Isotopic evidence for Fe cycling and repartitioning in ancient oxygen-deficient settings: Examples from black shales of the mid-to-late Devonian Appalachian basin

Yun Duan, Silke Severmann, Ariel Anbar, Timothy W. Lyons, Gwyneth Gordon, Bradley B. Sageman

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

We have measured iron (Fe) isotope compositions of bulk samples and chemically extracted pyrite in two black shale units: the Oatka Creek Formation (OCF) and the younger Geneseo Formation (GF) deposited in the Appalachian basin during the mid-to-late Devonian. The depositional redox conditions for these units are well established through multiple paleoproxies, including degree of pyritization (DOP) and ratios of total Fe to Al (FeT/Al), suggesting that both deposits reflect oxygen-deficient environments, but that euxinia (anoxia with hydrogen sulfide in the bottom waters) was more frequent and persistent during deposition of the OCF. Iron isotopes show systematic variations that are consistent with the inferred water column redox conditions. Samples from the OCF yield low and variable bulk Fe isotope compositions (- 0.44‰ to 0.03‰ in δ56Fe relative to average igneous rocks) that are inversely correlated with FeT/Al, whereas bulk δ56Fe values (δ56FeT) of the GF fall in a narrower range (- 0.09‰ to 0.12‰). δ56Fe values of pyrite (δ56FePy) display good correlation with δ56FeT in the OCF, but no such correlation is observed in the GF. The Fe isotope data and other paleo-redox indicators, when viewed collectively, point to a benthic Fe source on the shelf and shelf-to-basin transfer that operated during deposition of the OCF, similar to what has been observed in the modern Black Sea. For the first time this study confirms the strength of Fe isotopes in delineating this Fe enrichment mechanism in the ancient geological record and emphasizes the utility of the Fe isotope proxy for fingerprinting and quantifying ancient biogeochemical cycling of Fe.

Original languageEnglish (US)
Pages (from-to)244-253
Number of pages10
JournalEarth and Planetary Science Letters
Volume290
Issue number3-4
DOIs
StatePublished - Feb 20 2010

Fingerprint

shales
Isotopes
isotope
Oxygen
oxygen
cycles
basin
iron isotopes
isotopes
redox conditions
Iron Isotopes
pyrite
Igneous rocks
pyrites
Hydrogen Sulfide
shelves
Time and motion study
Water
iron
Shale

Keywords

  • black shales
  • iron isotopes
  • ocean redox
  • paleo-redox
  • pyrite

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics
  • Earth and Planetary Sciences (miscellaneous)
  • Space and Planetary Science

Cite this

Isotopic evidence for Fe cycling and repartitioning in ancient oxygen-deficient settings : Examples from black shales of the mid-to-late Devonian Appalachian basin. / Duan, Yun; Severmann, Silke; Anbar, Ariel; Lyons, Timothy W.; Gordon, Gwyneth; Sageman, Bradley B.

In: Earth and Planetary Science Letters, Vol. 290, No. 3-4, 20.02.2010, p. 244-253.

Research output: Contribution to journalArticle

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abstract = "We have measured iron (Fe) isotope compositions of bulk samples and chemically extracted pyrite in two black shale units: the Oatka Creek Formation (OCF) and the younger Geneseo Formation (GF) deposited in the Appalachian basin during the mid-to-late Devonian. The depositional redox conditions for these units are well established through multiple paleoproxies, including degree of pyritization (DOP) and ratios of total Fe to Al (FeT/Al), suggesting that both deposits reflect oxygen-deficient environments, but that euxinia (anoxia with hydrogen sulfide in the bottom waters) was more frequent and persistent during deposition of the OCF. Iron isotopes show systematic variations that are consistent with the inferred water column redox conditions. Samples from the OCF yield low and variable bulk Fe isotope compositions (- 0.44‰ to 0.03‰ in δ56Fe relative to average igneous rocks) that are inversely correlated with FeT/Al, whereas bulk δ56Fe values (δ56FeT) of the GF fall in a narrower range (- 0.09‰ to 0.12‰). δ56Fe values of pyrite (δ56FePy) display good correlation with δ56FeT in the OCF, but no such correlation is observed in the GF. The Fe isotope data and other paleo-redox indicators, when viewed collectively, point to a benthic Fe source on the shelf and shelf-to-basin transfer that operated during deposition of the OCF, similar to what has been observed in the modern Black Sea. For the first time this study confirms the strength of Fe isotopes in delineating this Fe enrichment mechanism in the ancient geological record and emphasizes the utility of the Fe isotope proxy for fingerprinting and quantifying ancient biogeochemical cycling of Fe.",
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AU - Duan, Yun

