Structure vs. composition: A solid-state H and Si NMR study of quenched glasses along the Na2O-SiO2-H2O join

A suite of six hydrous (7 wt.% H₂O) sodium silicate glasses spanning sodium octasilicate to sodium disilicate in composition were analyzed using ²⁹Si single pulse (SP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, ¹H-²⁹Si cross polarization (CP) MAS NMR, and fast MAS ¹H-NMR. From the ²⁹Si SPMAS data it is observed that at low sodium compositions dissolved water significantly depolymerizes the silicate network. At higher sodium contents, however, dissolved H₂O does not affect a significant increase in depolymerization over that predicted based on the Na/Si ratio alone. The fast MAS ¹H-NMR data reveal considerable complexity in proton environments in each of the glasses studied. The fast MAS ¹H-NMR spectra of the highest sodium concentration glasses do not exhibit evidence of signficantly greater fractions of dissolved water as molecular H₂O than the lower sodium concentration glasses requiring that the decrease in polymerization at high sodium contents involves a change in sodium solution mechanism. Variable contact time ¹H-²⁹Si cross polarization (CP) MAS NMR data reveal an increase in the rotating frame spin lattice relaxation rate constant (T_1ρ*) for various Qⁿ species with increasing sodium content that correlates with a reduction in the average ¹H-²⁹Si coupling strength. At the highest sodium concentration, however, T_1ρ* drops significantly, consistent with a change in the Na₂O solution mechanism.     

The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins

Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe³⁺ and Fe²⁺ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H₂O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi₂O₆, Ca_0.5AlSi₂O₆, and Mg_0.5AlSi₂O₆. Iron oxide was added in the form of Fe₂O₃, NaFeO₂, CaFe₂O₄, and MgFe₂O₄ with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe₂O₃. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe²⁺ and one of Fe³⁺. From the area ratios of the Fe²⁺ and Fe³⁺ absorption doublets, with corrections for differences in recoil-fractions of Fe³⁺ and Fe²⁺, the Fe³⁺/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe³⁺, δ_Fe³⁺, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, Δ_Fe³⁺, ranging from ∼1.2 to ∼1.6 mm/s. Both δ_Fe³⁺ and δ_Fe²⁺ are negatively correlated with total iron oxide content and Fe³⁺/ΣFe. The dominant oxygen coordination number Fe³⁺ changes from 4 to 6 with decreasing Fe³⁺/ΣFe. The distortion of the Fe³⁺-O polyhedra of the quenched melts (glasses) decreases as the Fe³⁺/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δ_Fe²⁺ and Δ_Fe²⁺ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe³⁺/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe²⁺ in a range of coordination states from 4- to 6-fold. The lower δ_Fe²⁺-values for the most oxidized melts are consistent with a larger proportion of Fe²⁺ in 4-fold coordination compared with more reduced glasses and melts.     

Estimation of an optimal mixed-phase inverse filter

Inverse filtering is applied to seismic data to remove the effect of the wavelet and to obtain an estimate of the reflectivity series. In many cases the wavelet is not known, and only an estimate of its autocorrelation function (ACF) can be computed. Solving the Yule-Walker equations gives the inverse filter which corresponds to a minimum-delay wavelet. When the wavelet is mixed delay, this inverse filter produces a poor result.
By solving the extended Yule-Walker equations with the ACF of lag α on the main diagonal of the filter equations, it is possible to decompose the inverse filter into a finite-length filter convolved with an infinite-length filter. In a previous paper we proposed a mixed-delay inverse filter where the finite-length filter is maximum delay and the infinite-length filter is minimum delay.
Here, we refine this technique by analysing the roots of the Z -transform polynomial of the finite-length filter. By varying the number of roots which are placed inside the unit circle of the mixed-delay inverse filter, at most 2 ^α different filters are obtained. Applying each filter to a small data set (say a CMP gather), we choose the optimal filter to be the one for which the output has the largest L ^p -norm, with p =5. This is done for increasing values of α to obtain a final optimal filter. From this optimal filter it is easy to construct the inverse wavelet which may be used as an estimate of the seismic wavelet.
The new procedure has been applied to a synthetic wavelet and to an airgun wavelet to test its performance, and also to verify that the reconstructed wavelet is close to the original wavelet. The algorithm has also been applied to prestack marine seismic data, resulting in an improved stacked section compared with the one obtained by using a minimum-delay filter.     

