Clay authigenesis in carbonate-rich sediments and its impact on carbonate diagenesis

The Mg (δ^(26) Mg), Ca (δ^(44) Ca), and Sr ((^87)Sr⁄(^86)Sr ) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate δ^(26) Mg and (^87)Sr⁄(^86)Sr from ODP Site 806 Hole B and pore fluid δ^(26) Mg from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid δ^(26)Mg, specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid δ^(26)Mg values at all three sites range from -0.83 to -0.13‰ and exhibit a systematic increase with depth. Bulk carbonate δ^(26)Mg generally decrease with depth, ranging from -3.60 to -5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (~250-500 μm) from Site 762 range between -5.08 and -4.36‰. Residual siliciclastics at depths of ~105 to 145 mbsf at Site 762 have δ^(26)Mg values (-0.09 to 0.27‰) that are markedly higher than carbonate and pore fluid δ^(26)Mg values. Simple 1-D reactive transport modeling suggests that the general increase in pore fluid δ^(26)Mg with depth, accompanied by a decrease in carbonate δ^(26)Mg, is a result of calcite recrystallization (assuming an isotopic fractionation factor of ~0.9955). However, subtle but significant deviations from the carbonate recrystallization-only scenario suggest that another process impacts δ^(26)Mg at all three sites. Scanning electron microscope images document clay particles embedded in nannofossils and foraminiferal tests at Site 762, which suggest that clay authigenesis is active in carbonate sediments and could affect pore fluid δ^(26)Mg. The formation of secondary clays preferentially sequesters isotopically heavy Mg (α_(clay-Mg^(2+) )≈1.0005), driving pore fluid δ^(26)Mg to lower values. An increase in carbonate δ^(26)Mg within the clay-rich layer at Site 762 and an increase in bulk carbonate Na/Ca supports the hypothesis that clay authigenesis also impacts the preservation of proxy archives. Multi-component reactive transport modeling suggests that authigenic rates of ~1·10^(-13) mol/m^3/s (~3.15 µmol/m^3/a; assuming that the authigenic clay is sepiolite) can generate deviations from the carbonate recrystallization-only case by several tenths of a permil, indicating that carbonate sediment-associated clay authigenesis (CSCA) may be more relevant in deep-sea carbonate sections than has been previously considered.

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Metadata

Work Title Clay authigenesis in carbonate-rich sediments and its impact on carbonate diagenesis
Access
Open Access
Creators
  1. Matthew Fantle
Keyword
  1. Diagenesis
  2. Reactive transport modeling
  3. Calcium carbonate
  4. Ocean Drilling Program
  5. Mg isotopes
  6. Sr isotopes
  7. Ca isotopes
License CC BY-NC-SA 4.0 (Attribution-NonCommercial-ShareAlike)
Work Type Article
Acknowledgments
  1. This work was supported by funding from NSF Grant EAR-OCE-1154839 awarded to M.S.F and by a Blaustein Visiting Professorship at Stanford University. This research used samples and data provided by the Ocean Drilling Program (ODP). Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. The Cameca Nano-SIMS 50L in the Stanford Nano Shared Facilities (SNSF) was supported by NSF award #1542152.
Publisher
  1. Elsevier
Publication Date 2023
Subject
  1. Geology
  2. Geochemistry
  3. Isotope geochemistry
Language
  1. English
Publisher Identifier (DOI)
  1. https://doi.org/10.1016/j.gca.2023.02.002
Deposited February 03, 2023

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Version 1
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  • Created
  • Updated
  • Updated Acknowledgments Show Changes
    Acknowledgments
    • This work was supported by funding from NSF Grant EAR-OCE-1154839 awarded to M.S.F and by a Blaustein Visiting Professorship at Stanford University. This research used samples and data provided by the Ocean Drilling Program (ODP). Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. The Cameca Nano-SIMS 50L in the Stanford Nano Shared Facilities (SNSF) was supported by NSF award #1542152.