AU - Severmann, Silke

AU - Anbar, Ariel

AU - Lyons, Timothy W.

AU - Gordon, Gwyneth

AU - Sageman, Bradley B.

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N2 - We have measured iron (Fe) isotope compositions of bulk samples and chemically extracted pyrite in two black shale units: the Oatka Creek Formation (OCF) and the younger Geneseo Formation (GF) deposited in the Appalachian basin during the mid-to-late Devonian. The depositional redox conditions for these units are well established through multiple paleoproxies, including degree of pyritization (DOP) and ratios of total Fe to Al (FeT/Al), suggesting that both deposits reflect oxygen-deficient environments, but that euxinia (anoxia with hydrogen sulfide in the bottom waters) was more frequent and persistent during deposition of the OCF. Iron isotopes show systematic variations that are consistent with the inferred water column redox conditions. Samples from the OCF yield low and variable bulk Fe isotope compositions (- 0.44‰ to 0.03‰ in δ56Fe relative to average igneous rocks) that are inversely correlated with FeT/Al, whereas bulk δ56Fe values (δ56FeT) of the GF fall in a narrower range (- 0.09‰ to 0.12‰). δ56Fe values of pyrite (δ56FePy) display good correlation with δ56FeT in the OCF, but no such correlation is observed in the GF. The Fe isotope data and other paleo-redox indicators, when viewed collectively, point to a benthic Fe source on the shelf and shelf-to-basin transfer that operated during deposition of the OCF, similar to what has been observed in the modern Black Sea. For the first time this study confirms the strength of Fe isotopes in delineating this Fe enrichment mechanism in the ancient geological record and emphasizes the utility of the Fe isotope proxy for fingerprinting and quantifying ancient biogeochemical cycling of Fe.

AB - We have measured iron (Fe) isotope compositions of bulk samples and chemically extracted pyrite in two black shale units: the Oatka Creek Formation (OCF) and the younger Geneseo Formation (GF) deposited in the Appalachian basin during the mid-to-late Devonian. The depositional redox conditions for these units are well established through multiple paleoproxies, including degree of pyritization (DOP) and ratios of total Fe to Al (FeT/Al), suggesting that both deposits reflect oxygen-deficient environments, but that euxinia (anoxia with hydrogen sulfide in the bottom waters) was more frequent and persistent during deposition of the OCF. Iron isotopes show systematic variations that are consistent with the inferred water column redox conditions. Samples from the OCF yield low and variable bulk Fe isotope compositions (- 0.44‰ to 0.03‰ in δ56Fe relative to average igneous rocks) that are inversely correlated with FeT/Al, whereas bulk δ56Fe values (δ56FeT) of the GF fall in a narrower range (- 0.09‰ to 0.12‰). δ56Fe values of pyrite (δ56FePy) display good correlation with δ56FeT in the OCF, but no such correlation is observed in the GF. The Fe isotope data and other paleo-redox indicators, when viewed collectively, point to a benthic Fe source on the shelf and shelf-to-basin transfer that operated during deposition of the OCF, similar to what has been observed in the modern Black Sea. For the first time this study confirms the strength of Fe isotopes in delineating this Fe enrichment mechanism in the ancient geological record and emphasizes the utility of the Fe isotope proxy for fingerprinting and quantifying ancient biogeochemical cycling of Fe.

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