Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts     

Jonathan F. Stebbins  Emily V. Dubinsky  Koji Kanehashi  Kimberly E. Kelsey 《Geochimica et cosmochimica acta》2008,72(3):910-925

Configurational changes with temperature are important for the thermodynamic and transport properties of most aluminosilicate melts, but in general are not well understood. Here, we present high-resolution ²⁷Al and ¹⁷O NMR data on several calcium aluminosilicate glasses prepared with varying quench rates and thus with fictive temperatures that span ranges up to about 200 K. In all compositions the content of five-coordinated aluminum increases with fictive temperature, in agreement with recent high temperature NMR data on melts. In a glass of CaAl₂Si₂O₈ (“anorthite”) composition, the content of non-bridging oxygens also increases with temperature; however this effect was not observed in a sample with a much higher CaO/Al₂O₃ ratio. We present a consistent notation for reactions among structural species in these systems that clarify why in some cases, high-coordinated network cations may appear on the same side of the reaction, while in others they occur on the opposite sides: the key difference is in accounting for all coordination changes for oxygens. Mixing of non-bridging oxygens and of high-coordinated aluminum make significant contributions to the overall configurational entropy and heat capacity of the melts, as does the mixing of various bridging oxygens and of tetrahedral network cations. Other, less well known, types of increase in disorder with temperature may be important as well.  相似文献   

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes     

Kenneth H. Dunton  Jonathan L. Goodall  Susan V. Schonberg  Jacqueline M. Grebmeier  David R. Maidment 《Deep Sea Research Part II: Topical Studies in Oceanography》2005,52(24-26):3462

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.  相似文献   

Feature modeling approach to simulating Loop Current Frontal Eddies     

Sergei A. Frolov  Lewis M. Rothstein 《Estuarine, Coastal and Shelf Science》2006,70(4):533

Loop Current Frontal Eddies (LCFE) in the Gulf of Mexico are simulated with a regional configuration of the Princeton Ocean Model using a feature-oriented initialization technique. The initialization procedure is based on a prior investigation of stability characteristics of the Loop Current (LC). Zonal channel experiments conducted with a multi-layer intermediate equations model allowed to identify conditions necessary for formation and growth of frontal eddies. The simulations were able to reproduce key features of LCFE-topography interaction in the DeSoto Canyon region observed during the “Eddy Intrusion” study.  相似文献   

JONSWAP's parameters: Sorting out the inconsistencies     

A.W. Lewis  R.N. Allos 《Ocean Engineering》1990,17(4)

The original prognostic equations for the JONSWAP-spectrum contained inconsistencies. A subsequent paper (Hasselmann et al., 1976, J. phys. Oceanogr.6, 200–208) attempted to regularise the situation. This paper shows that there were still inconsistencies in the prognostic equations giving overestimations of the first moment of the spectrum and consequently the significant wave height. The prognostic equations are reworked systematically and results presented. It is shown that variable σ_a, σ_b and γ must be used to achieve consistent results  相似文献   

The expression of CYP1A,vitellogenin and zona radiata proteins in Atlantic salmon (Salmo salar) after oral dosing with two commercial PBDE flame retardant mixtures: absence of short-term responses     

Boon JP  van Zanden JJ  Lewis WE  Zegers BN  Goksøyr A  Arukwe A 《Marine environmental research》2002,54(3-5):719-724

