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  • American Geophysical Union  (416)
  • Copernicus  (313)
  • Wiley-Blackwell  (268)
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  • 1
    Publication Date: 2012-10-23
    Print ISSN: 0886-6236
    Electronic ISSN: 1944-9224
    Topics: Biology , Chemistry and Pharmacology , Geography , Geosciences , Physics
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  • 2
    Publication Date: 2020-01-27
    Description: Although quantitative isotope data from speleothems has been used to evaluate isotope-enabled model simulations, currently no consensus exists regarding the most appropriate methodology through which to achieve this. A number of modelling groups will be running isotope-enabled palaeoclimate simulations in the framework of the Coupled Model Intercomparison Project Phase 6, so it is timely to evaluate different approaches to using the speleothem data for data–model comparisons. Here, we illustrate this using 456 globally distributed speleothem δ18O records from an updated version of the Speleothem Isotopes Synthesis and Analysis (SISAL) database and palaeoclimate simulations generated using the ECHAM5-wiso isotope-enabled atmospheric circulation model. We show that the SISAL records reproduce the first-order spatial patterns of isotopic variability in the modern day, strongly supporting the application of this dataset for evaluating model-derived isotope variability into the past. However, the discontinuous nature of many speleothem records complicates the process of procuring large numbers of records if data–model comparisons are made using the traditional approach of comparing anomalies between a control period and a given palaeoclimate experiment. To circumvent this issue, we illustrate techniques through which the absolute isotope values during any time period could be used for model evaluation. Specifically, we show that speleothem isotope records allow an assessment of a model’s ability to simulate spatial isotopic trends. Our analyses provide a protocol for using speleothem isotope data for model evaluation, including screening the observations to take into account the impact of speleothem mineralogy on δ18O values, the optimum period for the modern observational baseline and the selection of an appropriate time window for creating means of the isotope data for palaeo-time-slices.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2005. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 110 (2005): C09S16, doi:10.1029/2004JC002601.
    Description: Comparison of eight iron experiments shows that maximum Chl a, the maximum DIC removal, and the overall DIC/Fe efficiency all scale inversely with depth of the wind mixed layer (WML) defining the light environment. Moreover, lateral patch dilution, sea surface irradiance, temperature, and grazing play additional roles. The Southern Ocean experiments were most influenced by very deep WMLs. In contrast, light conditions were most favorable during SEEDS and SERIES as well as during IronEx-2. The two extreme experiments, EisenEx and SEEDS, can be linked via EisenEx bottle incubations with shallower simulated WML depth. Large diatoms always benefit the most from Fe addition, where a remarkably small group of thriving diatom species is dominated by universal response of Pseudo-nitzschia spp. Significant response of these moderate (10–30 μm), medium (30–60 μm), and large (〉60 μm) diatoms is consistent with growth physiology determined for single species in natural seawater. The minimum level of “dissolved” Fe (filtrate 〈 0.2 μm) maintained during an experiment determines the dominant diatom size class. However, this is further complicated by continuous transfer of original truly dissolved reduced Fe(II) into the colloidal pool, which may constitute some 75% of the “dissolved” pool. Depth integration of carbon inventory changes partly compensates the adverse effects of a deep WML due to its greater integration depths, decreasing the differences in responses between the eight experiments. About half of depth-integrated overall primary productivity is reflected in a decrease of DIC. The overall C/Fe efficiency of DIC uptake is DIC/Fe ∼ 5600 for all eight experiments. The increase of particulate organic carbon is about a quarter of the primary production, suggesting food web losses for the other three quarters. Replenishment of DIC by air/sea exchange tends to be a minor few percent of primary CO2 fixation but will continue well after observations have stopped. Export of carbon into deeper waters is difficult to assess and is until now firmly proven and quite modest in only two experiments.
