Boron, carbon, and oxygen isotopic composition of brachiopod shells: Intra-shell variability, controls, and potential as a paleo-pH recorder
The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extend...
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Published in | Chemical geology Vol. 340; pp. 32 - 39 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
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Elsevier B.V
01.02.2013
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Abstract | The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extending the boron isotope record as far back as the Cambrian. Here we present stable carbon, oxygen, and boron isotopic measurements of modern Terebratulid brachiopod calcite in comparison with environmental pH estimates calculated from oceanographic data. Geochemical transects along the length and depth of single shells confirm previously published trends in carbon and oxygen isotopic composition. In the outer surface (primary and outermost secondary layers), δ11B covaries with δ13C and δ18O, with more negative values in the outer and more positive values in the middle of the shell. However, δ11B deviates from δ13C and δ18O in the inner part of the secondary layer, where the δ13C and δ18O values are more positive and near equilibrium, whereas δ11B returns to more negative values. A comparison of different specimens of the species Terebratalia transversa (Sowerby, 1846) and Laqueus californianus (Küster, 1844) microsampled from the middle part of the fibrous secondary layer demonstrates a clear correlation to ambient pH with a sensitivity similar to other empirical calibration curves for cultured planktic foraminifers, corals, and inorganic calcite. The relationship in other species is less clear and significantly offset, necessitating the use of a single species or a cross-calibration method with other species in paleo-pH reconstructions.
► Brachiopod shells exhibit significant, systematic variability in boron, carbon, and oxygen isotopes. ► Significant offsets are found in boron isotopic composition of different brachiopod species. ► Two species show a correlation between δ11B and environmental pH similar to other carbonates. ► Brachiopod shell calcite is a promising archive for use in reconstructing paleo-pH in deep time. |
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AbstractList | The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO₂ on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extending the boron isotope record as far back as the Cambrian. Here we present stable carbon, oxygen, and boron isotopic measurements of modern Terebratulid brachiopod calcite in comparison with environmental pH estimates calculated from oceanographic data. Geochemical transects along the length and depth of single shells confirm previously published trends in carbon and oxygen isotopic composition. In the outer surface (primary and outermost secondary layers), δ¹¹B covaries with δ¹³C and δ¹⁸O, with more negative values in the outer and more positive values in the middle of the shell. However, δ¹¹B deviates from δ¹³C and δ¹⁸O in the inner part of the secondary layer, where the δ¹³C and δ¹⁸O values are more positive and near equilibrium, whereas δ¹¹B returns to more negative values. A comparison of different specimens of the species Terebratalia transversa (Sowerby, 1846) and Laqueus californianus (Küster, 1844) microsampled from the middle part of the fibrous secondary layer demonstrates a clear correlation to ambient pH with a sensitivity similar to other empirical calibration curves for cultured planktic foraminifers, corals, and inorganic calcite. The relationship in other species is less clear and significantly offset, necessitating the use of a single species or a cross-calibration method with other species in paleo-pH reconstructions. The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extending the boron isotope record as far back as the Cambrian. Here we present stable carbon, oxygen, and boron isotopic measurements of modern Terebratulid brachiopod calcite in comparison with environmental pH estimates calculated from oceanographic data. Geochemical transects along the length and depth of single shells confirm previously published trends in carbon and oxygen isotopic composition. In the outer surface (primary and outermost secondary layers), δ11B covaries with δ13C and δ18O, with more negative values in the outer and more positive values in the middle of the shell. However, δ11B deviates from δ13C and δ18O in the inner part of the secondary layer, where the δ13C and δ18O values are more positive and near equilibrium, whereas δ11B returns to more negative values. A comparison of different specimens of the species Terebratalia transversa (Sowerby, 1846) and Laqueus californianus (Küster, 1844) microsampled from the middle part of the fibrous secondary layer demonstrates a clear correlation to ambient pH with a sensitivity similar to other empirical calibration curves for cultured planktic foraminifers, corals, and inorganic calcite. The relationship in other species is less clear and significantly offset, necessitating the use of a single species or a cross-calibration method with other species in paleo-pH reconstructions. ► Brachiopod shells exhibit significant, systematic variability in boron, carbon, and oxygen isotopes. ► Significant offsets are found in boron isotopic composition of different brachiopod species. ► Two species show a correlation between δ11B and environmental pH similar to other carbonates. ► Brachiopod shell calcite is a promising archive for use in reconstructing paleo-pH in deep time. The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales. Because of their excellent preservation and extensive fossil record throughout the Phanerozoic, brachiopods are a promising candidate for extending the boron isotope record as far back as the Cambrian. Here we present stable carbon, oxygen, and boron isotopic measurements of modern Terebratulid brachiopod calcite in comparison with environmental pH estimates calculated from oceanographic data. Geochemical transects along the length and depth of single shells confirm previously published trends in carbon and oxygen isotopic composition. In the outer surface (primary and outermost secondary layers), delta 11B covaries with delta 13C and delta 18O, with more negative values in the outer and more positive values in the middle of the shell. However, delta 11B deviates from delta 13C and delta 18O in the inner part of the secondary layer, where the delta 13C and delta 18O values are more positive and near equilibrium, whereas delta 11B returns to more negative values. A comparison of different specimens of the species Terebratalia transversa (Sowerby, 1846) and Laqueus californianus (Kuester, 1844) microsampled from the middle part of the fibrous secondary layer demonstrates a clear correlation to ambient pH with a sensitivity similar to other empirical calibration curves for cultured planktic foraminifers, corals, and inorganic calcite. The relationship in other species is less clear and significantly offset, necessitating the use of a single species or a cross-calibration method with other species in paleo-pH reconstructions. |
Author | Hönisch, Bärbel Spero, Howard J. Rasbury, E. Troy Hemming, N. Gary Penman, Donald E. |
Author_xml | – sequence: 1 givenname: Donald E. surname: Penman fullname: Penman, Donald E. email: dpenman@ucsc.edu organization: Department of Earth and Environmental Sciences and Lamont-Doherty Earth Observatory of Columbia University, Palisades, NY, 10964-8000, USA – sequence: 2 givenname: Bärbel surname: Hönisch fullname: Hönisch, Bärbel organization: Department of Earth and Environmental Sciences and Lamont-Doherty Earth Observatory of Columbia University, Palisades, NY, 10964-8000, USA – sequence: 3 givenname: E. Troy surname: Rasbury fullname: Rasbury, E. Troy organization: Department of Geosciences, State University of New York at Stony Brook, Stony Brook, NY, 11794, USA – sequence: 4 givenname: N. Gary surname: Hemming fullname: Hemming, N. Gary organization: School of Earth and Environmental Sciences, Queen College, Flushing, NY, 11367-1597, USA – sequence: 5 givenname: Howard J. surname: Spero fullname: Spero, Howard J. organization: Department of Geology, University of California Davis, Davis, California, 95616, USA |
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Snippet | The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO2 on Pleistocene and Cenozoic timescales.... The boron isotopic composition of biogenic carbonates has been used to reconstruct seawater pH and atmospheric pCO₂ on Pleistocene and Cenozoic timescales.... |
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SubjectTerms | Boron Boron isotopes Brachiopod Brachiopoda Calcite Carbon carbonates corals Foraminifera Fossils isotopes Laqueus californianus Marine oxygen Reconstruction Recorders seawater Seawater pH Shells Stable isotopes Terebratalia transversa |
Title | Boron, carbon, and oxygen isotopic composition of brachiopod shells: Intra-shell variability, controls, and potential as a paleo-pH recorder |
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