  • Added Creator Matthew Fantle
  • Added Table 1.csv
  • Added Table 2.csv
  • Added Table 3.csv
  • Added Table 4.csv
  • Added Table 5.csv
  • Added Table 6.csv
  • Added Table 7.csv
  • Added Table 8.csv
  • Added Table 9.csv
  • Added 762B-12H_area3_large_pyramid_dp.txt
  • Added 762B-16H_area2_upper_left_dp.txt
  • Added Lammers2019_expt3_std_area2_DP1_dp.txt
  • Added Spar_calcite_std_area1_long-piece_DP1_dp.txt
  • Added Table S1.csv
  • Added Table S2.csv
  • Added Table S3.csv
  • Added Table S4.csv
  • Added Table S5.csv
  • Updated License Show Changes
    License
    • https://creativecommons.org/licenses/by/4.0/
  • Updated License Show Changes
    License
    • https://creativecommons.org/licenses/by/4.0/
    • https://creativecommons.org/licenses/by-nc-sa/4.0/
  • Updated Description Show Changes
    Description
    • The Mg (δ^26 Mg), Ca (δ^44 Ca), and Sr ((_^87)Sr⁄(_^86)Sr ) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate δ^26 Mg and (_^87)Sr⁄(_^86)Sr from ODP Site 806 Hole B and pore fluid δ^26 Mg from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid δ26Mg, specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid δ26Mg values at all three sites range from -0.83 to -0.13‰ and exhibit a systematic increase with depth. Bulk carbonate δ26Mg generally decrease with depth, ranging from -3.60 to -5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (~250-500 μm) from Site 762 range between -5.08 and -4.36‰. Residual siliciclastics at depths of ~105 to 145 mbsf at Site 762 have δ26Mg values (-0.09 to 0.27‰) that are markedly higher than carbonate and pore fluid δ26Mg values. Simple 1-D reactive transport modeling suggests that the general increase in pore fluid δ26Mg with depth, accompanied by a decrease in carbonate δ26Mg, is a result of calcite recrystallization (assuming an isotopic fractionation factor of ~0.9955). However, subtle but significant deviations from the carbonate recrystallization-only scenario suggest that another process impacts δ^26 Mg at all three sites. Scanning electron microscope images document clay particles embedded in nannofossils and foraminiferal tests at Site 762, which suggest that clay authigenesis is active in carbonate sediments and could affect pore fluid δ^26 Mg. The formation of secondary clays preferentially sequesters isotopically heavy Mg (α_(clay-Mg^(2+) )≈1.0005), driving pore fluid δ^26 Mg to lower values. An increase in carbonate δ26Mg within the clay-rich layer at Site 762 and an increase in bulk carbonate Na/Ca supports the hypothesis that clay authigenesis also impacts the preservation of proxy archives. Multi-component reactive transport modeling suggests that authigenic rates of ~1·10-13 mol/m3/s (~3.15 µmol/m3/a; assuming that the authigenic clay is sepiolite) can generate deviations from the carbonate recrystallization-only case by several tenths of a permil, indicating that carbonate sediment-associated clay authigenesis (CSCA) may be more relevant in deep-sea carbonate sections than has been previously considered.
    • The Mg (δ^(26) Mg), Ca (δ^(44) Ca), and Sr ((_^87)Sr⁄(_^86)Sr ) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate δ^(26) Mg and (_^87)Sr⁄(_^86)Sr from ODP Site 806 Hole B and pore fluid δ^(26) Mg from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid δ^(26)Mg, specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid δ^(26)Mg values at all three sites range from -0.83 to -0.13‰ and exhibit a systematic increase with depth. Bulk carbonate δ^(26)Mg generally decrease with depth, ranging from -3.60 to -5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (~250-500 μm) from Site 762 range between -5.08 and -4.36‰. Residual siliciclastics at depths of ~105 to 145 mbsf at Site 762 have δ^(26)Mg values (-0.09 to 0.27‰) that are markedly higher than carbonate and pore fluid δ^(26)Mg values. Simple 1-D reactive transport modeling suggests that the general increase in pore fluid δ^(26)Mg with depth, accompanied by a decrease in carbonate δ^(26)Mg, is a result of calcite recrystallization (assuming an isotopic fractionation factor of ~0.9955). However, subtle but significant deviations from the carbonate recrystallization-only scenario suggest that another process impacts δ^(26)Mg at all three sites. Scanning electron microscope images document clay particles embedded in nannofossils and foraminiferal tests at Site 762, which suggest that clay authigenesis is active in carbonate sediments and could affect pore fluid δ^(26)Mg. The formation of secondary clays preferentially sequesters isotopically heavy Mg (α_(clay-Mg^(2+) )≈1.0005), driving pore fluid δ^(26)Mg to lower values. An increase in carbonate δ^(26)Mg within the clay-rich layer at Site 762 and an increase in bulk carbonate Na/Ca supports the hypothesis that clay authigenesis also impacts the preservation of proxy archives. Multi-component reactive transport modeling suggests that authigenic rates of ~1·10-13 mol/m^3/s (~3.15 µmol/m^3/a; assuming that the authigenic clay is sepiolite) can generate deviations from the carbonate recrystallization-only case by several tenths of a permil, indicating that carbonate sediment-associated clay authigenesis (CSCA) may be more relevant in deep-sea carbonate sections than has been previously considered.
