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  • 1
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    Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba (2021)
    Nature Research
    Details
    Publication Date: 2022-05-26
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Mayfield, K. K., Eisenhauer, A., Santiago Ramos, D. P., Higgins, J. A., Horner, T. J., Auro, M., Magna, T., Moosdorf, N., Charette, M. A., Gonneea, M. E., Brady, C. E., Komar, N., Peucker-Ehrenbrink, B., & Paytan, A. Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba. Nature Communications, 12(1), (2021): 148-020-20248-3, doi:10.1038/s41467-020-20248-3.
    Description: Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models.
    Description: We thank A. Beck, H. Dulai, I. Santos, C. Benitez-Nelson, W. Moore, A. Martin, and H. Windom for sample access. We also thank A. Kolevica, A. Heuser, H. Pryer, J. Middleton, R. Franks, F. Lon, N. Slater, and O. Šebek for their laboratory and analytical assistance. This material is based upon research supported by the National Science Foundation Graduate Research Fellowship Program and an internship provided through the U.S. Geological Survey Graduate Research Internship Program (GRIP). This research was also supported by grants from: the German Academic Exchange Service (DAAD), Northern California chapter of the Achievement Rewards for College Scientists Foundation, International Association of GeoChemistry, Geological Society of America, Northern California Geological Society, Myers Trust, Friends of Long Marine Lab, and UC MEXUS (to K.K.M.). We acknowledge funding from EU-ITN Horizon project 643084 (to A.E. and T.M.) and NSF grant Award Number 1259440 (to A.P.). We also acknowledge funding from NSF grant award number OCE-1736949 (to T.J.H.). Any use of trade, firm or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government.
    Repository Name: Woods Hole Open Access Server
    Type: Article
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    PAPER (OA)
  • 2
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    Coupling of oceanic carbon and nitrogen facilitates spatially resolved quantitative reconstruction of nitrate inventories (2018)
    Nature Research
    In:  Nature Communications, 9 (Article number 1217).
    Details
    Publication Date: 2021-03-19
    Description: Anthropogenic impacts are perturbing the global nitrogen cycle via warming effects and pollutant sources such as chemical fertilizers and burning of fossil fuels. Understanding controls on past nitrogen inventories might improve predictions for future global biogeochemical cycling. Here we show the quantitative reconstruction of deglacial bottom water nitrate concentrations from intermediate depths of the Peruvian upwelling region, using foraminiferal pore density. Deglacial nitrate concentrations correlate strongly with downcore δ13C, consistent with modern water column observations in the intermediate Pacific, facilitating the use of δ13C records as a paleo-nitrate-proxy at intermediate depths and suggesting that the carbon and nitrogen cycles were closely coupled throughout the last deglaciation in the Peruvian upwelling region. Combining the pore density and intermediate Pacific δ13C records shows an elevated nitrate inventory of 〉10% during the Last Glacial Maximum relative to the Holocene, consistent with a δ13C-based and δ15N-based 3D ocean biogeochemical model and previous box modeling studies.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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    DOI: 10.1038/s41467-018-03647-5
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 3
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    Ice volume and climate changes from a 6000 year sea-level record in French Polynesia (2018)
    Nature Research
    In:  Nature Communications, 9 (285).
    Details
    Publication Date: 2021-02-08
    Description: Mid- to late-Holocene sea-level records from low-latitude regions serve as an important baseline of natural variability in sea level and global ice volume prior to the Anthropocene. Here, we reconstruct a high-resolution sea-level curve encompassing the last 6000 years based on a comprehensive study of coral microatolls, which are sensitive low-tide recorders. Our curve is based on microatolls from several islands in a single region and comprises a total of 82 sea-level index points. Assuming thermosteric contributions are negligible on millennial time scales, our results constrain global ice melting to be 1.5–2.5 m (sea-level equivalent) since ~5500 years before present. The reconstructed curve includes isolated rapid events of several decimetres within a few centuries, one of which is most likely related to loss from the Antarctic ice sheet mass around 5000 years before present. In contrast, the occurrence of large and flat microatolls indicates periods of significant sea-level stability lasting up to ~300 years.
    Type: Article , PeerReviewed
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    DOI: 10.1038/s41467-017-02695-7
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 4
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    No detectable Weddell Sea Antarctic Bottom Water export during the Last and Penultimate Glacial Maximum (2020)
    Nature Research
    Details
    Publication Date: 2023-02-08
    Description: Weddell Sea-derived Antarctic Bottom Water (AABW) is one of the most important deep water masses in the Southern Hemisphere occupying large portions of the deep Southern Ocean (SO) today. While substantial changes in SO-overturning circulation were previously suggested, the state of Weddell Sea AABW export during glacial climates remains poorly understood. Here we report seawater-derived Nd and Pb isotope records that provide evidence for the absence of Weddell Sea-derived AABW in the Atlantic sector of the SO during the last two glacial maxima. Increasing delivery of Antarctic Pb to regions outside the Weddell Sea traced SO frontal displacements during both glacial terminations. The export of Weddell Sea-derived AABW resumed late during glacial terminations, coinciding with the last major atmospheric CO2 rise in the transition to the Holocene and the Eemian. Our new records lend strong support for a previously inferred AABW overturning stagnation event during the peak Eemian interglacial.
