Al environment in tectosilicate and peraluminous glasses: A Al MQ-MAS NMR, Raman, and XANES investigation

Tecto-aluminosilicate and peraluminous glasses have been prepared by conventional and laser heating techniques, respectively, in the CaO-Al₂O₃-SiO₂ system. The structure of these glasses were studied using Raman spectroscopy, X-ray absorption at the Al K-edge and ²⁷Al NMR spectroscopy with two different high fields (400 and 750 MHz). Raman spectroscopy and X-ray absorption are techniques sensitive to the network polymerization and, in particular, show different signal as a function of silica content. However, these two techniques are less sensitive than NMR to describe the local aluminium environment. For tectosilicate glasses, aluminium in five-fold coordination, ^[5]Al, was found and a careful quantification allows the determination of a significant amount of ^[5]Al (7% in the anorthite glass). The proportion of ^[5]Al increases for the peraluminous glasses with small amounts (<2%) of six-fold coordination, ^[6]Al. The presence of ^[5]Al agrees with previous observations of the existence of nonbridging oxygens (NBOs) in tectosilicate compositions. However, the proportion of ^[5]Al in the present study indicates that no major proportion of triclusters (oxygen coordinated to three (Si,Al)O₄ tetrahedra) is required to explain these NBOS.     

Observation of mixed Rossby-gravity waves in the Western equatorial Pacific

During the IOP (Intensive Observation Period) of TOGA/COARE (Tropical Ocean and Global Atmosphere/Coupled Ocean Atmosphere Response Experiment) from December 1992 to February 1993, four Japanese moored ADCPs (Acoustic Doppler Current Profilers) measured vertical profiles of three-component velocities at the stations 2S (2°S, 156°E), 2N (2°N, 156°E), 154E (0°N, 154°E) and 147E (0°N, 147°E). Power spectra of the surface current showed a pronounced peak having a period of around 14 days for both the zonal and meridional velocities at the stations 2S and 2N near the equator, and for only the meridional velocity at the equator. This 14-day phenomenon is considered to be a kind of equatorial wave of the first baroclinic mode, from a comparison of the result of the vertical mode analysis and the vertical distribution of the standard deviation of band-pass filtered velocity fluctuations. A dispersion relationship obtained from the horizontal mode analysis of this wave confirmed that the 14-day phenomenon is a mixed Rossby-gravity wave with the westward propagating phase speed and eastward propagating group velocity. From the cross-spectral analysis of velocity data, the average phase speed and wavelength of the wave were estimated as 3.64 m s⁻¹ and 3939 km, respectively, for station pair 2S∼147E. These values were in good agreement with the average phase speed and wavelength of 3.58 m s⁻¹ and 3836 km estimated from the dispersion curve and the observed period. A northerly wind burst blew over all the mooring sites during the middle of the observation period. The mixed Rossby-gravity wave, which is anti-symmetric for the zonal velocity about the equator, is likely to be forced by this northerly wind burst crossing the equator. Generation of the oceanic mixed Rossby-gravity wave of the first baroclinic mode is discussed in association with the atmospheric Rossby wave having the same period.     

High Frequency PKKP<Subscript>BC</Subscript> Around 2.5 Hz Recorded Globally

Anomalous high frequency PKKP_BC signals (displaying a large amount of energy around 2.5 Hz), recorded globally for deep and intermediate depth earthquakes, are compared to PKKP_AB signals. The attenuation difference t_\textAB^* - t_\textBC^* t_{\text{AB}}^{*} - t_{\text{BC}}^{*} is evaluated from spectral amplitudes in the range 96–111°, being approximately twice the results provided by full-wave theory and PREM (with no low Q_μ zone in the lowermost mantle and a nearly infinite Q_K in the outer core). Most ray paths for such recordings are piercing the D″ region in the proximity of regions where ultra-low velocity zones (ULVZ) have been previously reported beneath the North Atlantic Ocean, the Southwest Pacific and the southwestern part of South America. If BC amplitudes around 2.5 Hz and at low frequencies (0.5–1.5 Hz) are comparable, the observed attenuation difference (in the frequency range 0.2–2.5 Hz) is small (around 0.25 s) and close to the PREM value. The particle motion of the high-frequency PKKP_BC at 2.5 Hz is quite similar to that of the raw recording, suggesting a deep source. An explanation for this might be scattering of the BC branch in some very restricted areas of the lowermost mantle. Alternately, the presence of a thin layer with high attenuation in the D″ region would most likely be associated with either the ultra-low velocity zone (ULVZ) or light sediments on the underside of the core-mantle boundary (CMB). Correlated to other methods to investigate the lowermost mantle, the high-frequency PKKP_BC can be used to map lateral variations of attenuation above the CMB, possibly associated with the boundary of the superplumes, especially when PKKP_AB is observed.     

