Isotopic evidence of environmental changes during the Devonian–Carboniferous transition in South China and its implications for the biotic crisis

The Devonian-Carboniferous (D-C) transition coincides with the Hangenberg Crisis, carbon isotope anomalies, and the enhanced preservation of organic matter associated with marine redox fluctuations. The proposed driving factors for the biotic extinction include variations in the eustatic sea level, paleoclimate fluctuation, climatic conditions, redox conditions, and the configuration of ocean basins. To investigate this phenomenon and obtain information on the paleo-ocean environment of different depositional facies, we studied a shallow-water carbonate section developed in the periplatform slope facies on the southern margin of South China, which includes a well-preserved succession spanning the D-C boundary. The integrated chemostratigraphic trends reveal distinct excursions in the isotopic compositions of bulk nitrogen, carbonate carbon, organic carbon, and total sulfur. A distinct negative δ15 N excursion (~-3.1‰) is recorded throughout the Middle Si. praesulcata Zone and the Upper Si. praesulcata Zone, when the Hangenberg mass extinction occurred. We attribute the nitrogen cycle anomaly to enhanced microbial nitrogen fixation, which was likely a consequence of intensified seawater anoxia associated with increased denitrification, as well as upwelling of anoxic ammonium-bearing waters. Negative excursions in the δ13 Ccarb and δ13 Corg values were identified in the Middle Si. praesulcata Zone and likely resulted from intense deep ocean upwelling that amplified nutrient fluxes and delivered 13 C-depleted anoxic water masses. Decreased δ34 S values during the Middle Si. praesulcata Zone suggests an increasing contribution of water-column sulfate reduction under euxinic conditions. Contributions of organic matter produced by anaerobic metabolisms to the deposition of shallow carbonate in the Upper Si. praesulcata Zone is recorded by the nadir of δ13 Corg values associated with maximal △13 C. The integrated δ15 N-δ13 C-δ34 S data suggest that significant ocean-redox variation was recorded in South China during the D-C transition; and that this prominent fluctuation was likely associated with intense upwelling of deep anoxic waters. The temporal synchrony between the development of euxinia/anoxia and the Hangenberg Event indicates that the redox oscillation was a key factor triggering manifestations of the biodiversity crisis.

[1]  B. Hart,et al.  Basin-scale reconstruction of euxinia and Late Devonian mass extinctions , 2023, Nature.

[2]  Ting Nie,et al.  Devonian-Carboniferous boundary in China , 2021, Palaeobiodiversity and Palaeoenvironments.

[3]  R. T. Becker,et al.  Review of Devonian-Carboniferous Boundary sections in the Rhenish Slate Mountains (Germany) , 2021, Palaeobiodiversity and Palaeoenvironments.

[4]  Wei Wei,et al.  Secular variation in the elemental composition of marine shales since 840 Ma: Tectonic and seawater influences , 2020 .

[5]  H. Schönlaub,et al.  Large environmental disturbances caused by magmatic activity during the Late Devonian Hangenberg Crisis , 2020 .

[6]  J. Marshall,et al.  UV-B radiation was the Devonian-Carboniferous boundary terrestrial extinction kill mechanism , 2020, Science Advances.

[7]  A. Anbar,et al.  Extensive marine anoxia associated with the Late Devonian Hangenberg Crisis , 2020, Earth and Planetary Science Letters.

[8]  Wenkun Qie,et al.  Intensified Ocean Deoxygenation During the end Devonian Mass Extinction , 2019, Geochemistry, Geophysics, Geosystems.

[9]  Shang Xu,et al.  Productivity or preservation? The factors controlling the organic matter accumulation in the late Katian through Hirnantian Wufeng organic-rich shale, South China , 2019, Marine and Petroleum Geology.

[10]  M. Joachimski,et al.  Late Devonian carbon isotope chemostratigraphy: A new record from the offshore facies of South China , 2019, Global and Planetary Change.

[11]  P. Wignall,et al.  Interpreting the Carbon Isotope Record of Mass Extinctions , 2019, Elements.

[12]  A. Anbar,et al.  Global-ocean redox variations across the Smithian-Spathian boundary linked to concurrent climatic and biotic changes , 2019, Earth-Science Reviews.

[13]  S. Carmichael,et al.  The Devonian-Carboniferous boundary in Vietnam: Sustained ocean anoxia with a volcanic trigger for the Hangenberg Crisis? , 2019, Global and Planetary Change.

[14]  V. Kanický,et al.  Tracing paleoredox conditions across the Devonian–Carboniferous boundary event: A case study from carbonate-dominated settings of Belgium, the Czech Republic, and northern France , 2019, Sedimentary Geology.

[15]  Huaichun Wu,et al.  How Did South China Connect to and Separate From Gondwana? New Paleomagnetic Constraints From the Middle Devonian Red Beds in South China , 2018, Geophysical Research Letters.

