Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ34S records

Bryant, R. N.; Jones, C.; Raven, M. R.; Owens, J. D.; Fike, D. A.

doi:10.1016/j.chemgeo.2020.119808

Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ³⁴S records

Journal Article · Thu Aug 06 00:00:00 EDT 2020 · Chemical Geology

DOI:https://doi.org/10.1016/j.chemgeo.2020.119808· OSTI ID:1851965

^[1]; Jones, C. ^[2]; Raven, M. R. ^[3]; Owens, J. D. ^[4]; Fike, D. A. ^[2]

Washington Univ., St. Louis, MO (United States); Univ. of Chicago, IL (United States); Washington Univ., St. Louis, MO (United States)
Washington Univ., St. Louis, MO (United States)
Washington Univ., St. Louis, MO (United States); Univ. of California, Santa Barbara, CA (United States)
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)

We report total reduced inorganic S isotope ratios (δ³⁴S_CRS) shift toward more negative values across much of the southern North Atlantic just before the onset of the Cenomanian-Turonian Ocean Anoxic Event (OAE-2). At the same time, there is no parallel isotopic change in the significantly larger pool of kerogen (organic) S, which indicates that the distribution and S-isotope composition of sulfide in the environment likely did not drive the change in δ³⁴S_CRS. Here, we investigate possible explanations for the negative shift in δ³⁴S_CRSvalues and their divergence from organic S by isolating iron sulfides for morphological identification and grain-specific isotopic analysis using secondary ion mass spectrometry (SIMS). In pre- and syn-OAE-2 sedimentary rocks from Demerara Rise, we find four distinct morphologies of iron sulfides: pyrite framboids (1–20 μm diameter), irregular pyrite aggregates (1–38 μm diameter), large cemented pyrite aggregates (~60 μm diameter), and irregular and cemented aggregates of the pyrite polymorph marcasite (1–45 μm diameter). These different textural groups have distinct S-isotopic compositions that are largely consistent through the onset of OAE-2. As such, the secular change in bulk δ³⁴S_CRS values likely reflects the changing proportions of these phases stratigraphically across OAE-2. All textural groups feature resolvable intra-grain δ³⁴S variability, suggesting that the environments in which they formed were characterized by dynamic sulfide δ³⁴S values and/or by partial closed-system distillation. We use grain-specific δ³⁴S distributions to rule out shoaling of the chemocline within the sediments as a mechanism for the observed decrease in δ³⁴S_CRS. Instead, we propose that changes in the reactivity of the iron species delivered to Demerara Rise over the ~200 kyr leading up to the onset of OAE-2 impacted the relative contributions of pyrite with S-isotope signatures reflecting the water column, shallow sediments, and deeper sediments to the bulk sedimentary δ³⁴S_CRS value. Specifically, the change in iron reactivity at the onset of OAE-2 favored the production of ³⁴S-depleted large, cemented aggregates and framboids at the expense of more ³⁴S-enriched irregular aggregates. Our results underscore that bulk δ³⁴S_CRS measurements integrate multiple reduced phases that form via distinct reaction mechanisms and potentially in different parts of the depositional environment. Grain-specific SIMS analyses dramatically enrich our ability to interpret pyrite isotopic patterns in the geologic record.

View Accepted Manuscript (DOE)

Research Organization:: Washington Univ., St. Louis, MO (United States)

Sponsoring Organization:: American Chemical Society Petroleum Research; National Science Foundation (NSF); State of Florida; USDOE Office of Science (SC), Biological and Environmental Research (BER); Washington University

Grant/Contract Number:: SC0014613

OSTI ID:: 1851965

Alternate ID(s):: OSTI ID: 1810899

Journal Information:: Chemical Geology, Journal Name: Chemical Geology Journal Issue: C Vol. 553; ISSN 0009-2541