    Description: This research was supported by the European Union through programs CARUSO (1998– 2001), IRONAGES (1999 –2003), and COMET (2000–2003); the Netherlands- Bremen Oceanography program NEBROC-1; and the Netherlands Organization for Research NWO through the Netherlands Antarctic Program project FePath. Both the U.S. National Science Foundation and the U.S. Department of Energy provided significant support for the SOFeX program. M.R.L. acknowledges the U.S. National Science Foundation for support of IronEx and SOFeX projects and related studies (OCE-9912230, -9911765, and -0322074).
    Keywords: Iron ; Fertilization ; Phytoplankton
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 4
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 12 (2011): Q03001, doi:10.1029/2010GC003322.
    Description: In situ secondary ion mass spectrometry (SIMS) analyses of δ7Li, Li/Ca, and Mg/Ca were performed on five synthetic aragonite samples precipitated from seawater at 25°C at different rates. The compositions of δ7Li in bulk aragonites and experimental fluids were measured by multicollector inductively coupled plasma–mass spectrometry (MC-ICP-MS). Both techniques yielded similar δ7Li in aragonite when SIMS analyses were corrected to calcium carbonate reference materials. Fractionation factors α7Li/6Li range from 0.9895 to 0.9923, which translates to a fractionation between aragonite and fluid from −10.5‰ to −7.7‰. The within-sample δ7Li range determined by SIMS is up to 27‰, exceeding the difference between bulk δ7Li analyses of different aragonite precipitates. Moreover, the centers of aragonite hemispherical bundles (spherulites) are enriched in Li/Ca and Mg/Ca relative to spherulite fibers by up to factors of 2 and 8, respectively. The Li/Ca and Mg/Ca ratios of spherulite fibers increase with aragonite precipitation rate. These results suggest that precipitation rate is a potentially important consideration when using Li isotopes and elemental ratios in natural carbonates as a proxy for seawater composition and temperature.
    Description: SIMS analyses were supported by U.S. NSF, EAR, Instrumentation and Facilities Program. The development of the method for bulk d7Li analysis and the MC‐ICP‐MS measurements were covered by NSF grant EAR/IF‐0318137. Precipitation experiments were supported by NSF through grants OCE‐0402728, OCE‐0527350, and OCE‐0823527 to Glenn Gaetani and Anne Cohen and through grant EAR‐0337481 to Bruce Watson.
    Keywords: Isotope ; Aragonite ; Rate ; SIMS ; Magnesium ; Lithium
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
    Publication Date: 2022-05-27
    Description: Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research-Oceans 124, (2019): 9141-9170, doi: 10.1029/2019JC015210.
    Description: The observational network around the North Atlantic has improved significantly over the last few decades with subsurface profiling floats and satellite observations and the recent efforts to monitor the Atlantic Meridional Overturning Circulation (AMOC). These have shown decadal time scale changes across the North Atlantic including in heat content, heat transport, and the circulation. However, there are still significant gaps in the observational coverage. Ocean reanalyses integrate the observations with a dynamically consistent ocean model and can be used to understand the observed changes. However, the ability of the reanalyses to represent the dynamics must also be assessed. We use an ensemble of global ocean reanalyses to examine the time mean state and interannual‐decadal variability of the North Atlantic ocean since 1993. We assess how well the reanalyses are able to capture processes and whether any understanding can be gained. In particular, we examine aspects of the circulation including convection, AMOC and gyre strengths, and transports. We find that reanalyses show some consistency, in particular showing a weakening of the subpolar gyre and AMOC at 50°N from the mid‐1990s until at least 2009 (related to decadal variability in previous studies), a strengthening and then weakening of the AMOC at 26.5°N since 2000, and impacts of circulation changes on transports. These results agree with model studies and the AMOC observations at 26.5°N since 2005. We also see less spread across the ensemble in AMOC strength and mixed layer depth, suggesting improvements as the observational coverage has improved.
