Brachiopod δ34SCAS microanalyses indicate a dynamic, climate-influenced Permo-Carboniferous sulfur cycle

Johnson, Daniel L.; Grossman, Ethan L.; Webb, Samuel M.; Adkins, Jess F.

doi:10.1016/j.epsl.2020.116428

Title: Brachiopod δ³⁴S_CAS microanalyses indicate a dynamic, climate-influenced Permo-Carboniferous sulfur cycle

Journal Article · Tue Jul 07 00:00:00 EDT 2020 · Earth and Planetary Science Letters

DOI:https://doi.org/10.1016/j.epsl.2020.116428· OSTI ID:1656542

^[1];

^[2]; Webb, Samuel M. ^[3]; Adkins, Jess F. ^[1]

California Institute of Technology (CalTech), Pasadena, CA (United States)
Texas A & M Univ. at College Station, TX (United States)
Stanford Univ., CA (United States)

Early isotopic studies of sulfate in carbonate minerals (carbonate associated sulfate; CAS) suggested that carbonates can provide a reliable, well-dated archive of the marine sulfur cycle through time. However, subsequent research has shown that diagenetic alteration can impose highly heterogeneous CAS sulfur isotopic compositions (δ³⁴S_CAS) among different carbonate phases within sediments. Such alteration necessitates targeted sampling of well-preserved, primary carbonate phases. Here, we present a new record of Carboniferous and Early Permian brachiopod δ³⁴S_CAS generated from over 130 measurements of microsampled brachiopod shells. Our record refines existing brachiopod δ³⁴S_CAS records and confirms a large, ~6.5‰ δ³⁴S_CAS decrease in the Early Carboniferous. Importantly, the record also features a novel 3–5‰ increase in δ³⁴S_CAS near the Serpukhovian-Bashkirian boundary (323.4 Ma) that coincides with carbonate δ¹³C and δ¹⁸O increases. Variability in δ³⁴S_CAS is minor both within (≤0.3‰) and among (≤2‰) individual co-depositional brachiopod specimens. A taxon-specific δ³⁴S_CAS offset is present one species (Composita subtilita) that also exhibits a δ¹³C offset, supporting the existence of biological “vital effects” on δ³⁴S_CAS. Geologic evidence and mathematical modeling of the Permo-Carboniferous carbon and sulfur cycles suggest that changes in the burial ratio of organic carbon to pyrite sulfur (R_C:S) are insufficient to explain the observed mid-Carboniferous δ³⁴S_CAS record. We find that changes in the ³⁴S depletion of pyrite relative to seawater sulfate (³⁴ε) or in the δ³⁴S of the input to the ocean (δ³⁴S_in) are also needed. Large additions of O₂ from organic carbon burial during the Permo-Carboniferous cannot be entirely compensated for with sulfur cycle changes; lower than modern late Visean pO₂ and/or additional O₂ sinks are needed to keep pO₂ at plausible levels. Based on the geologic context surrounding our record's mid-Carboniferous δ³⁴S_CAS increase, we advocate for simultaneous changes in pyrite burial, ³⁴ε, and δ³⁴S_in, driven by sea level or tectonically induced changes in environments of sulfur burial, as a viable mechanism to produce rapid seawater δ³⁴S changes.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Aeronautics and Space Administration (NASA); National Science Foundation (NSF)

Grant/Contract Number:: OCE-1559215; OCE-1450528; OCE-1737404; MGG-1834492; NNN12AA01C; AC02-76SF00515

OSTI ID:: 1656542

Alternate ID(s):: OSTI ID: 1702335

Journal Information:: Earth and Planetary Science Letters, Vol. 546; ISSN 0012-821X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

References (57)