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

Geochemical characterization of black shales from the Tarfaya Basin Kolonic, Sadat; Sinninghe Damsté, Jaap S.; Böttcher, Michael Ernst PANGAEA https://doi.org/10.1594/pangaea.735991	collection	January 2002
Biogeochemical sulfur cycling during Cretaceous oceanic anoxic events: A comparison of OAE1a and OAE2: CRETACEOUS OCEAN ANOXIA AND SULFUR Gomes, Maya L.; Hurtgen, Matthew T.; Sageman, Bradley B. Paleoceanography, Vol. 31, Issue 2 https://doi.org/10.1002/2015PA002869	journal	February 2016
Investigation of the quasi-simultaneous arrival (QSA) effect on a CAMECA IMS 7f-GEO: Investigation of the QSA effect on a CAMECA IMS 7f-GEO Jones, Clive; Fike, David A.; Peres, Paula Rapid Communications in Mass Spectrometry, Vol. 31, Issue 7 https://doi.org/10.1002/rcm.7828	journal	March 2017
Sulfur isotope analysis of microcrystalline iron sulfides using secondary ion mass spectrometry imaging: Extracting local paleo-environmental information from modern and ancient sediments Bryant, Roger N.; Jones, Clive; Raven, Morgan R. Rapid Communications in Mass Spectrometry, Vol. 33, Issue 5 https://doi.org/10.1002/rcm.8375	journal	February 2019
Determination of the absolute32S/34S ratio of IAEA-S-1 reference material and V-CDT sulfur isotope standard Ding, Tiping; Bai, Ruimei; Li, Yanhe Science in China Series D: Earth Sciences, Vol. 42, Issue 1 https://doi.org/10.1007/BF02878497	journal	August 1999
The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales Canfield, Donald E.; Raiswell, Robert; Westrich, Joseph T. Chemical Geology, Vol. 54, Issue 1-2 https://doi.org/10.1016/0009-2541(86)90078-1	journal	January 1986
Kinetic controls on depth variations in localised pyrite formation Raiswell, R. Chemical Geology, Vol. 107, Issue 3-4 https://doi.org/10.1016/0009-2541(93)90233-9	journal	July 1993
A warm, equable Cretaceous: The nature of the problem Barron, Eric J. Earth-Science Reviews, Vol. 19, Issue 4 https://doi.org/10.1016/0012-8252(83)90001-6	journal	August 1983
A theoretical model of the stable sulfur isotope distribution in marine sediments Jorgensen, Bo Barker Geochimica et Cosmochimica Acta, Vol. 43, Issue 3 https://doi.org/10.1016/0016-7037(79)90201-1	journal	March 1979
Marcasite precipitation from hydrothermal solutions Murowchick, James B.; Barnes, H. L. Geochimica et Cosmochimica Acta, Vol. 50, Issue 12 https://doi.org/10.1016/0016-7037(86)90214-0	journal	December 1986
The size distribution of framboidal pyrite in modern sediments: An indicator of redox conditions Wilkin, R. T.; Barnes, H. L.; Brantley, S. L. Geochimica et Cosmochimica Acta, Vol. 60, Issue 20 https://doi.org/10.1016/0016-7037(96)00209-8	journal	October 1996
Biogeochemical cycles of carbon and sulfur and their effect on atmospheric oxygen over phanerozoic time Berner, Robert A. Global and Planetary Change, Vol. 1, Issue 1-2 https://doi.org/10.1016/0921-8181(89)90018-0	journal	January 1989
Sulfide oxidation and iron dissolution kinetics during the reaction of dissolved sulfide with ferrihydrite Poulton, Simon W. Chemical Geology, Vol. 202, Issue 1-2 https://doi.org/10.1016/S0009-2541(03)00237-7	journal	December 2003
Reaction pathways in the Fe–S system below 100°C Benning, Liane G.; Wilkin, Rick T.; Barnes, H. L. Chemical Geology, Vol. 167, Issue 1-2 https://doi.org/10.1016/S0009-2541(99)00198-9	journal	June 2000