    Type: Article , PeerReviewed
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 5
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    Permian–Triassic mass extinction pulses driven by major marine carbon cycle perturbations (2020)
    Nature Research
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    Publication Date: 2023-02-08
    Description: The Permian/Triassic boundary approximately 251.9 million years ago marked the most severe environmental crisis identified in the geological record, which dictated the onwards course for the evolution of life. Magmatism from Siberian Traps is thought to have played an important role, but the causational trigger and its feedbacks are yet to be fully understood. Here we present a new boron-isotope-derived seawater pH record from fossil brachiopod shells deposited on the Tethys shelf that demonstrates a substantial decline in seawater pH coeval with the onset of the mass extinction in the latest Permian. Combined with carbon isotope data, our results are integrated in a geochemical model that resolves the carbon cycle dynamics as well as the ocean redox conditions and nitrogen isotope turnover. We find that the initial ocean acidification was intimately linked to a large pulse of carbon degassing from the Siberian sill intrusions. We unravel the consequences of the greenhouse effect on the marine environment, and show how elevated sea surface temperatures, export production and nutrient input driven by increased rates of chemical weathering gave rise to widespread deoxygenation and sporadic sulfide poisoning of the oceans in the earliest Triassic. Our findings enable us to assemble a consistent biogeochemical reconstruction of the mechanisms that resulted in the largest Phanerozoic mass extinction.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 6
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    Early Diagenetic Imprint on Temperature Proxies in Holocene Corals: A Case Study From French Polynesia (2020)
    Frontiers
    Details
    Publication Date: 2023-02-08
    Description: Coral-based reconstructions of sea surface temperatures (SSTs) using Sr/Ca, U/Ca and δ18O are important tools for quantitative analysis of past climate variabilities. However, post-depositional alteration of coral aragonite, particularly early diagenesis, restrict the accuracy of calibrated proxies even on young corals. Considering the diagenetic effects, we present new Mid to Late Holocene SST reconstructions on well-dated (U/Th: ∼70 yr to 5.4 ka) fossil Porites sp. collected from the Society Islands, French Polynesia. For few corals, quality pre-screening routines revealed the presence of secondary aragonite needles inside primary pore space, resulting in a mean increase in Sr/Ca ratios between 5-30%, in contrast to the massive skeletal parts. Characterized by a Sr/Ca above 10 mmol/mol, we interpret this value as the threshold between diagenetically altered and unaltered coral material. At a high-resolution, observed intra-skeletal variability of 5.4 to 9.9 mmol/mol probably reflects the physiological control of corals over their trace metal uptake, and individual variations controlled by CaCO3– precipitation rates. Overall, the Sr/Ca, U/Ca and δ18O trends are well correlated, but we observed a significant offset up to ± 7°C among the proxies on derived palaeo-SST estimates. It appears that the related alteration process tends to amplify temperature extremes, resulting in increased SST-U/Ca and SST-Sr/Ca gradients, and consequently their apparent temperature sensitivities. A relative SST reconstruction is still feasible by normalizing our records to their individual mean value defined as ΔSST. This approach shows that ΔSST records derived from different proxies agree with an amplitudinal variability of up to ± 2°C with respect to their Holocene mean value. Higher ΔSST values than the mean SSTs (Holocene warm periods) were recorded from ∼1.8 to ∼2.8 ka (Interval I), ∼3.7 to 4.0 ka (Interval III) and before ∼5 ka, while lower ΔSST values (Holocene cold periods, Interval II and IV) were recorded in between. The ensuing SST periodicity of ∼1.5 ka in the Society Islands record is in line with the solar activity reconstructed from 10Be and 14C production (Vonmoos et al., 2006), emphasizing the role of solar activity on climate variability during the Late Holocene.
    Type: Article , PeerReviewed
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 7
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    Organic Heterogeneities in Foraminiferal Calcite Traced Through the Distribution of N, S, and I Measured With NanoSIMS: A New Challenge for Element-Ratio-Based Paleoproxies? (2019)
    Frontiers
    In:  Frontiers in Earth Science, 7 (175).
