Molybdenum isotope constraints on the extent of late Paleoproterozoic ocean euxinia

Brian Kendall, Gwyneth Gordon, Simon W. Poulton, Ariel Anbar

Research output: Contribution to journalArticle

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Abstract

The expansion of anoxic and sulfidic (euxinic) deep oceans may explain the termination of global large iron formation (IF) deposition at ~1.85Ga, but the areal extent of late Paleoproterozoic ocean euxinia is poorly constrained. Here, we use the molybdenum (Mo) isotope composition (δ98/95Mo) of black shales from the <1.84Ga Rove Formation (Animikie Group, Lake Superior region) to place constraints on the extent of late Paleoproterozoic ocean euxinia. Black shales from the lower Rove Formation have ratios of highly reactive Fe to total Fe (FeHR/FeT typically >0.38) and ratios of pyrite Fe to highly reactive Fe (FePY/FeHR typically <0.8) that are consistent with a water column that was generally anoxic and Fe2+-rich. Because the FePY/FeHR ratios do not imply sustained water column euxinia, the conversion of molybdate (MoO4 2-) to tetrathiomolybdate (MoS4 2-) in bottom waters and sediments was probably not quantitative and thus the δ98/95Mo (±0.1 to +0.8‰) from these shales provides only a minimum estimate for coeval seawater. By contrast, black shales from the middle Rove Formation have high FePY/FeHR (>0.8) and FeHR/FeT (>0.38), which implies persistent water column euxinia. Concentrations of free sulfide may have been sufficient to result in near-quantitative formation of tetrathiomolybdate and its removal from bottom waters. The observed narrow range in δ98/95Mo of 1.19±0.28‰ (2SD) defined by most euxinic shales is thus inferred to represent the Mo isotope composition of late Paleoproterozoic global seawater. Mass-balance modeling suggests that organic-rich sediments deposited beneath euxinic bottom waters represented a substantial fraction of the oceanic Mo sink at 1.8Ga. The modeling results suggest that euxinic marine environments were common along late Paleoproterozoic ocean margins. These environments could have served as efficient sinks for Fe2+ (aq) upwelling from anoxic deeper waters. Hence, the Mo isotope data are consistent with Fe speciation and other geochemical evidence that suggest an expansion of euxinic environments led to the cessation of global large IF deposition after ~1.85Ga.

Original languageEnglish (US)
Pages (from-to)450-460
Number of pages11
JournalEarth and Planetary Science Letters
Volume307
Issue number3-4
DOIs
StatePublished - Jul 15 2011

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molybdenum isotopes
Molybdenum
molybdenum
Isotopes
oceans
shales
euxinic environment
isotope
bottom water
Water
water column
ocean
water
seawater
sinks
iron
Seawater
sediments
Sediments
sediment

Keywords

  • Black shale
  • Euxinic
  • Iron formation
  • Molybdenum isotopes
  • Paleoproterozoic
  • Rove Formation

ASJC Scopus subject areas

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

Cite this

Molybdenum isotope constraints on the extent of late Paleoproterozoic ocean euxinia. / Kendall, Brian; Gordon, Gwyneth; Poulton, Simon W.; Anbar, Ariel.

In: Earth and Planetary Science Letters, Vol. 307, No. 3-4, 15.07.2011, p. 450-460.

Research output: Contribution to journalArticle

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AB - The expansion of anoxic and sulfidic (euxinic) deep oceans may explain the termination of global large iron formation (IF) deposition at ~1.85Ga, but the areal extent of late Paleoproterozoic ocean euxinia is poorly constrained. Here, we use the molybdenum (Mo) isotope composition (δ98/95Mo) of black shales from the <1.84Ga Rove Formation (Animikie Group, Lake Superior region) to place constraints on the extent of late Paleoproterozoic ocean euxinia. Black shales from the lower Rove Formation have ratios of highly reactive Fe to total Fe (FeHR/FeT typically >0.38) and ratios of pyrite Fe to highly reactive Fe (FePY/FeHR typically <0.8) that are consistent with a water column that was generally anoxic and Fe2+-rich. Because the FePY/FeHR ratios do not imply sustained water column euxinia, the conversion of molybdate (MoO4 2-) to tetrathiomolybdate (MoS4 2-) in bottom waters and sediments was probably not quantitative and thus the δ98/95Mo (±0.1 to +0.8‰) from these shales provides only a minimum estimate for coeval seawater. By contrast, black shales from the middle Rove Formation have high FePY/FeHR (>0.8) and FeHR/FeT (>0.38), which implies persistent water column euxinia. Concentrations of free sulfide may have been sufficient to result in near-quantitative formation of tetrathiomolybdate and its removal from bottom waters. The observed narrow range in δ98/95Mo of 1.19±0.28‰ (2SD) defined by most euxinic shales is thus inferred to represent the Mo isotope composition of late Paleoproterozoic global seawater. Mass-balance modeling suggests that organic-rich sediments deposited beneath euxinic bottom waters represented a substantial fraction of the oceanic Mo sink at 1.8Ga. The modeling results suggest that euxinic marine environments were common along late Paleoproterozoic ocean margins. These environments could have served as efficient sinks for Fe2+ (aq) upwelling from anoxic deeper waters. Hence, the Mo isotope data are consistent with Fe speciation and other geochemical evidence that suggest an expansion of euxinic environments led to the cessation of global large IF deposition after ~1.85Ga.

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