Periodicity in Stem Growth and Litterfall in Tidal Freshwater Forested Wetlands: Influence of Salinity and Drought on Nitrogen Recycling

Many tidally influenced freshwater forested wetlands (tidal swamps) along the south Atlantic coast of the USA are currently undergoing dieback and decline. Salinity often drives conversion of tidal swamps to marsh, especially under conditions of regional drought. During this change, alterations in nitrogen (N) uptake from dominant vegetation or timing of N recycling from the canopy during annual litter senescence may help to facilitate marsh encroachment by providing for greater bioavailable N with small increases in salinity. To monitor these changes along with shifts in stand productivity, we established sites along two tidal swamp landscape transects on the lower reaches of the Waccamaw River (South Carolina) and Savannah River (Georgia) representing freshwater (≤0.1 psu), low oligohaline (1.1–1.6 psu), and high oligohaline (2.6–4.1 psu) stands; the latter stands have active marsh encroachment. Aboveground tree productivity was monitored on all sites through monthly litterfall collection and dendrometer band measurements from 2005 to 2009. Litterfall samples were pooled by season and analyzed for total N and carbon (C). On average between the two rivers, freshwater, low oligohaline, and high oligohaline tidal swamps returned 8,126, 3,831, and 1,471 mg N?m^?2 year^?1, respectively, to the forest floor through litterfall, with differences related to total litterfall volume rather than foliar N concentrations. High oligohaline sites were most inconsistent in patterns of foliar N concentrations and N loading from the canopy. Leaf N content generally decreased and foliar C/N generally increased with salinization (excepting one site), with all sites being fairly inefficient in resorbing N from leaves prior to senescence. Stands with higher salinity also had greater flood frequency and duration, lower basal area increments, lower tree densities, higher numbers of dead or dying trees, and much reduced leaf litter fall (103 vs. 624 g?m^?2 year^?1) over the five study years. Our data suggest that alternative processes, such as the rate of decomposition and potential for N mineralization, on tidal swamp sites undergoing salinity-induced state change may be more important for controlling N biogeochemical cycling in soils than differences among sites in N loading via litterfall.     

Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li⁺ and Na⁺ also participate in ionic transport. At superliquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism.     

Anisotropy of heterogeneity scale lengths in the lower mantle from PKIKP precursors

The anisotropy of heterogeneity scale lengths in the lower mantle is investigated by modelling its effect on the high-frequency precursors of PKIKP scattered by the heterogeneities. Although models having either an isotropic or an anisotropic distribution of scale lengths can fit the observed coda shapes of short-period precursors, the frequency content of broad-band PKIKP precursors favours a dominantly isotropic distribution of scale lengths. Precursor coda shapes are consistent with 1 per cent fluctuations in P velocity in the wavenumber band 0.05–0.5  km⁻¹ extending to 1000  km above the core–mantle boundary, and with a D" region open to circulation throughout the lower mantle. The level of excitation of PKIKP precursors observed in the frequency band 0.02–2  Hz requires a power spectrum of heterogeneity that is nearly white or slowly increasing with wavenumber. Anisotropy of scale lengths may exist in a D" layer having larger horizontal than vertical scale lengths and produce little or no detectable effects on PKIKP precursors for P -velocity perturbations as high as 3 per cent when averaged over a vertical scale of several kilometres, and much higher when averaged over scales of hundreds of metres or less.