    Details
    Publication Date: 2022-01-31
    Description: Oceanic oxygen decline due to anthropogenic climate change is a matter of growing concern. A quantitative oxygen proxy is highly desirable in order to identify and monitor recent dynamics as well as to reconstruct pre-Anthropocene changes in amplitude and extension of oxygen depletion. Geochemical proxies like foraminiferal I/Ca ratios seem to be promising redox proxies. Nevertheless, recent studies on microanalyses of benthic foraminiferal I/Ca ratios at the Peruvian oxygen minimum zone (OMZ) measured with secondary-ion mass spectrometry (SIMS) revealed a possible association of iodine with organic accumulations within the test. Here, we present a new study on the micro-distribution of nitrogen, sulfur, and iodine within the test walls of Uvigerina striata from the Peruvian OMZ measured with Nano-SIMS. A quantification of the foraminiferal I/Ca ratios from our NanoSIMS study is in good agreement with quantitative results from a previous SIMS study. Additionally, we compared uncleaned specimens with specimens that have been treated with an oxidative cleaning procedure. Both nitrogen and sulfur, which are used as tracer for organic matter, show a patchy distribution within the test walls of the uncleaned specimens and a statistically significant correlation with the iodine distribution. This patchy organic-rich phase has a different geochemical signature than the pristine calcitic parts of the test and another phase that shows a banding-like structure and that is characterized by a strong sulfur enrichment. All three elements, sulfur, nitrogen, and iodine, are strongly depleted in the cleaned specimens, even within the massive parts of the test walls that lack the connection with the test pores. These results indicate that the organic parts of the test walls are located inside a microporous framework within the foraminiferal calcite. This has to be considered in the interpretation of geochemical proxies on foraminiferal calcite, especially for microanalytical methods, since the chemical signature of these organic parts likely alters some element-to-calcium ratios within the foraminiferal test.
    Type: Article , PeerReviewed
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    DOI: 10.3389/feart.2019.00175
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 8
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    Calcite fibre formation in modern brachiopod shells (2019)
    Nature Research
    In:  Scientific Reports, 9 (598).
    Details
    Publication Date: 2022-01-31
    Description: The fibrous calcite layer of modern brachiopod shells is a hybrid composite material and forms a substantial part of the hard tissue. We investigated how cells of the outer mantle epithelium (OME) secrete calcite material and generate the characteristic fibre morphology and composite microstructure of the shell. We employed AFM, FE-SEM, and TEM imaging of embedded/etched, chemically fixed/decalcified and high-pressure frozen/freeze substituted samples. Calcite fibres are secreted by outer mantle epithelium (OME) cells. Biometric analysis of TEM micrographs indicates that about 50% of these cells are attached via hemidesmosomes to an extracellular organic membrane present at the proximal, convex surface of the fibres. At these sites, mineral secretion is not active. Instead, ion transport from OME cells to developing fibres occurs at regions of closest contact between cells and fibres, however only at sites where the extracellular membrane at the proximal fibre surface is not developed yet. Fibre formation requires the cooperation of several adjacent OME cells. It is a spatially and temporally changing process comprising of detachment of OME cells from the extracellular organic membrane, mineral secretion at detachment sites, termination of secretion with formation of the extracellular organic membrane, and attachment of cells via hemidesmosomes to this membrane.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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    DOI: 10.1038/s41598-018-36959-z
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 9
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    Endolithic Algae Affect Modern Coral Carbonate Morphology and Chemistry (2019)
    Frontiers
    In:  Frontiers in Earth Science, 7 (304).
    Details
    Publication Date: 2022-01-31
    Description: While burial diagenetic processes of tropical corals are well investigated, current knowledge about factors initiating early diagenesis remains fragmentary. In the present study, we focus on recent Porites microatolls, growing in the intertidal zone. This growth form represents a model organism for elevated sea surface temperatures (SSTs) and provides important but rare archives for changes close to the seawater/atmosphere interface with exceptional precision on sea level reconstruction. As other coral growth forms, microatolls are prone to the colonization by endolithic green algae. In this case, the algae can facilitate earliest diagenetic alteration of the coral skeleton. Algae metabolic activity not only results in secondary coral porosity due to boring activities, but may also initiate reprecipitation of secondary aragonite within coral pore space, a process not exclusively restricted to microatoll settings. In the samples of this initial study, we quantified a mass transfer from primary to secondary aragonite of around 4% within endolithic green algae bands. Using δ18O, δ13C, Sr/Ca, U/Ca, Mg/Ca, and Li/Mg systematics suggests that the secondary aragonite precipitation followed abiotic precipitation principles. According to their individual distribution coefficients, the different isotope and element ratios showed variable sensitivity to the presence of secondary aragonite in bulk samples, with implications for microatoll-based SST reconstructions. The secondary precipitates formed on an organic template, presumably originating from endolithic green algae activity. Based on laboratory experiments with the green algae Ostreobium quekettii, we propose a conceptual model that secondary aragonite formation is potentially accelerated by an active intracellular calcium transport through the algal thallus from the location of dissolution into coral pore spaces. The combined high-resolution imaging and geochemical approach applied in this study shows that endolithic algae can possibly act as a main driver for earliest diagenesis of coral aragonite starting already during a coral’s life span.
    Type: Article , PeerReviewed
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    Format: other
    DOI: 10.3389/feart.2019.00304
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 10
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    No freshwater-filled glacial Arctic Ocean (2022)
    Nature Research
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    Publication Date: 2024-02-07
    Type: Article , PeerReviewed
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    OceanRep: Article in a Scientific Journal - peer-reviewed
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