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  • 1
    Publication Date: 2020-07-10
    Description: The alkenone-pCO2 method is one of the most widely used approaches to reconstruct atmospheric CO2 in the Cenozoic. The method depends upon fractionation of stable carbon isotopes during algal photosynthesis, expressed as ep37:2, and a physiological scaling parameter, b, that accounts for biological factors such as growth rate, cell size, and membrane permeability. Alkenone-derived CO2 records for the late Pleistocene, however, are poorly correlated with ice core CO2, challenging the classic model that considers most of the CO2 used for coccolithophore photosynthesis to be acquired through simple diffusion. In this study, we investigate the nature of the b term and the underlying patterns of the sensitivity of ep37:2 to pCO2 changes. We generated two new ep37:2 records from the South China Sea (MD01-2392) and tropical Atlantic Ocean (ODP 668B) and compiled other published ep37:2 records over glacial-interglacial cycles. Using the ep37:2 data, ocean temperature estimates, and ice core CO2, we were able to back-calculate the corresponding values of b. At all locations, b varies over glacial cycles. The highest values of b correspond to peak interglacial stages, indicating that the phytoplankton growth rate is faster or cell size is smaller during interglacials than during glacial periods. We further show that the range of ep37:2 between glacial and interglacial conditions, Dep37:2, scales with growth conditions, consistent with the predictions of the carbon isotope fractionation model based on CO2 diffusion. In other words, the sensitivity of ep37:2 to pCO2 changes increases where the modern b values are large, contradicting the recommendations that oligotrophic sites are the best for alkenone-CO2 applications because of the presumed stability of b. Using the average back-calculated b value for each site, the composite pCO2 estimates from MD01-2392 and ODP 668B – the two sites with adequate Dep37:2 sensitivity – show broad agreement with the ice core CO2 record.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 2
    Publication Date: 2014-06-25
    Description: wo commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3–4°C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0–1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0°C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the “true” (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 3
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    Elsevier
    In:  EPIC3Encyclopedia of Ocean Sciences, Encyclopedia of Ocean Sciences, Third Edition, Vol 1, Elsevier, 10 p., pp. 235-244, ISBN: 978-0-12-813081-0
    Publication Date: 2019-05-20
    Repository Name: EPIC Alfred Wegener Institut
    Type: Inbook , peerRev
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 72 (2008): 4577-4594, doi:10.1016/j.gca.2008.06.021.
    Description: Understanding the supply and preservation of glycerol dibiphytanyl glycerol tetraethers (GDGTs) in marine sediments helps inform their use in paleoceanography. Compound-specific radiocarbon measurements of sedimentary alkenones from multiple environments have been used to gain insight into processes that affect paleo-temperature reconstructions. Similar analyses are warranted to investigate how analogous processes affecting GDGTs impact TEX86 paleotemperatures. Here we present radiocarbon measurements on individual GDGTs from Bermuda Rise and Santa Monica Basin sediments and discuss the results in the context of previous studies of co-depositional alkenones and foraminifera. The 149 C contents of GDGTs and planktonic foraminifera in Bermuda Rise are very similar, suggesting a local source; and TEX86- derived temperatures agree more closely with foraminiferal temperatures than do temperatures. In contrast, GDGTs in Santa Monica Basin are depleted in 1412 C relative to both alkenones and foraminifera, and TEX86 temperatures agree poorly with known surface water values. We propose three possible factors that could explain these results: (i) GDGTs may be labile relative to alkenones during advective transport through oxic waters; (ii) archaeal production deep in the water column may contribute 1416 C-depleted GDGTs to sediments; and (iii) some GDGTs also may derive from sedimentary archaeal communities. Each of these three processes is likely to occur with varying relative importance depending on geographic location. The latter two may help to explain why TEX86 temperature reconstructions from Santa Monica Basin do not appear to reflect actual sea surface temperatures. Terrigenous GDGTs are unlikely to be major contributors to Bermuda Rise or Santa Monica Basin sediments, based on values of the BIT index. The results also indicate that the crenarchaeol regioisomer is governed by processes different from other GDGTs. Individual measurements of the crenarchaeol regioisomer are significantly depleted in 1424 C relative to co-occurring GDGTs, indicating an alternative origin for this compound that presently remains unknown. Re-examination of the contribution of crenarchaeol regioisomer to the TEX86 index shows that it is a significant influence on the sensitivity of temperature reconstructions.
    Description: This work was supported by the David & Lucille Packard Foundation and by NSF-OCE-0241363 and EAR-0311937 (to A.P.).
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2009. 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 10 (2009): Q03012, doi:10.1029/2008GC002221.