Late Pennsylvanian seasonality reflected in the 18O and elemental composition of a brachiopod shell Mii, Horng-Sheng; Grossman, Ethan L. Geology, Vol. 22, Issue 7 https://doi.org/10.1130/0091-7613(1994)022<0661:LPSRIT>2.3.CO;2	journal	January 1994
Large Carbonate Associated Sulfate isotopic variability between brachiopods, micrite, and other sedimentary components in Late Ordovician strata Present, Theodore M.; Paris, Guillaume; Burke, Andrea Earth and Planetary Science Letters, Vol. 432 https://doi.org/10.1016/j.epsl.2015.10.005	journal	December 2015
The sulfur isotopic evolution of Phanerozoic seawater based on the analysis of structurally substituted sulfate in carbonates Kampschulte, A.; Strauss, H. Chemical Geology, Vol. 204, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2003.11.013	journal	April 2004
Sulfur isotopes of iron sulfides in Devonian-Mississippian shales of the Appalachian Basin; control by rate of sedimentation Maynard, J. B. American Journal of Science, Vol. 280, Issue 8 https://doi.org/10.2475/ajs.280.8.772	journal	October 1980
Neoarchean carbonate-associated sulfate records positive 33S anomalies Paris, G.; Adkins, J. F.; Sessions, A. L. Science, Vol. 346, Issue 6210 https://doi.org/10.1126/science.1258211	journal	November 2014
Evaporite tectonics and the late Paleozoic stratigraphic development of the Cumberland basin, Appalachians of Atlantic Canada Waldron, J. W. F.; Rygel, M. C.; Gibling, M. R. Geological Society of America Bulletin, Vol. 125, Issue 5-6 https://doi.org/10.1130/B30718.1	journal	January 2013
Multiple sulfur isotopes (δ34S, Δ33S) and trace elements (Mo, U, V) reveal changing palaeoenvironments in the mid-Carboniferous Chokier Formation, Belgium Siedenberg, Katharina; Strauss, Harald; Littke, Ralf Chemical Geology, Vol. 441 https://doi.org/10.1016/j.chemgeo.2016.08.017	journal	November 2016
Stratigraphic imprint of the Late Palaeozoic Ice Age in eastern Australia: a record of alternating glacial and nonglacial climate regime Fielding, Christopher R.; Frank, Tracy D.; Birgenheier, Lauren P. Journal of the Geological Society, Vol. 165, Issue 1 https://doi.org/10.1144/0016-76492007-036	journal	January 2008
Pyrite sulfur isotopes reveal glacial−interglacial environmental changes Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina Proceedings of the National Academy of Sciences, Vol. 114, Issue 23 https://doi.org/10.1073/pnas.1618245114	journal	May 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
Brachiopod geochemical records from across the Carboniferous seas of North America: Evidence for salinity gradients, stratification, and circulation patterns Roark, Andrew; Flake, Ryan; Grossman, Ethan L. Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 485 https://doi.org/10.1016/j.palaeo.2017.06.009	journal	November 2017
Sulfate Burial Constraints on the Phanerozoic Sulfur Cycle Halevy, I.; Peters, S. E.; Fischer, W. W. Science, Vol. 337, Issue 6092 https://doi.org/10.1126/science.1220224	journal	July 2012
Stable-isotope stratigraphy of brachiopods from Pennsylvanian shales in Texas Grossman, Ethan L.; Zhang, Chuanlun; Yancey, Thomas E. Geological Society of America Bulletin, Vol. 103, Issue 7 https://doi.org/10.1130/0016-7606(1991)103<0953:SISOBF>2.3.CO;2	journal	July 1991
Compilation and time-series analysis of a marine carbonate δ18O, δ13C, 87Sr/86Sr and δ34S database through Earth history Prokoph, A.; Shields, G. A.; Veizer, J. Earth-Science Reviews, Vol. 87, Issue 3-4 https://doi.org/10.1016/j.earscirev.2007.12.003	journal	March 2008
Terrestrial-marine teleconnections in the Devonian: links between the evolution of land plants, weathering processes, and marine anoxic events Algeo, Thomas J.; Scheckler, Stephen E. Philosophical Transactions of the Royal Society of London. Series B: Biological Sciences, Vol. 353, Issue 1365 https://doi.org/10.1098/rstb.1998.0195	journal	January 1998
The sulphur isotopic composition of trace sulphates in Carboniferous brachiopods: implications for coeval seawater, correlation with other geochemical cycles and isotope stratigraphy Kampschulte, A.; Bruckschen, P.; Strauss, H. Chemical Geology, Vol. 175, Issue 1-2 https://doi.org/10.1016/S0009-2541(00)00367-3	journal	May 2001
δ34S and Δ33S records of Paleozoic seawater sulfate based on the analysis of carbonate associated sulfate Wu, Nanping; Farquhar, James; Strauss, Harald Earth and Planetary Science Letters, Vol. 399 https://doi.org/10.1016/j.epsl.2014.05.004	journal	August 2014