Mechanisms and Model Diversity of Trade-Wind Shallow Cumulus Cloud Feedbacks: A Review

Shallow cumulus clouds in the trade-wind regions are at the heart of the long standing uncertainty in climate sensitivity estimates. In current climate models, cloud feedbacks are strongly influenced by cloud-base cloud amount in the trades. Therefore, understanding the key factors controlling cloudiness near cloud-base in shallow convective regimes has emerged as an important topic of investigation. We review physical understanding of these key controlling factors and discuss the value of the different approaches that have been developed so far, based on global and high-resolution model experimentations and process-oriented analyses across a range of models and for observations. The trade-wind cloud feedbacks appear to depend on two important aspects: (1) how cloudiness near cloud-base is controlled by the local interplay between turbulent, convective and radiative processes; (2) how these processes interact with their surrounding environment and are influenced by mesoscale organization. Our synthesis of studies that have explored these aspects suggests that the large diversity of model responses is related to fundamental differences in how the processes controlling trade cumulus operate in models, notably, whether they are parameterized or resolved. In models with parameterized convection, cloudiness near cloud-base is very sensitive to the vigor of convective mixing in response to changes in environmental conditions. This is in contrast with results from high-resolution models, which suggest that cloudiness near cloud-base is nearly invariant with warming and independent of large-scale environmental changes. Uncertainties are difficult to narrow using current observations, as the trade cumulus variability and its relation to large-scale environmental factors strongly depend on the time and/or spatial scales at which the mechanisms are evaluated. New opportunities for testing physical understanding of the factors controlling shallow cumulus cloud responses using observations and high-resolution modeling on large domains are discussed.     

An Improved Method for Modeling Spatial Distribution of δD in Surface Snow over Antarctic Ice Sheet

Using the recent compilation of the isotopic composition data of surface snow of Antarctic ice sheet, we proposed an improved interpolation method of δD, which utilizes geographical factors (i.e., latitude and altitude) as the primary predictors and incorporates inverse distance weighting (IDW) technique. The method was applied to a high-resolution digital elevation model (DEM) to produce a grid map of multi-year mean δD values with 1km spatial resolution for Antarctic& The mean absolute deviation between observed and estimated data in the map is about 5.4‰, and the standard deviation is 9‰. The resulting δD pattern resembles well known characteristics such as the depletion of the heavy isotopes with increasing latitude and distance from coast line, but also reveals the complex topographic effects.     

Use of voltammetric solid-state (micro)electrodes for studying biogeochemical processes: Laboratory measurements to real time measurements with an in situ electrochemical analyzer (ISEA)

Solid-state voltammetric (micro)electrodes have been used in a variety of environments to study biogeochemical processes. Here we show the wealth of information that has been obtained in the study of sediments, microbial mats, cultures and the water column including hydrothermal vents. Voltammetric analyzers have been developed to function with operator guidance and in unattended mode for temporal studies with an in situ electrochemical analyzer (ISEA). The electrodes can detect the presence (or absence) of a host of redox species and trace metals simultaneously. The multi-species capacity of the voltammetric electrode can be used to examine complex heterogeneous environments such as the root zone of salt marsh sediments. The data obtained with these systems clearly show that O₂ and Mn²⁺ profiles in marine sedimentary porewaters and in microbial biofilms on metal surfaces rarely overlap indicating that O₂ is not a direct oxidant for Mn²⁺. This lack of overlap was suggested originally by Joris Gieskes' group. In waters emanating from hydrothermal vents, Fe²⁺, H₂S and soluble molecular FeS clusters (FeS_aq) are detected indicating that the reactants for the pyrite formation reaction are H₂S and soluble molecular FeS clusters. Using the ISEA with electrodes at fixed positions, data collected continuously over three days near a Riftia pachyptila tubeworm field generally show that O₂ and H₂S anti-correlate and that H₂S and temperature generally correlate. Unlike sedimentary environments, the data clearly show that Riftia live in areas where both O₂ and H₂S co-exist so that its endosymbiont bacteria can perform chemosynthesis. However, physical mixing of diffuse flow vent waters with oceanic bottom waters above or to the side of the tubeworm field can dampen these correlations or even reverse them. Voltammetry is a powerful technique because it provides chemical speciation data (e.g.; oxidation state and different elemental compounds/ions) as well as quantitative data. Because (micro)organisms occupy environmental niches due to the system's chemistry, it is necessary to know chemical speciation. Voltammetric methods allow us to study how chemistry drives biology and how biology can affect chemistry for its own benefit.     