Modeling atmospheric O2 over Phanerozoic time Berner, R. A. Geochimica et Cosmochimica Acta, Vol. 65, Issue 5 https://doi.org/10.1016/S0016-7037(00)00572-X	journal	March 2001
Oxidation of detrital pyrite as a cause for Marcasite Formation in marine lag deposits from the Devonian of the eastern US Schieber, Juergen Deep Sea Research Part II: Topical Studies in Oceanography, Vol. 54, Issue 11-13 https://doi.org/10.1016/j.dsr2.2007.04.005	journal	June 2007
Amino acid biogeochemistry and organic matter degradation state across the Pakistan margin oxygen minimum zone Vandewiele, Sandra; Cowie, Greg; Soetaert, Karline Deep Sea Research Part II: Topical Studies in Oceanography, Vol. 56, Issue 6-7 https://doi.org/10.1016/j.dsr2.2008.05.035	journal	March 2009
Experimental syntheses of framboids—a review Ohfuji, Hiroaki; Rickard, David Earth-Science Reviews, Vol. 71, Issue 3-4 https://doi.org/10.1016/j.earscirev.2005.02.001	journal	August 2005
Empirical links between trace metal cycling and marine microbial ecology during a large perturbation to Earth's carbon cycle Owens, Jeremy D.; Reinhard, Christopher T.; Rohrssen, Megan Earth and Planetary Science Letters, Vol. 449 https://doi.org/10.1016/j.epsl.2016.05.046	journal	September 2016
Quantifying the missing sink for global organic carbon burial during a Cretaceous oceanic anoxic event Owens, Jeremy D.; Lyons, Timothy W.; Lowery, Christopher M. Earth and Planetary Science Letters, Vol. 499 https://doi.org/10.1016/j.epsl.2018.07.021	journal	October 2018
Paired organic matter and pyrite δ34S records reveal mechanisms of carbon, sulfur, and iron cycle disruption during Ocean Anoxic Event 2 Raven, Morgan Reed; Fike, David A.; Bradley, Alexander S. Earth and Planetary Science Letters, Vol. 512 https://doi.org/10.1016/j.epsl.2019.01.048	journal	April 2019
Cretaceous black shales as active bioreactors: A biogeochemical model for the deep biosphere encountered during ODP Leg 207 (Demerara Rise) Arndt, Sandra; Brumsack, Hans-Jürgen; Wirtz, Kai W. Geochimica et Cosmochimica Acta, Vol. 70, Issue 2 https://doi.org/10.1016/j.gca.2005.09.010	journal	January 2006
Effect of electron donors on the fractionation of sulfur isotopes by a marine Desulfovibrio sp. Sim, Min Sub; Ono, Shuhei; Donovan, Katie Geochimica et Cosmochimica Acta, Vol. 75, Issue 15 https://doi.org/10.1016/j.gca.2011.05.021	journal	August 2011
Basin-scale controls on the molybdenum-isotope composition of seawater during Oceanic Anoxic Event 2 (Late Cretaceous) Dickson, Alexander J.; Jenkyns, Hugh C.; Porcelli, Donald Geochimica et Cosmochimica Acta, Vol. 178 https://doi.org/10.1016/j.gca.2015.12.036	journal	April 2016
Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems Eldridge, D. L.; Guo, W.; Farquhar, J. Geochimica et Cosmochimica Acta, Vol. 195 https://doi.org/10.1016/j.gca.2016.09.021	journal	December 2016
Microscale reservoir effects on microbial sulfur isotope fractionation Louca, Stilianos; Crowe, Sean A. Geochimica et Cosmochimica Acta, Vol. 203 https://doi.org/10.1016/j.gca.2017.01.007	journal	April 2017
Oxygen and sulfur isotopes in sulfate in modern euxinic systems with implications for evaluating the extent of euxinia in ancient oceans Gomes, Maya L.; Johnston, David T. Geochimica et Cosmochimica Acta, Vol. 205 https://doi.org/10.1016/j.gca.2017.02.020	journal	May 2017