    Description: Recently, two new proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) were proposed, i.e., the TEX86 proxy for sea surface temperature reconstructions and the BIT index for reconstructing soil organic matter input to the ocean. In this study, fifteen laboratories participated in a round robin study of two sediment extracts with a range of TEX86 and BIT values to test the analytical reproducibility and repeatability in analyzing these proxies. For TEX86 the repeatability, indicating intra-laboratory variation, was 0.028 and 0.017 for the two sediment extracts or ±1–2°C when translated to temperature. The reproducibility, indicating among-laboratory variation, of TEX86 measurements was substantially higher, i.e., 0.050 and 0.067 or ±3–4°C when translated to temperature. The latter values are higher than those obtained in round robin studies of Mg/Ca and U37 k′ paleothermometers, suggesting the need to primarily improve compatibility between labs. The repeatability of BIT measurements for the sediment with substantial amounts of soil organic matter input was relatively small, 0.029, but reproducibility was large, 0.410. This large variance could not be attributed to specific equipment used or a particular data treatment. We suggest that this may be caused by the large difference in the molecular weight in the GDGTs used in the BIT index, i.e., crenarchaeol versus the branched GDGTs. Potentially, this difference gives rise to variable responses in the different mass spectrometers used. Calibration using authentic standards is needed to establish compatibility between labs performing BIT measurements.
    Keywords: TEX86 ; BIT ; Round robin ; HPLC/MS
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 6
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution October 1999
    Description: Compound-specific carbon isotopic (δ13C and Δ14C) data are reported for lipid biomarkers isolated from Santa Monica Basin (SMB) and Santa Barbara Basin (SBB) surface sediments. These organic compounds represent phytoplanktonic, zooplanktonic, bacterial, archaeal, terrestrial, and fossil carbon sources. The lipids include long-chain n-alkanes, fatty acids (as FAMEs), n-alcohols, C30 mid-chain ketols and diols, sterols, hopanols, and ether-linked C4o-biphytanes of Archaea. The data show that the carbon source for most of the biomarkers is marine euphotic zone primary production or subsequent heterotrophic consumption of this biomass. Two lipid classes represent exceptions to this finding. Δ14C values for the n-alkanes are consistent with mixed fossil and contemporary terrestrial plant sources. The archaeal isoprenoid data reflect chemoautotrophic growth below the euphotic zone. The biomarker class most clearly representing marine phytoplanktonic production is the sterols. It is suggested, therefore, that the sterols could serve as paleoceanographic tracers for surface-water DIC. The isotopic data are used to construct two algebraic models. The first calculates the contributions of fossil and modem vascular plant carbon to 5MB n-alkanes. This model indicates that the Δ14C of the modern component is +235% (post-bomb) or 0% (pre-bomb). The second model uses these values to determine the origin of sedimentary TOC. The results are comparable to estimates based on other approaches and suggest that ~60% of SMB TOC is of marine origin, modern terrestrial and fossil sources contribute ~10% each, and the remaining ~20% is of unknown origin.
    Description: This work was supported by National Science Foundation grants to T. I. Eglinton (OCE-94l5568, OCE-9809624, OCE-9708478), a National Institute of Standards and Technology contract to T. I. Eglinton (43NANB615740), and the NOSAMS National Science Foundation cooperative agreements (OCE-930l0l5, OCE-9807266). I received support from an MIT Ida Green Graduate Student Fellowship and a US EPA STAR Graduate Student Fellowship.
    Keywords: Carbon ; Isotopes ; Biochemical markers ; Biogeochemistry ; Roger Revelle (Ship) Cruise Pulse-32
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 7
    Publication Date: 2022-05-26
    Description: Author Posting. © American Geophysical Union, 2013. 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 14 (2013): 5263–5285, doi:10.1002/2013GC004904.
    Description: Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility ±3–4°C when translated to temperature) but a large spread in BIT measurements (reproducibility ±0.41 on a scale of 0–1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0°C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the “true” (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.
    Description: S.S. thanks the Netherlands Organisation for Scientific Research (NWO) for financial support through a VICI grant and Jaap van der Meer for advice and support on the statistical analysis. A.P. thanks Susan Carter for laboratory assistance and NSF-OCE for funding. A.R.M. thanks Jordi Coello and N uria Moraleda for advice and support on the statistical analysis and Spanish Ministry for research and innovation (MICIIN) for funding. V.G. thanks Xavier Philippon and Carl Johnson for technical assistance. K.G. and M.W. thank the Australian Research Council and John de Laeter Centre for funding toward the LC-MS system, and ARC Fellowship awarded to K.G. C.L.Z. thanks the State Key Laboratory of Marine Geology and the Chinese ‘‘National Thousand Talents’’ program for supporting the LC-MS work performed at Tongji University.
    Description: 2014-06-20
    Keywords: TEX86 ; BIT ; GDGT ; Round robin
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: text/plain
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  • 8
    Publication Date: 2022-10-26
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Elling, F. J., Hemingway, J. D., Kharbush, J. J., Becker, K. W., Polik, C. A., & Pearson, A. Linking diatom-diazotroph symbioses to nitrogen cycle perturbations and deep-water anoxia: insights from Mediterranean sapropel events. Earth and Planetary Science Letters, 571, (2021): 117110, https://doi.org/10.1016/j.epsl.2021.117110.