    Description: This work was initiated through the EU COST‐EOS‐1402 project which supported the development of this paper by funding project meetings, both in person and virtual. We would like to thank Aida Azcarate for organizing the funding for the meetings and would like to thank Martha Buckley, Gokhan Danabasoglu, and Simon Josey for useful discussions. Jackson, Storto and Zuo were partially funded, by the Copernicus Marine Environment Monitoring Service (CMEMS: 23‐GLO‐RAN) and Zuo was partially funded by the Copernicus Climate Change Service. Jackson was also partially funded by the joint UK BEIS/Defra Met Office Hadley Centre Climate Programme (GA01101). Haines and Robson acknowledge funding under the NERC RAPID projects RAMOC and DYNAMOC (NE/M005127/1) respectively, and Robson also acknowledges funding from the ACSIS project. Mignac was supported for PhD scholarship by the CAPES Foundation, Ministry of Education of Brazil (Proc. BEX 1386/15‐8). Forget acknowledges support from the Simons Foundation (549931) and the NASA IDS program (6937342). Work by Piecuch was carried out under the ECCO project, funded by the NASA Physical Oceanography, Cryospheric Science, and Modeling, Analysis and Prediction programs, and supported by the Independent Research and Development Program at Woods Hole Oceanographic Institution. Wilson was funded by the NERC UK‐OSNAP project (NE/K010875.1) as part of the international OSNAP program. NorCPM‐v1 reanalysis was cofunded by the Center for Climate Dynamics at the Bjerknes Center, the Norwegian Research Council under the EPOCASA (229774/E10) and SFE (270733) research projects, the NordForsk under the Nordic Centre of Excellence (ARCPATH, 76654), and the Trond Mohn Foundation under the project BFS2018TMT01. NorCPM‐v1 reanalysis received a grant for computer time from the Norwegian Program for supercomputer (NOTUR2, project NN9039K) and a storage grant (NORSTORE, NS9039K). Data for the figures are available to download (from https://doi.org/10.5281/zenodo.2598509). Data from some reanalysis products are available to download (from http://marine.copernicus.eu/services-portfolio/access-to-products/) under product names GLOBAL_REANALYSIS_PHY_001_025 (GLORYS2v4), GLOBAL_REANALYSIS_PHY_001_026 (C‐GLORSv7, GLORYS2v4, GloSea5 and ORAS5) and GLOBAL_REANALYSIS_PHY_001_030 (GLORYS12V1).
    Description: 2020-05-06
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 6
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 22 (2008): GB2026, doi:10.1029/2007GB002963.
    Description: We explored the role of aquatic systems in the global N cycle using a spatially distributed, within-basin, aquatic nitrogen (N) removal model, implemented within the Framework for Aquatic Modeling in the Earth System (FrAMES-N). The model predicts mean annual total N (TN) removal by small rivers (with drainage areas from 2.6–1000 km2), large rivers, lakes, and reservoirs, using a 30′ latitude × longitude river network to route and process material from continental source areas to the coastal zone. Mean annual aquatic TN removal (for the mid-1990s time period) is determined by the distributions of aquatic TN inputs, mean annual hydrological characteristics, and biological activity. Model-predicted TN concentrations at basin mouths corresponded well with observations (median relative error = −12%, interquartile range of relative error = 85%), an improvement over assumptions of uniform aquatic removal across basins. Removal by aquatic systems globally accounted for 14% of total N inputs to continental surfaces, but represented 53% of inputs to aquatic systems. Integrated aquatic removal was similar in small rivers (16.5% of inputs), large rivers (13.6%), and lakes (15.2%), while large reservoirs were less important (5.2%). Bias related to runoff suggests improvements are needed in nonpoint N input estimates and/or aquatic biological activity. The within-basin approach represented by FrAMES-N will improve understanding of the freshwater nutrient flux response to anthropogenic change at global scales.
    Description: This work was funded by NASA-IDS (NNXO7AF28G, NNG04GH75G), NSF-LTER OCE-9726921, and NOAA (NA17RJ2612 – 344 to Princeton University).