Fe(III):S(-II) concentration ratio controls the pathway and the kinetics of pyrite formation during sulfidation of ferric hydroxides Wan, Moli; Schröder, Christian; Peiffer, Stefan Geochimica et Cosmochimica Acta, Vol. 217 https://doi.org/10.1016/j.gca.2017.08.036	journal	November 2017
Dynamics of pyrite formation and organic matter sulfurization in organic-rich carbonate sediments Shawar, Lubna; Halevy, Itay; Said-Ahmad, Ward Geochimica et Cosmochimica Acta, Vol. 241 https://doi.org/10.1016/j.gca.2018.08.048	journal	November 2018
Reprint of “The effect of biogeochemical processes on pH” Soetaert, Karline; Hofmann, Andreas F.; Middelburg, Jack J. Marine Chemistry, Vol. 106, Issue 1-2 https://doi.org/10.1016/j.marchem.2007.06.008	journal	July 2007
Paleo-redox conditions during OAE 2 reflected in Demerara Rise sediment geochemistry (ODP Leg 207) Hetzel, Almut; Böttcher, Michael E.; Wortmann, Ulrich G. Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 273, Issue 3-4 https://doi.org/10.1016/j.palaeo.2008.11.005	journal	March 2009
Crystal Growth of Pyrite in Aqueous Solutions. Inhibition by Organophosphorus Compounds Harmandas, N. G.; Navarro Fernandez, E.; Koutsoukos, P. G. Langmuir, Vol. 14, Issue 5 https://doi.org/10.1021/la970354c	journal	February 1998
Stable organic carbon isotope stratigraphy across Oceanic Anoxic Event 2 of Demerara Rise, western tropical Atlantic: CARBON ISOTOPE STRATIGRAPHY Erbacher, Jochen; Friedrich, Oliver; Wilson, Paul A. Geochemistry, Geophysics, Geosystems, Vol. 6, Issue 6 https://doi.org/10.1029/2004GC000850	journal	June 2005
Geochemistry of oceanic anoxic events: REVIEW Jenkyns, Hugh C. Geochemistry, Geophysics, Geosystems, Vol. 11, Issue 3 https://doi.org/10.1029/2009GC002788	journal	March 2010
The mid-Cretaceous North Atlantic nutrient trap: Black shales and OAEs: MID-CRETACEOUS N. ATLANTIC NUTRIENT TRAP Trabucho Alexandre, João; Tuenter, Erik; Henstra, Gijs A. Paleoceanography, Vol. 25, Issue 4 https://doi.org/10.1029/2010PA001925	journal	October 2010
Black shale deposition, atmospheric CO ₂ drawdown, and cooling during the Cenomanian-Turonian Oceanic Anoxic Event: CO ₂ DRAWDOWN AND COOLING DURING OAE2 Jarvis, Ian; Lignum, John S.; Gröcke, Darren R. Paleoceanography, Vol. 26, Issue 3 https://doi.org/10.1029/2010PA002081	journal	July 2011
Iron isotope and trace metal records of iron cycling in the proto-North Atlantic during the Cenomanian-Turonian oceanic anoxic event (OAE-2): OAE-2 Fe ISOTOPES Owens, Jeremy D.; Lyons, Timothy W.; Li, Xiaona Paleoceanography, Vol. 27, Issue 3 https://doi.org/10.1029/2012PA002328	journal	August 2012
Evaluating structure selection in the hydrothermal growth of FeS2 pyrite and marcasite Kitchaev, Daniil A.; Ceder, Gerbrand Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13799	journal	December 2016
A unifying model for Neoproterozoic–Palaeozoic exceptional fossil preservation through pyritization and carbonaceous compression Schiffbauer, James D.; Xiao, Shuhai; Cai, Yaoping Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6754	journal	December 2014
Hydrothermal vents as a kinetically stable source of iron-sulphide-bearing nanoparticles to the ocean Yücel, Mustafa; Gartman, Amy; Chan, Clara S. Nature Geoscience, Vol. 4, Issue 6 https://doi.org/10.1038/ngeo1148	journal	May 2011
Warm saline intermediate waters in the Cretaceous tropical Atlantic Ocean Friedrich, Oliver; Erbacher, Jochen; Moriya, Kazuyoshi Nature Geoscience, Vol. 1, Issue 7 https://doi.org/10.1038/ngeo217	journal	May 2008