青藏高原各拉丹冬冰芯记录的季节气温变化

A 70-year history of precipitation δ18O record has been retrieved using an ice core drilled from a plat portion of the firn area in the Guoqu Glacier (33o34′37.8″ N, 91o10′35.3″ E, 5720 m a.s.l.) on Mt. Geladaindong (the source region of Yangtze River) during October and November, 2005. Based on the seasonality of δ18O records and the significant positive relationships between monsoon/non-monsoon δ18O values and summer/spring air temperature from the nearby meteorological stations, the history of summer and spring air temperature have been reconstructed for the last 70 years. The results show that both summer and spring air temperature variations present similar trends during the last 70 years. Regression analysis indicates that the slope of the temperature-δ18O relationship is 1.3℃/‰ for non-monsoon δ18O values and spring air temperature, and 0.4℃/‰ for monsoon δ18O values and summer air temperature. Variation of air temperature recorded in the ice core is consistent with that in the Northern Hemisphere (NH), however, the warming trend in the Geladaindong region is more intense than that in the NH, reflecting a higher sensitivity to global warming in the high elevation regions. In addition, warming trend is greater in spring than in summer.     

Channel evolution of Des Moines Lobe till drainage ditches in southern Minnesota (USA)

Some drainage ditches in the intensively managed row-crop agricultural region of southern Minnesota evolved from a trapezoidal form to multi-staged channel forms similar to natural streams. Older ditches constructed in cohesive sediment of the Des Moines Lobe till tend to follow a channel evolution model developed by Simon and Hupp. Site cross sections, longitudinal water and bed profiles and bed material particle size were determined according to Harrelson and others at 24 older ditch reaches, 5 newly constructed ditch reaches and 13 natural stream reaches. Morphological features were hypothesized to change from trapezoidal form to flat bench banks, similar to benches found in natural stream channels. All data were statistically analyzed with respect to drainage area using regression, because channel form is directly related to drainage area for a given climate, geology and land use. Results show similar regression slope and intercept for bankfull channel width and bankfull cross-sectional area (CSA) of older ditches and natural streams compared to typical trapezoidal designed ditches. Evolved ditches developed a small floodplain bench above the ditch bed and adjusted their bankfull widths similar to natural stream channels with respect to drainage area. Old ditches showed a relatively strong R ² (0.82, 0.68) for channel CSA and width, a weaker R ² (0.45) for water surface slope, and little to no correlation with bed particle size. Channel form appears to have adjusted more quickly than bed facets and/or bed particle size distribution. However, stepwise regression determined that D₈₄, width/depth ratio and mean bankfull depth explained 83?% of the variability of channel features across varying drainage areas. Findings suggest a possible reduction of long-term maintenance costs if older ditches are allowed to evolve over time. A stable ditch form similar to natural streams is typically self-sustaining, suggesting that prior to a scheduled clean-out, the ditch should be examined for hydraulic capacity, sediment transport and bank stability.     

Sediment Response to 25?Years of Persistent Hypoxia

We investigated the impact of persistent hypoxia on sediment chemistry by comparing total, reactive (extractible with 1?M hydroxylamine?Chydrochloride in 25?% acetic acid), and dissolved forms of the redox-sensitive elements Mn, Fe, and As in cores recovered between 1982 and 2007 at two sites in the Lower St. Lawrence Estuary (LSLE) where the bottom water has been severely hypoxic since the early 1980s. The data reveal that the concentrations and the vertical distributions of total solid-phase and dissolved Mn as well as total solid-phase Fe and As were not significantly affected by persistent hypoxia. In contrast, the composition of solid-phase Fe and As changed significantly as did the pore-water concentrations of both these elements. The relative amounts of solid-phase reactive Fe and As increased, and the abundance of pyrite and pyritic?CAs decreased in the sediment layer that accumulated since 1982. We propose that persistent hypoxic conditions restrict the supply of oxygen to the sediment and increase the relative contribution of alternate electron acceptors??Mn(IV), Fe(III), and sulfate??to microbial oxidation of organic matter. In marine iron-rich environments, such as the LSLE sediment, increased sulfate reduction may promote conversion of less reactive Fe phases to more reactive Fe phases which, in turn, interfere with pyrite formation. Consequently, a chalcophile element such as As, which would normally be sequestered with authigenic pyrite, remains available for recycling across the oxic?Canoxic boundary in the sediment.