    Keywords: Nitrogen ; River network ; Global
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 14 (1975), S. 2025-2033 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism of Ac-(Ala)x-OMe and H-Lys-(Lys)x-OH with x = 1, 2, 3, and 4 has been measured in aqueous solutions. The oligomers with x = 4 show similar circular dichroism spectra in water when the lysyl amino groups are protonated, and they respond in similar fashion to heating and to sodium perchlorate. Both oligomers at 15°C exhibit a positive circular dichroism band at 217-218 nm, which is eliminated by the isothermal addition of 4 M sodium perchlorate or by heating. The positive circular dichroism of the lysine oligomer is also eliminated when the pH is elevated to deprotonate the amino groups. Positive circular dichroism is still observed for Ac-(Ala)4-OMe at elevated pH. Circular dichroism spectra have been estimated for poly(L-alanine) and poly(L-lysine) as statistical coils under the above conditions, based on the trends established with the oligomers. Poly(L-lysine) and poly(L-alanine) are predicted to exhibit similar circular dichroism behavior in aqueous solution so long as the lysyl amino groups are protonated. The circular dichroism of the statistical coil of poly(L-lysine), but not poly(L-alanine), is predicted to change when the pH is elevated sufficiently to deprotonate the lysyl amino groups. These results suggest that the unionized lysyl side chains participate in interactions that are not available to poly(L-alanine). Hydrophobic interactions may occur between the unionized lysyl side chains. Protonation of the lysyl amino groups is proposed to disrupt these interactions, causing poly(L-alanine) and protonated poly(L-lysine) to have similar circular dichroism properties.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 21 (1982), S. 1153-1166 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic studies of the binding of adamantanecarboxylate to cyclodextrins have been made as a function of temperature and added organic cosolvent (methanol) using flow microcalorimetry. The negative heat capacity change associated with the adamantanecar-boxylate/β-cyclodextrin interaction and the fact that the interaction is weakened by the addition of methanol implicate the binding process as being a hydrophobically driven one. The negative enthalpy change (ΔH0 = -5.5 kcal/mol) and near-zero entropy change (ΔS0 = 1.5 cal/mol deg) are quite different from the values normally expected for a hydrophobic bond, indicating that other bonding forces are important in addition to the hydrophobic effect. The relative contribution of the hydrophobic effect and other bonding forces (most likely van der Waals forces) to the overall binding was judged from an analysis of the dependence of the thermodynamics of the association process on the surface tension of the water-methanol mixtures following a model for “solvophobic” bonding described by Sinanoglu [Molecular Associations in Biology (1968) Academic Press, New York, pp. 427-445]. From this analysis, adamantane-carboxylate/cyclodextrin complex formation is found to be driven to the extent of -1.9 kcal/mol by the hydrophobic effect. Furthermore, the hydrophobic driving force is found to be characterized by a positive ΔS0 of 10 cal/mol deg. The remaining free energy of binding (and the ΔH0 of binding of ∼-6 kcal/mol) is then due to the intrinsic (surface-tension-independent) van der Waals interaction between the ligand and cyclodextrin cavity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 100 (1967), S. 271-279 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Der Diphenoxy-phosphoryl-Rest ist eine zur Blockierung der 2-Aminogruppen in Aminozuckern geeignete Schutzgruppe, die die Koenigs-Knorr-Synthese zu 1→3-verknüpften Disacchariden mit zwei Aminozucker-Einheiten ermöglicht. Kondensation von 2-[Diphenoxy-phosphorylamino]-3.4.6-tri-O-acetyl-2-desoxy-α-D-glucopypyranosylbromid (5) mit der an der 3-Hydroxylgruppe unblockierten Verbindung 2 führt bevorzugt zum 1→3-β-verknüpften Disaccharid 8a. Über eine Reihe von Entblockierungsschritten ist daraus 2-Acetamino-3-O-[2-acetamino-2-desoxy-β-D-glucopyranosyl]-2-desoxy-α-D-glucopyranose (12) in kristallisierter Form erhältlich.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 11 (1977), S. 1043-1043 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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