Calculation of Si NMR shifts of silicate complexes with carbohydrates, amino acids, and muhicarboxylic acids: potential role in biological silica utilization

The existence of ether or ester-like complexes of silicate with organic compounds has long been debated in the literature on biological utilization of silicon. Comparison of theoretically calculated ²⁹Si NMR chemical shifts for such complexes with experimentally measured values in biological systems could provide a diagnostic tool for identifying which, if any of these molecules exist under physiological conditions. Results are presented here for ab initio molecular orbital calculations of ²⁹Si NMR shifts and formation energies of silicate complexes with polyalcohols, sugar-acids, pyranose sugars, amino acids and multicarboxylic acids. The effects of functional group and molecular structure including ligand size, denticity, ring size, silicon polymerization and coordination number on calculated ²⁹Si shifts were considered. The potential role of such compounds in biological silica utilization pathways is discussed.²⁹Si NMR shifts and energies were calculated at the HF/6-311+G(2d,p)//HF/6-31G* level. The main result is that only five-membered rings containing penta- and hexa-coordinated Si can explain experimentally observed resonances at ∼ −101 and −141 ppm. Further, the heptet observed in ¹H-²⁹Si coupled spectra can only be explained by structures where Si bonds to oxygens atoms in H-C-O-Si linkages with six symmetrically equivalent H atoms.While compounds containing quadra-coordinated silicon may exist in intracellular silicon storage pools within diatoms, calculated reaction energies suggest that the organism has no thermodynamic advantage in taking up extracellular organ-silicate compounds, instead of silicic acid, from the ambient aqueous environment. Hyper-coordinated complexes are deemed unlikely for transport and storage, though they may exist as transient reactive intermediates or activated complexes during enzymatically- catalyzed silica polymerization, as known previously from sol-gel silica synthesis studies.     

Tidal and solar cycle effects on the OI 5577 Å, NaD and OH(8,3) airglow emissions observed at 23°S

The upper mesosphere airglow emissions OI 5577, NaD and OH have been observed at Cachoeira Paulista (22.7°S; 45.0°W) Brazil. Nocturnal variations and their seasonal dependencies in amplitude and phase, and the annual variations of these emissions are presented, analysing the data obtained from 1977 to 1982 during the ascending phase of the last solar cycle. The nocturnal variations of the OI 5577 emission and the OH rotational temperature showed a significant semidiurnal oscillation, with the phase of maximum moving from midnight in January to early morning in June. Semiannual variation of the OI 5577 and NaD emissions with the maximum intensities in April/May and October/November were observed. The OH rotational temperature, however, showed an annual variation, maximum in summer and minimum in winter, while no significant seasonal variation was found in the OH emission intensities. Long-term intensity variations are also presented with the solar sunspot numbers and the 10.7 cm flux.     

Thermospheric Meridional Wind Control on Equatorial Scintillations and the Role of the Evening F-Region Height Rise, E?×?B Drift Velocities and F2-Peak Density Gradients

The possible role, on L-band scintillation activity, played by the nighttime magnetic meridional component of the thermospheric horizontal neutral winds, the post-sunset F-layer base height, the electrical field pre-reversal enhancement (PRE) and the latitudinal gradients of the F2-layer peak density is analyzed, considering different cases of scintillation occurrence (and their latitudinal extent) during August and September 2002. The meridional winds were derived over low-latitudes from a modified form of the nonlinear time-dependent servo-model. A chain of two scintillation monitors and three digital ionosondes was operational in Brazil and used to collect, respectively, global positioning system signal amplitude scintillation and ionospheric height (h′F; hpF2) and frequency (foF2) parameters. From the overall behavior in the 2 months analyzed, the results suggest that high near sunset upward vertical plasma drifts are conducive for the generation of spread-F irregularities, whereas large poleward meridional winds tend to suppress the development of plasma bubble irregularities and the occurrence of their associated scintillations. Even when generated, a reduced fountain effect, due to weak electric field PRE, acts for the bubbles to be expanded less effectively to higher latitudes. The results also reveal that high F-layer base and peak heights (at equatorial and off-equatorial latitudes), and intense gradients in the F2-peak density between the dip equator and the equatorial anomaly crests, are favorable conditions for the generation of F-region irregularities and increased scintillation activity. Other distinct features of the controlling factors in the cases of occurrence and non-occurrence of equatorial scintillations are presented and discussed.     