Sulfur Isotopic Composition of Cenozoic Seawater Sulfate Paytan, A. Science, Vol. 282, Issue 5393 https://doi.org/10.1126/science.282.5393.1459	journal	November 1998
Silurian records of carbon and sulfur cycling from Estonia: The importance of depositional environment on isotopic trends Richardson, Jocelyn A.; Keating, Colin; Lepland, Aivo Earth and Planetary Science Letters, Vol. 512 https://doi.org/10.1016/j.epsl.2019.01.055	journal	April 2019
Correlation of and secular variations Veizer, Ján; Holser, William T.; Wilgus, Cheryl K. Geochimica et Cosmochimica Acta, Vol. 44, Issue 4 https://doi.org/10.1016/0016-7037(80)90250-1	journal	April 1980
Experimental determination of carbonate-associated sulfate δ ³⁴ S in planktonic foraminifera shells Paris, Guillaume; Fehrenbacher, Jennifer S.; Sessions, Alex L. Geochemistry, Geophysics, Geosystems, Vol. 15, Issue 4 https://doi.org/10.1002/2014GC005295	journal	April 2014
isotopic evolution of Lower Carboniferous seawater: Dinantian of western Europe Bruckschen, P.; Bruhn, F.; Veizer, J. Sedimentary Geology, Vol. 100, Issue 1-4 https://doi.org/10.1016/0037-0738(95)00103-4	journal	December 1995
Records of carbon and sulfur cycling during the Silurian Ireviken Event in Gotland, Sweden Rose, Catherine V.; Fischer, Woodward W.; Finnegan, Seth Geochimica et Cosmochimica Acta, Vol. 246 https://doi.org/10.1016/j.gca.2018.11.030	journal	February 2019
Isotope stratigraphy of the European Carboniferous: proxy signals for ocean chemistry, climate and tectonics Bruckschen, Peter; Oesmann, Susanne; Veizer, Ján Chemical Geology, Vol. 161, Issue 1-3 https://doi.org/10.1016/S0009-2541(99)00084-4	journal	September 1999
Late Proterozoic rise in atmospheric oxygen concentration inferred from phylogenetic and sulphur-isotope studies Canfield, Donald E.; Teske, Andreas Nature, Vol. 382, Issue 6587 https://doi.org/10.1038/382127a0	journal	July 1996
The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur Canfield, D.; Thamdrup, B. Science, Vol. 266, Issue 5193 https://doi.org/10.1126/science.11540246	journal	December 1994
?Background? ?34S values of Kupferschiefer sulphides in Poland: pyrite-marcasite nodules Jowett, E. C.; Roth, T.; Rydzewski, A. Mineralium Deposita, Vol. 26, Issue 2 https://doi.org/10.1007/BF00195254	journal	April 1991
The source of sulfate in brachiopod calcite: Insights from μ-XRF imaging and XANES spectroscopy Richardson, Jocelyn A.; Newville, Matthew; Lanzirotti, Antonio Chemical Geology, Vol. 529 https://doi.org/10.1016/j.chemgeo.2019.119328	journal	December 2019
Glaciation, aridification, and carbon sequestration in the Permo-Carboniferous: The isotopic record from low latitudes Grossman, Ethan L.; Yancey, Thomas E.; Jones, Thomas E. Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 268, Issue 3-4 https://doi.org/10.1016/j.palaeo.2008.03.053	journal	October 2008
The Late Paleozoic Ice Age: An Evolving Paradigm Montañez, Isabel P.; Poulsen, Christopher J. Annual Review of Earth and Planetary Sciences, Vol. 41, Issue 1 https://doi.org/10.1146/annurev.earth.031208.100118	journal	May 2013
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
The isotopic composition of sedimentary sulfur through time Strauss, H. Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 132, Issue 1-4 https://doi.org/10.1016/S0031-0182(97)00067-9	journal	August 1997
Micro- and nanostructures reflect the degree of diagenetic alteration in modern and fossil brachiopod shell calcite: A multi-analytical screening approach (CL, FE-SEM, AFM, EBSD) Casella, L. A.; Griesshaber, E.; Simonet Roda, M. Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 502 https://doi.org/10.1016/j.palaeo.2018.03.011	journal	August 2018
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
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
Kinetic and thermodynamic factors controlling the distribution of SO₃²⁻ and Na⁺ in calcites and selected aragonites Busenberg, Eurybiades; Niel Plummer, L. Geochimica et Cosmochimica Acta, Vol. 49, Issue 3, p. 713-725 https://doi.org/10.1016/0016-7037(85)90166-8	journal	March 1985
Carbonic anhydrase, coral calcification and a new model of stable isotope vital effects Chen, Sang; Gagnon, Alexander C.; Adkins, Jess F. Geochimica et Cosmochimica Acta, Vol. 236 https://doi.org/10.1016/j.gca.2018.02.032	journal	September 2018
