract</p> <p>Background</p> <p>Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H₂O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra.</p> <p>Results</p> <p>Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes.</p> <p>Conclusion</p> <p>Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO₂[CO₃]₃^5-ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO₂²⁺can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to ¹³C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids.</p

Structure-function mapping of a heptameric module in the nuclear pore complex.

The nuclear pore complex (NPC) is a multiprotein assembly that serves as the sole mediator of nucleocytoplasmic exchange in eukaryotic cells. In this paper, we use an integrative approach to determine the structure of an essential component of the yeast NPC, the ~600-kD heptameric Nup84 complex, to a precision of ~1.5 nm. The configuration of the subunit structures was determined by satisfaction of spatial restraints derived from a diverse set of negative-stain electron microscopy and protein domain-mapping data. Phenotypic data were mapped onto the complex, allowing us to identify regions that stabilize the NPC's interaction with the nuclear envelope membrane and connect the complex to the rest of the NPC. Our data allow us to suggest how the Nup84 complex is assembled into the NPC and propose a scenario for the evolution of the Nup84 complex through a series of gene duplication and loss events. This work demonstrates that integrative approaches based on low-resolution data of sufficient quality can generate functionally informative structures at intermediate resolution

Oxidative cyclization of tertiary pentenol derivatives forming 2,5,5-trisubstituted THF rings and the total synthesis of cyclocapitelline

The synthesis of 2,5,5-trisubstituted tetrahydrofuran rings was accomplished via the Mukaiyama aerobic oxidative cyclization of tertiary 5-pentenols employing the Co(nmp)2catalyst. A variety of THFs were formed in moderate to good yield and diastereoselectivity. The method developed herein was successfully applied to an enantioselective total synthesis of cyclocapitelline

New Insights on the Sequence Stratigraphic Architecture of the Dakota Formation in Kansas–Nebraska–Iowa from a Decade of Sponsored Research Activity

The Cretaceous Dakota Formation in the areas of Kansas, Nebraska, and Iowa contains a rich and well-preserved microflora of fossil palynomorphs. A comprehensive listing of these taxa is presented in this publication as part of a continuing effort to develop a refined biostratigraphic scheme for mid-Cretaceous terrestrial deposits in North America. The Dakota Formation in this region contains four distinctive Albian-Cenomanian palynostratigraphic zones that are used to partition the unit into successive depositional cycles, and each zone records deposition in fluvial-estuarine environments. The late Albian Kiowa-Skull Creek depositional cycle at the base of the Dakota Formation is recognized throughout the study area, and is also recognized in other parts of the Cretaceous North American Western Interior basin. The overlying newly recognized latest Albian "Muddy-Mowry Cycle" is formally defined for the first time in this paper and correlates with depositional cycles recognized by other workers in other parts of the Western Interior basin. The Cenomanian lower Greenhorn Cycle is already widely recognized by many other workers throughout the Western Interior basin. Laterally extensive thin zones of pervasive carbonate mineral cementation are noted in fluvial-estuarine deposits in the Dakota Formation. They are believed to have formed as synsedimentary cements that precipitated below estuarine marine-flooding surfaces in settings related to discharging paleoground waters. The existence of these early diagenetic cementation zones has important implications for the recognition of diagenetic barriers and baffles to modern fluid flow in the Dakota Formation. New stable isotopic data on these authigenic cements are reported in this paper and add to a body of published data on the δ18O of mid-Cretaceous paleoprecipitation in North America

Spectral Models for Early Time SN 2011fe Observations

We use observed UV through near IR spectra to examine whether SN 2011fe can be understood in the framework of Branch-normal SNe Ia and to examine its individual peculiarities. As a benchmark, we use a delayed-detonation model with a progenitor metallicity of Z_solar/20. We study the sensitivity of features to variations in progenitor metallicity, the outer density profile, and the distribution of radioactive nickel. The effect of metallicity variations in the progenitor have a relatively small effect on the synthetic spectra. We also find that the abundance stratification of SN 2011fe resembles closely that of a delayed detonation model with a transition density that has been fit to other Branch-normal Type Ia supernovae. At early times, the model photosphere is formed in material with velocities that are too high, indicating that the photosphere recedes too slowly or that SN 2011fe has a lower specific energy in the outer ~0.1 M_sun than does the model. We discuss several explanations for the discrepancies. Finally, we examine variations in both the spectral energy distribution and in the colors due to variations in the progenitor metallicity, which suggests that colors are only weak indicators for the progenitor metallicity, in the particular explosion model that we have studied. We do find that the flux in the U band is significantly higher at maximum light in the solar metallicity model than in the lower metallicity model and the lower metallicity model much better matches the observed spectrum.Comment: 9 pages, 14 figures, MNRAS, in press, fixed typ