Deep exploration using long-offset transient electromagnetics: interpretation of field data in time and frequency domain

In the framework of the Deep Electromagnetic Soundings for Mineral Exploration project, we conducted ground-based long-offset transient-electromagnetic measurements in a former mining area in eastern Thuringia, Germany. The large-scale survey resulted in an extensive dataset acquired with multiple high-power transmitters and a high number of electric and magnetic field receivers. The recorded data exhibit a high data quality over several decades of time and orders of magnitude. Although the obtained subsurface models indicate a strong multi-dimensional subsurface with variations in resistivity over three orders of magnitude, the electrical field step-on transients are well fitted using a conventional one-dimensional inversion. Due to superimposed induced polarization effects, the transient step-off data are not interpretable with conventional electromagnetic inversion. For further interpretation in one and two dimensions, a new approach to evaluate the long-offset transient-electromagnetic data in frequency domain is realized. We present a detailed workflow for data processing in both domains and give an overview of technical obstructions that can occur in one domain or the other. The derived one-dimensional inversion models of frequency-domain data show strong multi-dimensional effects and are well comparable with the conventional time domain inversion results. To adequately interpret the data, a 2.5D frequency-domain inversion using the open source algorithm MARE2DEM (Modeling with Adaptively Refined Elements for 2-D EM) is carried out. The inversion leads to a consistent subsurface model with shallow and deep conductive structures, which are confirmed by geology and additional geophysical surveys.     

Role of ocean–atmosphere interaction on northward propagation of Indian summer monsoon intra-seasonal oscillations (MISO)

Atmospheric dynamical mechanisms have been prevalently used to explain the characteristics of the summer monsoon intraseasonal oscillation (MISO), which dictates the wet and dry spells of the monsoon rainfall. Recent studies show that ocean–atmosphere coupling has a vital role in simulating the observed amplitude and relationship between precipitation and sea surface temperature (SST) at the intraseasonal scale. However it is not clear whether this role is simply ‘passive’ response to the atmospheric forcing alone, or ‘active’ in modulating the northward propagation of MISO, and also whether the extent to which it modulates is considerably noteworthy. Using coupled NCEP–Climate Forecast System (CFSv2) model and its atmospheric component the Global Forecast System (GFS), we investigate the relative role of the atmospheric dynamics and the ocean–atmosphere coupling in the initiation, maintenance, and northward propagation of MISO. Three numerical simulations are performed including (1) CFSv2 coupled with high frequency interactive SST, the GFS forced with both (2) observed monthly SST (interpolated to daily) and (3) daily SST obtained from the CFSv2 simulations. Both CFSv2 and GFS simulate MISO of slightly higher period (~60 days) than observations (~45 days) and have reasonable seasonal rainfall over India. While MISO simulated by CFSv2 has realistic northward propagation, both the GFS model experiments show standing mode of MISO over India with no northward propagation of convection from the equator. The improvement in northward propagation in CFSv2, therefore, may not be due to improvement of the model physics in the atmospheric component alone. Our analysis indicates that even with the presence of conducive vertical wind shear, the absence of meridional humidity gradient and moistening of the atmosphere column north of convection hinders the northward movement of convection in GFS. This moistening mechanism works only in the presence of an ‘active’ ocean. In CFSv2, the lead-lag relationship between the atmospheric fluxes, SST and convection are maintained, while such lead-lag is unrealistic in the uncoupled simulations. This leads to the conclusion that high frequent and interactive ocean–atmosphere coupling is a necessary and crucial condition for reproducing the realistic northward propagation of MISO in this particular model.     