  • Updated Description Show Changes
    Description
    • The Mg (δ^(26) Mg), Ca (δ^(44) Ca), and Sr ((_^87)Sr⁄(_^86)Sr ) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate δ^(26) Mg and (_^87)Sr⁄(_^86)Sr from ODP Site 806 Hole B and pore fluid δ^(26) Mg from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid δ^(26)Mg, specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid δ^(26)Mg values at all three sites range from -0.83 to -0.13‰ and exhibit a systematic increase with depth. Bulk carbonate δ^(26)Mg generally decrease with depth, ranging from -3.60 to -5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (~250-500 μm) from Site 762 range between -5.08 and -4.36‰. Residual siliciclastics at depths of ~105 to 145 mbsf at Site 762 have δ^(26)Mg values (-0.09 to 0.27‰) that are markedly higher than carbonate and pore fluid δ^(26)Mg values. Simple 1-D reactive transport modeling suggests that the general increase in pore fluid δ^(26)Mg with depth, accompanied by a decrease in carbonate δ^(26)Mg, is a result of calcite recrystallization (assuming an isotopic fractionation factor of ~0.9955). However, subtle but significant deviations from the carbonate recrystallization-only scenario suggest that another process impacts δ^(26)Mg at all three sites. Scanning electron microscope images document clay particles embedded in nannofossils and foraminiferal tests at Site 762, which suggest that clay authigenesis is active in carbonate sediments and could affect pore fluid δ^(26)Mg. The formation of secondary clays preferentially sequesters isotopically heavy Mg (α_(clay-Mg^(2+) )≈1.0005), driving pore fluid δ^(26)Mg to lower values. An increase in carbonate δ^(26)Mg within the clay-rich layer at Site 762 and an increase in bulk carbonate Na/Ca supports the hypothesis that clay authigenesis also impacts the preservation of proxy archives. Multi-component reactive transport modeling suggests that authigenic rates of ~1·10-13 mol/m^3/s (~3.15 µmol/m^3/a; assuming that the authigenic clay is sepiolite) can generate deviations from the carbonate recrystallization-only case by several tenths of a permil, indicating that carbonate sediment-associated clay authigenesis (CSCA) may be more relevant in deep-sea carbonate sections than has been previously considered.
    • The Mg (δ^(26) Mg), Ca (δ^(44) Ca), and Sr ((_^87)Sr⁄(_^86)Sr ) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate δ^(26) Mg and (_^87)Sr⁄(_^86)Sr from ODP Site 806 Hole B and pore fluid δ^(26) Mg from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid δ^(26)Mg, specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid δ^(26)Mg values at all three sites range from -0.83 to -0.13‰ and exhibit a systematic increase with depth. Bulk carbonate δ^(26)Mg generally decrease with depth, ranging from -3.60 to -5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (~250-500 μm) from Site 762 range between -5.08 and -4.36‰. Residual siliciclastics at depths of ~105 to 145 mbsf at Site 762 have δ^(26)Mg values (-0.09 to 0.27‰) that are markedly higher than carbonate and pore fluid δ^(26)Mg values. Simple 1-D reactive transport modeling suggests that the general increase in pore fluid δ^(26)Mg with depth, accompanied by a decrease in carbonate δ^(26)Mg, is a result of calcite recrystallization (assuming an isotopic fractionation factor of ~0.9955). However, subtle but significant deviations from the carbonate recrystallization-only scenario suggest that another process impacts δ^(26)Mg at all three sites. Scanning electron microscope images document clay particles embedded in nannofossils and foraminiferal tests at Site 762, which suggest that clay authigenesis is active in carbonate sediments and could affect pore fluid δ^(26)Mg. The formation of secondary clays preferentially sequesters isotopically heavy Mg (α_(clay-Mg^(2+) )≈1.0005), driving pore fluid δ^(26)Mg to lower values. An increase in carbonate δ^(26)Mg within the clay-rich layer at Site 762 and an increase in bulk carbonate Na/Ca supports the hypothesis that clay authigenesis also impacts the preservation of proxy archives. Multi-component reactive transport modeling suggests that authigenic rates of ~1·10^(-13) mol/m^3/s (~3.15 µmol/m^3/a; assuming that the authigenic clay is sepiolite) can generate deviations from the carbonate recrystallization-only case by several tenths of a permil, indicating that carbonate sediment-associated clay authigenesis (CSCA) may be more relevant in deep-sea carbonate sections than has been previously considered.
  • Updated Publisher Identifier (DOI) Show Changes
    Publisher Identifier (DOI)
    • https://doi.org/10.1016/j.gca.2023.02.002
  • Published
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Version 2
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Version 3
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  • Added CrunchTope_inputs_and_database_entries.txt
  • Added README_models.txt
  • Deleted README_model_files.txt
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  • Added Chanda2023_supplemental_material_v6.pdf
  • Added Chanda2023_manuscript_v8_clean.pdf
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  • Updated Publisher, Publication Date Show Changes
    Publisher
    • Elsevier
    • Geochimica et Cosmochimica Acta
    Publication Date
    • 2023
    • 2023-02-08
  • Updated Creator Matthew Fantle
  • Added Creator Piyali Chanda
  • Added Creator Arjun Kohli
  • Added Creator Fang-Zhen Teng
  • Updated