The short-term effects of the commercial PBDE flame retardant mixtures Penta-BDE and cta-BDE on the expression of cytochrome P450 1A (CYP1A), vitellogenin (Vtg) and zona radiata proteins (Zrp) were investigated in juvenile salmon (Salmo salar). For this purpose, groups of fish were dosed twice (oral intake at days I and 4) with 10 and 50 mg/kg body weight of both commercial mixtures. The fishes were sacrificed at day 7 (n = 5 for each group) and 14 (n = 6 for each group), and blood, liver, fillet, and brain were collected. Blanks and positive controls were also part of the experiment. The expressions of Vtg, Zrp, and CYPIA were measured with several techniques (EROD, ELISA, Western, Northern and Slot Blot). The values in the groups of fish treated with Penta-BDE or Octa-BDE did not significantly differ from the reference group for any of the parameters tested. In contrast, the positive control groups treated with estradiol-17beta for Vtg and Zrp expression, and beta-naphthoflavone for CYP1A expression did show a significant response, indicating the potential sensitivity of the fishes for the parameters measured. Since the results of the chemical analyses showed concentrations of a number of PBDE congeners in liver, fillet, and brain that were about three orders of magnitude above those of fish from the North Sea, it is concluded that the short-term toxicity of both commercial PBDE mixtures for these endpoints was low.  相似文献   

Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay     

Brent L. Lewis  Brian T. Glazer  Paul J. Montbriand  George W. Luther III  Donald B. Nuzzio  Timothy Deering  Shufen Ma  Stephen Theberge 《Marine Chemistry》2007,105(3-4):296-308

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.  相似文献   

Southern elephant seal trajectories, fronts and eddies in the Brazil/Malvinas Confluence     

Claudio Campagna  Alberto R. Piola  Maria Rosa Marin  Mirtha Lewis  Teresita Fernndez 《Deep Sea Research Part I: Oceanographic Research Papers》2006,53(12):1907-1924

This study describes the association between transient, mesoscale hydrographic features along the axis of the Brazil–Malvinas Confluence, in the SW Atlantic, and the foraging behavior of 2–3-year-old (focal) juvenile southern elephant seals, Mirounga leonina, from Península Valdés, Argentina. Departing from the dominant pattern of foraging on predictable bathymetric fronts on the Patagonian shelf and slope, three females out of 12 satellite-tracked juveniles remained at the edge of young warm-core eddies and near the outer core of cold-core eddies, coinciding with the most productive areas of these temperature fronts. Seal trajectories along high-temperature gradients were always consistent with the speed and direction of surface currents inferred from the temperature distribution and confirmed by surface drifters. Movements of foraging seals were compared with those of surface drifters, coinciding in time and space and yielding independent and consistent data on regional water circulation parameters. The diving pattern recorded for one focal seal yielded shallower dives and a loose diel pattern in the eddy, and a marked diurnal cycle compatible with foraging on vertically migrating prey in the cold waters of the Malvinas Current. Pre-reproductive females that use the mesoscale fronts of the Argentine Basin as an alternative foraging area would benefit from lower competition with more experienced seals and with other top predators that reproduce along the coast of Patagonia.  相似文献   

A practical salinity scale     

N. P. Fofonoff  E. L. Lewis 《Journal of Oceanography》1979,35(1):63-64

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Voltammetric estimation of iron(III) thermodynamic stability constants for catecholate siderophores isolated from marine bacteria and cyanobacteria     

Brent L. Lewis  Pamela D. Holt  Steven W. Taylor  Steven W. Wilhelm  Charles G. Trick  Alison Butler  George W. Luther  III 《Marine Chemistry》1995,50(1-4)

Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.  相似文献   

Gravity field analysis of Sio Guyot: An isostatically compensated seamount in the Mid-Pacific Mountains     

James N. Kellogg  I. Jonathan Ogujiofor 《Geo-Marine Letters》1985,5(2):91-97

Positive gravity anomalies indicate two dense conduits or eruptive centers beneath the northern summit of Sio Guyot, western Mid-Pacific Mountains. The low amplitude of the positive anomalies and the gravity lows flanking the guyot can be explained by crust 2.5 times the normal Pacific Ocean crustal thickness extending to a depth of 22 ± 2 km. The excess mass of the seamount is 100% locally isostatically compensated by the mass deficit below; this compensation may result from flexural loading and voluminous sill injection near a former ridge-crest transform fault system trending roughly ENE and NNW.  相似文献