Volcanic triggering of a biogeochemical cascade during Oceanic Anoxic Event 2 Adams, Derek D.; Hurtgen, Matthew T.; Sageman, Bradley B. Nature Geoscience, Vol. 3, Issue 3 https://doi.org/10.1038/ngeo743	journal	January 2010
Global niche of marine anaerobic metabolisms expanded by particle microenvironments Bianchi, Daniele; Weber, Thomas S.; Kiko, Rainer Nature Geoscience, Vol. 11, Issue 4 https://doi.org/10.1038/s41561-018-0081-0	journal	March 2018
Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record Leavitt, W. D.; Halevy, I.; Bradley, A. S. Proceedings of the National Academy of Sciences, Vol. 110, Issue 28 https://doi.org/10.1073/pnas.1218874110	journal	June 2013
Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous Oceanic Anoxic Event 2 Owens, J. D.; Gill, B. C.; Jenkyns, H. C. Proceedings of the National Academy of Sciences, Vol. 110, Issue 46 https://doi.org/10.1073/pnas.1305304110	journal	October 2013
SQUID-SIMS is a useful approach to uncover primary signals in the Archean sulfur cycle Fischer, W. W.; Fike, D. A.; Johnson, J. E. Proceedings of the National Academy of Sciences, Vol. 111, Issue 15 https://doi.org/10.1073/pnas.1322577111	journal	April 2014
Intracellular metabolite levels shape sulfur isotope fractionation during microbial sulfate respiration Wing, Boswell A.; Halevy, Itay Proceedings of the National Academy of Sciences, Vol. 111, Issue 51 https://doi.org/10.1073/pnas.1407502111	journal	October 2014
Phanerozoic cycles of sedimentary carbon and sulfur Garrels, R. M.; Lerman, A. Proceedings of the National Academy of Sciences, Vol. 78, Issue 8 https://doi.org/10.1073/pnas.78.8.4652	journal	August 1981
Secondary Ion Mass Spectrometry Methodology for Isotopic Ratio Measurement of Micro‐Grains in Thin Sections: True Grain Size Estimation and Deconvolution of Inter‐Grain Size Gradients and Intra‐Grain Radial Gradients Jones, Clive; Fike, David A.; Meyer, Katja M. Geostandards and Geoanalytical Research, Vol. 43, Issue 1 https://doi.org/10.1111/ggr.12247	journal	December 2018
Geochemical Characterization of Cenomanian/Turonian Black Shales from the Tarfaya Basin (sw Morocco). Relationships Between Palaeoenvironmental Conditions and Early Sulphurization of Sedimentary Organic Matter1 Kolonic, S.; Sinninghe Damste, J. S.; Bottcher, M. E. Journal of Petroleum Geology, Vol. 25, Issue 3 https://doi.org/10.1111/j.1747-5457.2002.tb00012.x	journal	July 2002
Constraining the rate of oceanic deoxygenation leading up to a Cretaceous Oceanic Anoxic Event (OAE-2: ~94 Ma) Ostrander, Chadlin M.; Owens, Jeremy D.; Nielsen, Sune G. Science Advances, Vol. 3, Issue 8 https://doi.org/10.1126/sciadv.1701020	journal	August 2017
Seawater Sulfur Isotope Fluctuations in the Cretaceous Paytan, A. Science, Vol. 304, Issue 5677 https://doi.org/10.1126/science.1095258	journal	June 2004
Large Sulfur Isotope Fractionation Does Not Require Disproportionation Sim, M. S.; Bosak, T.; Ono, S. Science, Vol. 333, Issue 6038 https://doi.org/10.1126/science.1205103	journal	June 2011
Pyritization of soft-bodied fossils: Beecher's Trilobite Bed, Upper Ordovician, New York State Briggs, Derek E. G.; Bottrell, Simon H.; Raiswell, Robert Geology, Vol. 19, Issue 12 https://doi.org/10.1130/0091-7613(1991)019<1221:POSBFB>2.3.CO;2	journal	January 1991