Diagenetic controls on the isotopic composition of carbonate‐associated sulphate in the Permian Capitan Reef Complex, West Texas Present, Theodore M.; Gutierrez, Melissa; Paris, Guillaume Sedimentology, Vol. 66, Issue 7 https://doi.org/10.1111/sed.12615	journal	June 2019
A paired sulfate–pyrite δ34S approach to understanding the evolution of the Ediacaran–Cambrian sulfur cycle Fike, D. A.; Grotzinger, J. P. Geochimica et Cosmochimica Acta, Vol. 72, Issue 11 https://doi.org/10.1016/j.gca.2008.03.021	journal	June 2008
Depositional and diagenetic constraints on the abundance and spatial variability of carbonate-associated sulfate Richardson, Jocelyn A.; Newville, Matthew; Lanzirotti, Antonio Chemical Geology, Vol. 523 https://doi.org/10.1016/j.chemgeo.2019.05.036	journal	September 2019
Burial of organic carbon and pyrite sulfur in sediments over phanerozoic time: a new theory Berner, Robert A.; Raiswell, Robert Geochimica et Cosmochimica Acta, Vol. 47, Issue 5 https://doi.org/10.1016/0016-7037(83)90151-5	journal	May 1983
Sulfur isotope change across the Early Mississippian K–O (Kinderhookian–Osagean) δ13C excursion Maharjan, Dev; Jiang, Ganqing; Peng, Yongbo Earth and Planetary Science Letters, Vol. 494 https://doi.org/10.1016/j.epsl.2018.04.043	journal	July 2018
A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts Stolper, Daniel A.; Keller, C. Brenhin Nature, Vol. 553, Issue 7688 https://doi.org/10.1038/nature25009	journal	January 2018
A new model for atmospheric oxygen over Phanerozoic time Berner, R. A.; Canfield, D. E. American Journal of Science, Vol. 289, Issue 4 https://doi.org/10.2475/ajs.289.4.333	journal	April 1989
MC-ICP-MS measurement of δ34S and ∆33S in small amounts of dissolved sulfate Paris, Guillaume; Sessions, Alex L.; Subhas, Adam V. Chemical Geology, Vol. 345 https://doi.org/10.1016/j.chemgeo.2013.02.022	journal	May 2013
Cenozoic record of δ34S in foraminiferal calcite implies an early Eocene shift to deep-ocean sulfide burial Rennie, Victoria C. F.; Paris, Guillaume; Sessions, Alex L. Nature Geoscience, Vol. 11, Issue 10 https://doi.org/10.1038/s41561-018-0200-y	journal	August 2018
Sulfur-isotope variations in Pennsylvanian shales of the midwestern United States Coveney, Jr., Raymond M.; Shaffer, Nelson R. Geology, Vol. 16, Issue 1 https://doi.org/10.1130/0091-7613(1988)016<0018:SIVIPS>2.3.CO;2	journal	January 1988
Secular variation in seawater chemistry and the origin of calcium chloride basinal brines Lowenstein, Tim K.; Hardie, Lawrence A.; Timofeeff, Michael N. Geology, Vol. 31, Issue 10 https://doi.org/10.1130/G19728R.1	journal	January 2003
Evidence for global (glacial-eustatic) control over upper Carboniferous (Pennsylvanian) cyclothems in midcontinent North America Heckel, Philip H. Geological Society, London, Special Publications, Vol. 55, Issue 1 https://doi.org/10.1144/GSL.SP.1990.055.01.02	journal	January 1990
Speciation and distribution of sulfur in a mollusk shell as revealed by in situ maps using X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge Dauphin, Y. American Mineralogist, Vol. 90, Issue 11-12 https://doi.org/10.2138/am.2005.1640	journal	November 2005
Glacial weathering, sulfide oxidation, and global carbon cycle feedbacks Torres, Mark A.; Moosdorf, Nils; Hartmann, Jens Proceedings of the National Academy of Sciences, Vol. 114, Issue 33 https://doi.org/10.1073/pnas.1702953114	journal	July 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
Delayed fungal evolution did not cause the Paleozoic peak in coal production Nelsen, Matthew P.; DiMichele, William A.; Peters, Shanan E. Proceedings of the National Academy of Sciences, Vol. 113, Issue 9 https://doi.org/10.1073/pnas.1517943113	journal	January 2016
87Sr/86Sr, δ13C and δ18O evolution of Phanerozoic seawater Veizer, Ján; Ala, Davin; Azmy, Karem Chemical Geology, Vol. 161, Issue 1-3 https://doi.org/10.1016/S0009-2541(99)00081-9	journal	September 1999
Global rates of marine sulfate reduction and implications for sub-sea-floor metabolic activities Bowles, M. W.; Mogollon, J. M.; Kasten, S. Science, Vol. 344, Issue 6186 https://doi.org/10.1126/science.1249213	journal	May 2014
Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa Cusack, Maggie; Dauphin, Yannicke; Cuif, Jean-Pierre Chemical Geology, Vol. 253, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2008.05.007	journal	August 2008
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