Cosmological Results from High-z Supernovae

The High-z Supernova Search Team has discovered and observed 8 new supernovae in the redshift interval z=0.3-1.2. These independent observations, confirm the result of Riess et al. (1998a) and Perlmutter et al. (1999) that supernova luminosity distances imply an accelerating universe. More importantly, they extend the redshift range of consistently observed SN Ia to z~1, where the signature of cosmological effects has the opposite sign of some plausible systematic effects. Consequently, these measurements not only provide another quantitative confirmation of the importance of dark energy, but also constitute a powerful qualitative test for the cosmological origin of cosmic acceleration. We find a rate for SN Ia of 1.4+/-0.5E-04 h^3/Mpc^3/yr at a mean redshift of 0.5. We present distances and host extinctions for 230 SN Ia. These place the following constraints on cosmological quantities: if the equation of state parameter of the dark energy is w=-1, then H0 t0 = 0.96+/-0.04, and O_l - 1.4 O_m = 0.35+/-0.14. Including the constraint of a flat Universe, we find O_m = 0.28+/-0.05, independent of any large-scale structure measurements. Adopting a prior based on the 2dF redshift survey constraint on O_m and assuming a flat universe, we find that the equation of state parameter of the dark energy lies in the range -1.48-1, we obtain w<-0.73 at 95% confidence. These constraints are similar in precision and in value to recent results reported using the WMAP satellite, also in combination with the 2dF redshift survey.Comment: 50 pages, AAS LateX, 15 figures, 15 tables. Accepted for publication by Astrophysical Journa

Predicting Roof Pressures on a Low-Rise Structure From Freestream Turbulence Using Artificial Neural Networks

This paper presents a generalized approach for predicting (i.e., interpolating) the magnitude and distribution of roof pressures near separated flow regions on a low-rise structure based on freestream turbulent flow conditions. A feed-forward multilayer artificial neural network (ANN) using a backpropagation (BP) training algorithm is employed to predict the mean, root-mean-square (RMS), and peak pressure coefficients on three geometrically scaled (1:50, 1:30, and 1:20) low-rise building models for a family of upwind approach flow conditions. A comprehensive dataset of recently published boundary layer wind tunnel (BLWT) pressure measurements was utilized for training, validation, and evaluation of the ANN model. On average, predicted ANN peak pressure coefficients for a group of pressure taps located near the roof corner were within 5.1, 6.9, and 7.7% of BLWT observations for the 1:50, 1:30, and 1:20 models, respectively. Further, very good agreement was found between predicted ANN mean and RMS pressure coefficients and BLWT data

Imaging and Demography of the Host Galaxies of High-Redshift Type Ia Supernovae

We present the results of a study of the host galaxies of high redshift Type Ia supernovae (SNe Ia). We provide a catalog of 18 hosts of SNe Ia observed with the Hubble Space Telescope (HST) by the High-z Supernova Search Team (HZT), including images, scale-lengths, measurements of integrated (Hubble equivalent) BVRIZ photometry in bands where the galaxies are brighter than m ~ 25 mag, and galactocentric distances of the supernovae. We compare the residuals of SN Ia distance measurements from cosmological fits to measurable properties of the supernova host galaxies that might be expected to correlate with variable properties of the progenitor population, such as host galaxy color and position of the supernova. We find mostly null results; the current data are generally consistent with no correlations of the distance residuals with host galaxy properties in the redshift range 0.42 < z < 1.06. Although a subsample of SN hosts shows a formally significant (3-sigma) correlation between apparent V-R host color and distance residuals, the correlation is not consistent with the null results from other host colors probed by our largest samples. There is also evidence for the same correlations between SN Ia properties and host type at low redshift and high redshift. These similarities support the current practice of extrapolating properties of the nearby population to high redshifts pending more robust detections of any correlations between distance residuals from cosmological fits and host properties.Comment: 35 pages, 12 figures, 4 tables, accepted for publication in A