Pyrite formation in the water column and sediments of a meromictic lake Suits, Neil S.; Wilkin, Rick T. Geology, Vol. 26, Issue 12 https://doi.org/10.1130/0091-7613(1998)026<1099:PFITWC>2.3.CO;2	journal	January 1998
Nd isotopic excursion across Cretaceous ocean anoxic event 2 (Cenomanian-Turonian) in the tropical North Atlantic MacLeod, Kenneth G.; Martin, Ellen E.; Blair, Susanna W. Geology, Vol. 36, Issue 10 https://doi.org/10.1130/G24999A.1	journal	January 2008
Evolution of middle to Late Cretaceous oceans—A 55 m.y. record of Earth's temperature and carbon cycle Friedrich, Oliver; Norris, Richard D.; Erbacher, Jochen Geology, Vol. 40, Issue 2 https://doi.org/10.1130/G32701.1	journal	February 2012
Rethinking the Ancient Sulfur Cycle Fike, David A.; Bradley, Alexander S.; Rose, Catherine V. Annual Review of Earth and Planetary Sciences, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-earth-060313-054802	journal	May 2015
Variability in the Raman Spectrum of Unpolished Growth and Fracture Surfaces of Pyrite Due to Laser Heating and Crystal Orientation Bryant, Roger N.; Pasteris, Jill D.; Fike, David A. Applied Spectroscopy, Vol. 72, Issue 1 https://doi.org/10.1177/0003702817736516	journal	October 2017
Marcasite in Black Shales--a Mineral Proxy for Oxygenated Bottom Waters and Intermittent Oxidation of Carbonaceous Muds Schieber, J. Journal of Sedimentary Research, Vol. 81, Issue 7 https://doi.org/10.2110/jsr.2011.41	journal	June 2011
Questioning the biogenicity of Neoproterozoic superheavy pyrite by SIMS Cui, Huan; Kitajima, Kouki; Spicuzza, Michael J. American Mineralogist, Vol. 103, Issue 9 https://doi.org/10.2138/am-2018-6489	journal	September 2018
Kinetics and mechanism of pyrite formation at low temperatures Rickard, D. T. American Journal of Science, Vol. 275, Issue 6 https://doi.org/10.2475/ajs.275.6.636	journal	June 1975
Pyrite texture, isotopic composition and the availability of iron Raiswell, R. American Journal of Science, Vol. 282, Issue 8 https://doi.org/10.2475/ajs.282.8.1244	journal	October 1982
The reactivity of sedimentary iron minerals toward sulfide Canfield, D. E.; Raiswell, R.; Bottrell, S. H. American Journal of Science, Vol. 292, Issue 9 https://doi.org/10.2475/ajs.292.9.659	journal	November 1992
The evolution of the Earth surface sulfur reservoir Canfield, D. E. American Journal of Science, Vol. 304, Issue 10 https://doi.org/10.2475/ajs.304.10.839	journal	December 2004

Similar Records

Paired organic matter and pyrite δ³⁴S records reveal mechanisms of carbon, sulfur, and iron cycle disruption during Ocean Anoxic Event 2

Journal Article · Tue Feb 12 19:00:00 EST 2019 · Earth and Planetary Science Letters · OSTI ID:1529254

Sulfur isotope variability in biogenic pyrite: Reflections of heterogeneous bacterial colonization?

Journal Article · Sat Oct 31 23:00:00 EST 1998 · American Mineralogist · OSTI ID:329216

Sedimentation and early sulfide diagenesis of Harmon Member

Conference · Tue Feb 28 23:00:00 EST 1989 · AAPG (Am. Assoc. Pet. Geol.) Bull.; (United States) · OSTI ID:6376555

Related Subjects

58 GEOSCIENCES
Fe sulfides
Marcasite
OAE-2
Pyrite
Raman
S isotopes
SIMS

Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ34S records

Citation Formats

References (65)

Similar Records

Related Subjects

Shifting modes of iron sulfidization at the onset of OAE-2 drive regional shifts in pyrite δ³⁴S records