Correlations between OH,NaD and OI 5577 Å emissions in the airglow

Simultaneous measurements of the night airglow OI 5577 Å and OH (8,3) band have been carried out at Cachoeira Paulista (23°S, 45°W), Brazil since 1976. Cross correlation analyses between the nocturnal variations of these emissions and also with the OH rotational temperature (ROT) for various time shifts are presented. It is found that OH (8,3) is well correlated with ROT but with a time lag of about 1 h. The variations of OI 5577 Å lead OH (8,3) by about 2–3 h and ROT covaries with 5577 Å with a time lag less than 1 h. For the sake of comparison, OI 5577 Å, OH and NaD data from a number of IQSY stations have been analysed. It is noted that (1) OI 5577 Å leads OH by about 2 h at mid-latitude stations and (2) OH is well correlated with Na 5893 Å with a time lag of less than 1 h. The presence of the phase lagged correlation patterns between OH/5577 Å, OH/ROT and OH/NaD indicates vertical propagation of a wavelike perturbation of the upper atmosphere.     

Inorganic synthesis of Fe–Ca–Mg carbonates at low temperature

A set of free-drift experiments was undertaken to synthesize carbonates of mixed cation content (Fe, Ca, Mg) from solution at 25 and 70 °C to better understand the relationship between the mineralogy and composition of these phases and the solutions from which they precipitate. Metastable solid solutions formed at 25 °C which are not predicted from the extrapolation of higher temperature equilibrium assemblages; instead, solids formed that were intermediary in chemical composition to known magnesite–siderite and dolomite solid solutions. A calcite–siderite solid solution precipitated at 25 °C, with the percentage of CaCO₃ in the solid being proportional to the aqueous Ca/Fe ratio of the solution, while Mg was excluded from the crystal structure except at relatively high aqueous Mg/Ca and Mg/Fe ratios and a low Ca content. Alternatively, at 70 °C Mg was the predominant cation of the solid solutions. These results are compatible with the hypothesis that the relative dehydration energies of Fe, Ca and Mg play an important role in the formation of mixed cation carbonates in nature.     

Generalized thermostatistics and wavelet analysis of solar wind and proton density variability

In this paper, we analyze the probability density function (PDF) of solar wind velocity and proton density, based on generalized thermostatistics (GT) approach, comparing theoretical results with observational data. The time-series analyzed were obtained from the SOHO satellite mission where measurements were sampled every hour. We present in the investigations data for two years of different solar activity: (a) moderate activity (MA) period (1997) and (b) high activity (HA) period (2000). For the MA period, the results show good agreement between experimental data and GT model. For the HA period, the agreement between experimental and theoretical PDFs was fairly good, but some distortions were observed, probably due to intermittent characteristics of turbulent processes. As a complementary analysis, the global wavelet spectrum (GWS) was obtained, allowing the characterization of the predominant temporal variability scales for both periods and the stochastic aspects of the nonlinear solar wind variability are discussed.     

Hydraulic response of a tidally forced coastal aquifer, Pontal do Paraná, Brazil

The unconfined aquifer supported by the extensive Holocene coastal plain of southern Brazil is found dissected at several places by tidally forced streams. One such unit of coastal plain, falling within the watershed limits of Perequê Stream in Paraná state, was analyzed using MODFLOW to assess the surface and subsurface water components under different stress conditions. The steady-state simulation suggests that ~23,000 m³/day of water forms the total budget of the designated aquifer zone and this zone discharges ~16,000 m³/day across the interface between the freshwater aquifer zone and the sea as direct submarine discharge. The maximum evaporation loss was assumed to be 2,700 m³/day. Any change in effective aquifer storage was insignificant, as there is no large-scale exploitation of local groundwater reserves. A calibration exercise, based on field measurements lasting 1 year, supports validity of the model considered. Simulations representing two different transient conditions point to the dynamic hydraulic response exhibited by the aquifer. A schematic map, showing directions and velocity of subsurface flows, and a three-dimensional model of the groundwater reserve helped to visualize the hydrogeologic changes and to formulate management plans.