Similar Records

The Brachiopod δ¹¹B Record Across the Carboniferous-Permian Climate Transition

Journal Article · Sat Sep 12 00:00:00 EDT 2020 · Paleoceanography and Paleoclimatology · OSTI ID:1656542

Legett, Shelbie A.; Rasbury, E. T.; Grossman, E. L.; +2 more

Chemical and Isotopic Evidence for Organic Matter Sulfurization in Redox Gradients Around Mangrove Roots

Journal Article · Wed May 08 00:00:00 EDT 2019 · Frontiers in Earth Science · OSTI ID:1656542

Raven, M. R.; Fike, D. A.; Gomes, M. L.; +1 more

Diagenesis of an upper Devonian carbonate-evaporite sequence: Birdbear Formation, southern interior plains, Canada

Journal Article · Sun Sep 01 00:00:00 EDT 1996 · Journal of Sedimentary Research, Section A: Sedimentary Petrology and Processes · OSTI ID:1656542

Whittaker, S G; Mountjoy, E W

Related Subjects

54 ENVIRONMENTAL SCIENCES
biogeochemical cycles
sulfur isotope geochemistry
carbonate associated sulfate
brachiopods
Permo-Carboniferous

Title: Brachiopod δ34SCAS microanalyses indicate a dynamic, climate-influenced Permo-Carboniferous sulfur cycle

Citation Formats

References (57)

Similar Records

Related Subjects

Title: Brachiopod δ³⁴S_CAS microanalyses indicate a dynamic, climate-influenced Permo-Carboniferous sulfur cycle