    Description: Elevated organic matter (OM) export flux promotes marine anoxia, thus increasing carbon sequestration efficiency and decreasing atmospheric carbon dioxide levels. However, the mechanisms that trigger and sustain anoxic events—particularly those associated with nutrient-poor, oligotrophic surface waters—remain poorly constrained. Mediterranean Sea sapropels are well-preserved sediments deposited during episodic anoxic events throughout the Plio-Pleistocene; as such, they may provide unique insight into the biogeochemical and ecological drivers of—and responses to—marine anoxia. Using biomarker distributions, we demonstrate that anaerobic ammonium oxidizing (anammox) bacteria and diazotrophic endosymbionts of mat- and/or raft-forming diatoms were both abundant during sapropel events, particularly in the Ionian and Libyan seas. In these sapropels, the carbon isotope compositions of anammox biomarkers directly capture progressive 13C-depletion in deep-water dissolved inorganic carbon, indicating sustained carbon sequestration. To explain these observations, we propose a reinforcing feedback whereby initial nutrient and/or circulation perturbations promote fixed nitrogen loss via intensified anammox and heterotrophic denitrification, which in turn favors proliferation of rapidly sinking diatom-diazotroph symbiotic consortia, increases OM burial flux, and sustains anoxia. This mechanism resolves the long-standing conundrum that small and buoyant diazotrophs are apparently associated with high OM export during periods of marine anoxia and oligotrophy.
    Description: This work was funded through the Gordon and Betty Moore Foundation and US National Science Foundation grants 1843285, 1702262 and 1349126 (to A.P.). Additional financial support was provided by the Postdoctoral Program at the Woods Hole Oceanographic Institution and U.S. Geological Survey (K.W.B.).
    Keywords: Nammox ; Anoxia ; Compound-specific, δ13, C ; Diatom-diazotroph symbioses ; N2-fixation ; Mediterranean sapropels
    Repository Name: Woods Hole Open Access Server
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  • 9
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    Unknown
    PANGAEA
    In:  Supplement to: Hurley, Sarah J; Close, Hilary G; Elling, Felix J; Jasper, C E; Gospodinova, K; McNichol, Ann P; Pearson, Ann (2019): CO2-dependent carbon isotope fractionation in Archaea, Part II: The marine water column. Geochimica et Cosmochimica Acta, 261, 383-395, https://doi.org/10.1016/j.gca.2019.06.043
    Publication Date: 2023-02-18
    Description: Stable carbon isotope ratios of archaeal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids have been proposed as a proxy to infer past changes in the carbon isotope composition (δ13C) of dissolved inorganic carbon (DIC). The premise for reconstructing paleo-δ13CDIC from GDGTs is based on observations of relatively constant δ13CGDGT values in recent depositional environments. Marine Thaumarchaeota, thought to be the dominant source of GDGTs to marine sediments, fix inorganic carbon using the 3-hydroxypropionate/4-hydroxybutyrate (3HP/4HB) pathway, which is specific to HCO3- as the substrate. Bicarbonate-dependent autotrophy has been the basis for predicting that the stable carbon isotopic composition of GDGTs (δ13CGDGT) should vary in parallel with water column δ13CDIC values, because HCO3- is by far the dominant fraction of DIC in modern seawater. However, this relationship has never been systematically tested. Here we examine the carbon isotopic composition of GDGTs from four water column profiles in the Southwest and Equatorial Atlantic Ocean. Values of δ13CGDGT increase with depth in the water column, in contrast to the characteristic decrease in δ13CDIC values. These divergent trends imply a decrease in the observed total biosynthetic isotope effect (𝜀Ar) with depth, i.e., the offset between δ13CDIC and δ13CGDGT is not constant. Instead, we find that values of 𝜀Ar specifically correlate with oceanographic variables associated with extent of organic remineralization, decreasing as CO2 concentration increases. This observed relationship is consistent in both magnitude and direction with the results of an isotope flux-balance model for Thaumarchaeota that suggests 𝜀Ar should be sensitive to growth rate (µ) and CO2 availability under conditions of atmospheric pCO2 〈 4 times the pre-anthropogenic Holocene level. Further tests of the sensitivity of 𝜀Ar to µ and CO2 in the modern marine environment will be essential to exploring the potential for a new, archaeal lipid-derived pCO2 paleobarometer.
    Keywords: compound-specific carbon isotopic composition; crenarchaeol; GDGT
    Type: Dataset
    Format: application/zip, 3 datasets
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  • 10
    Publication Date: 2023-02-18
    Keywords: 20130328_2309_001; 20130329_1202_001; 20130329_1905_001; 20130405_2046_001; 20130417_2317_001; 20130504_0334_001; compound-specific carbon isotopic composition; crenarchaeol; Date/time end; Date/time start; DEPTH, sediment/rock; Event label; GDGT; KN210-04; Knorr; McLane Pump; McLP; Number; Sample code/label; Station label; δ13C, dissolved inorganic carbon; δ13C, dissolved inorganic carbon, standard deviation
    Type: Dataset
    Format: text/tab-separated-values, 287 data points
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