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  • nitrogen isotopes  (2)
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  • 1
    Publication Date: 2023-01-21
    Description: Fossil‐bound organic material holds great potential for the reconstruction of past changes in nitrogen (N) cycling. Here, with a series of laboratory experiments, we assess the potential effect of oxidative degradation, fossil dissolution, and thermal alteration on the fossil‐bound N isotopic composition of different fossil types, including deep and shallow water scleractinian corals, foraminifera, diatoms and tooth enamel. Our experiments show that exposure to different oxidizing reagents does not significantly affect the N isotopic composition or N content of any of the fossil types analyzed, demonstrating that organic matter is well protected from changes in the surrounding environment by the mineral matrix. In addition, we show that partial dissolution (of up to 70%–90%) of fossil aragonite, calcite, opal, or enamel matrixes has a negligible effect on the N isotopic composition and N content of the fossils. These results suggest that the isotopic composition of fossil‐bound organic material is relatively uniform, and also that N exposed during dissolution is lost without significant isotopic discrimination. Finally, our heating experiments show negligible changes in the N isotopic composition and N content of all fossil types at 100°C. At 200°C and hotter, any N loss and associated nitrogen isotope changes appear to be directly linked to the sensitivity of the mineral matrix to thermal stress, which depends on the biomineral type. These results suggest that, so long as high temperature does not compromise the mineral structure, the biomineral matrix acts as a closed system with respect to N, and the N isotopic composition of the fossil remains unchanged.
    Description: Plain Language Summary: The ratio of the heavy and light isotopes of nitrogen (15N and 14N) in the organic material contained within the mineral structure of fossils can be used to reconstruct past changes in biological and chemical processes. With a series of laboratory experiments, we evaluate the potential effects of chemical conditions, fossil dissolution, and heating on the nitrogen isotopic composition (15N/14N ratio) of corals, foraminifera, diatoms and tooth enamel. Our results indicate that these processes do not have a significant effect on the 15N/14N of fossils, suggesting that the mineral matrix provides a barrier that isolates a fossil's organic nitrogen from the surrounding environment, preventing alteration of its 15N/14N. In addition, we show that if part of the fossil‐bound organic nitrogen is exposed by dissolution or heating, it is lost without affecting the 15N/14N of the organic material that remains in the mineral. These findings imply that the original 15N/14N ratio incorporated by the organism is preserved in the geologic record. Therefore, measurements of the nitrogen isotopes on fossils can provide faithful biological, ecological, and environmental information about the past.
    Description: Key Points: Fossil‐bound organic matter is well protected by the mineral matrix from chemical changes in the surrounding environment. Partial dissolution of fossil calcite, aragonite, opal, and enamel has a negligible effect on their N isotopic composition and N content. During heating, fossil N content and isotopic composition remains unchanged if the structure of the inorganic matrix is not compromised.
    Description: Max Planck Society
    Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
    Description: US National Science Foundation
    Description: Paul Crutzen Nobel Prize Fellowship
    Description: https://doi.org/10.5281/zenodo.6884681
    Keywords: ddc:551.9 ; nitrogen isotopes ; diagenesis ; foraminifera ; corals ; diatoms ; teeth
    Language: English
    Type: doc-type:article
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  • 2
    Publication Date: 2021-09-29
    Description: Bulk sediment δ15N records from the eastern tropical Pacific (ETP) extending back to the last ice age most often show low glacial δ15N, then a deglacial δ15N maximum, followed by a gradual decline to a late Holocene δ15N that is typically higher than that of the Last Glacial Maximum (LGM). The lower δ15N of the LGM has been interpreted to reflect an ice age reduction in water column denitrification. We report foraminifera shell‐bound nitrogen isotope (FB‐δ15N) measurements for the two species Neogloboquadrina dutertrei and Neogloboquadrina incompta over the last 35 ka in two sediment cores from the eastern equatorial Pacific (EEP), both of which have the typical LGM‐to‐Holocene increase in bulk sediment δ15N. FB‐δ15N contrasts with bulk sediment δ15N by not indicating a lower δ15N during the LGM. Instead, the FB‐δ15N records are dominated by a deglacial δ15N maximum, with comparable LGM and Holocene values. The lower LGM δ15N of the bulk sediment records may be an artifact, possibly related to greater exogenous N inputs and/or weaker sedimentary diagenesis during the LGM. The new data raise the possibility that the previously inferred glacial reduction in ETP water column denitrification was incorrect. A review of reconstructed ice age conditions and geochemical box model output provides mechanistic support for this possibility. However, equatorial ocean circulation and nitrate‐rich surface water overlying both core sites allow for other possible interpretations, calling for replication at non‐equatorial ETP sites.
    Description: Plain Language Summary: The 15N/14N ratio of sediments provides information on the past marine nitrogen (N) cycle through the production of N‐bearing organic matter in the surface ocean and its burial in the sediments. Previous measurements of the sedimentary 15N/14N ratio in the eastern equatorial Pacific (EEP) indicate lower values during the last ice age compared to the Holocene (the current warm period). This has been interpreted to reflect an ice age reduction in the oceanic N loss process known as “denitrification” that occurs between 200 and 500 m depth in this region of the ocean. However, the 15N/14N ratio measured on the whole sediment can be biased by biological and chemical processes in the sediments and by foreign N inputs. To avoid these complications, we measured the 15N/14N ratio of organic N embedded in the calcite shell of unicellular zooplankton (foraminifera) in two sediment cores from the EEP. We found similar foraminifera‐bound 15N/14N ratios during the last ice and the Holocene. This may argue against the long‐held interpretation of a reduction in denitrification during the last ice age. However, the oceanographic setting of these equatorial cores leaves open alternative interpretations, calling for further work at other eastern tropical Pacific sites.
    Description: Key Points: Foraminifera‐bound δ15N was similar during the last ice age and the Holocene in the eastern equatorial Pacific, unlike bulk sedimentary δ15N. Bulk sediment δ15N is likely biased to lower ice age values by foreign N inputs and weaker sedimentary diagenesis. The foraminifera‐bound δ15N data may reflect that water column denitrification was not reduced during the last glacial period.
    Description: Swiss National Science Foundation
    Description: US National Science Foundation
    Description: Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung http://dx.doi.org/10.13039/501100001711
    Description: National Science Foundation http://dx.doi.org/10.13039/100000001
    Keywords: 551.9 ; Pacific Ocean ; nitrogen isotopes ; denitrification ; suboxia ; Last Glacial Maximum ; Holocene
    Type: map
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