[16]  Xiaoying Shi,et al.  Nitrogen isotope constraints on the early Ediacaran ocean redox structure , 2018, Geochimica et Cosmochimica Acta.

[17]  Wen-Yi Guo,et al.  Devonian integrative stratigraphy and timescale of China , 2018, Science China Earth Sciences.

[18]  P. Zong,et al.  Hangenberg Black Shale with cymaclymeniid ammonoids in the terminal Devonian of South China , 2018, Palaeobiodiversity and Palaeoenvironments.

[19]  M. Droser,et al.  A stable and productive marine microbial community was sustained through the end‐Devonian Hangenberg Crisis within the Cleveland Shale of the Appalachian Basin, United States , 2018, Geobiology.

[20]  Linda C. Kah,et al.  Proterozoic carbonates of the Vindhyan Basin, India: Chemostratigraphy and diagenesis , 2018 .

[21]  V. Kanický,et al.  Fine-scale LA-ICP-MS study of redox oscillations and REEY cycling during the latest Devonian Hangenberg Crisis (Moravian Karst, Czech Republic) , 2017 .

[22]  G. Reichart,et al.  Definition of new trace-metal proxies for the controls on organic matter enrichment in marine sediments based on Mn, Co, Mo and Cd concentrations , 2016 .

[23]  Wenkun Qie,et al.  Latest Devonian to earliest Carboniferous conodont and carbon isotope stratigraphy of a shallow‐water sequence in South China , 2016 .

[24]  R. Buick,et al.  The evolution of Earth's biogeochemical nitrogen cycle , 2016 .

[25]  A. J. Kaufman,et al.  Environmental context for the terminal Ediacaran biomineralization of animals , 2016, Geobiology.

[26]  A. J. Kaufman,et al.  Sulfur isotope constraints on marine transgression in the lacustrine Upper Cretaceous Songliao Basin, northeastern China , 2016 .

[27]  J. Marshall,et al.  Greenhouse to icehouse: a biostratigraphic review of latest Devonian–Mississippian glaciations and their global effects , 2016, Special Publications.

[28]  Wenkun Qie,et al.  Changes in marine nitrogen fixation and denitrification rates during the end-Devonian mass extinction , 2016 .

[29]  Jinzhuang Xue,et al.  Comparative study of Late Devonian (Famennian) brachiopod assemblages, sea level changes, and geo-events in northwestern and southern China , 2016 .

[30]  S. Carmichael,et al.  Climate instability and tipping points in the Late Devonian: Detection of the Hangenberg Event in an open oceanic island arc in the Central Asian Orogenic Belt , 2016 .

[31]  L. Sallan,et al.  Body-size reduction in vertebrates following the end-Devonian mass extinction , 2015, Science.

[32]  M. Gomes,et al.  Sulfur isotope fractionation in modern euxinic systems: Implications for paleoenvironmental reconstructions of paired sulfate–sulfide isotope records , 2015 .

[33]  Wenkun Qie,et al.  Local overprints on the global carbonate δ13C signal in Devonian–Carboniferous boundary successions of South China , 2015 .

[34]  A. J. Kaufman,et al.  Large sulfur isotope fractionations associated with Neoarchean microbial sulfate reduction , 2014, Science.

[35]  P. Wignall,et al.  Large igneous provinces and mass extinctions: An update , 2014 .

[36]  O. Bábek,et al.  Sea-level and environmental changes around the Devonian–Carboniferous boundary in the Namur–Dinant Basin (S Belgium, NE France): A multi-proxy stratigraphic analysis of carbonate ramp archives and its use in regional and interregional correlations , 2014 .

[37]  S. Bowring,et al.  High‐precision U–Pb age and duration of the latest Devonian (Famennian) Hangenberg event, and its implications , 2014 .

[38]  G. Gong,et al.  Concentration dependent nitrogen isotope fractionation during ammonium uptake by phytoplankton under an algal bloom condition in the Danshuei estuary, northern Taiwan , 2013 .

[39]  Xiaoying Shi,et al.  Nitrogen Isotope Evidence for Redox Variations at the Ediacaran-Cambrian Transition in South China , 2013, The Journal of Geology.

[40]  Linda C. Kah,et al.  Carbon isotope records in a Mesoproterozoic epicratonic sea: Carbon cycling in a low-oxygen world , 2013 .

[41]  S. Kurkiewicz,et al.  Deciphering the upper Famennian Hangenberg Black Shale depositional environments based on multi-proxy record , 2012 .

[42]  S. Strobl,et al.  Palaeoenvironmental conditions during deposition of the Upper Cretaceous oil shale sequences in the Songliao Basin (NE China): Implications from geochemical analysis , 2012 .

[43]  Linda C. Kah,et al.  Chemostratigraphy of the Late Mesoproterozoic Atar Group, Taoudeni Basin, Mauritania: Muted isotopic variability, facies correlation, and global isotopic trends , 2012 .

[44]  R. Robinson,et al.  Dominant eukaryotic export production during ocean anoxic events reflects the importance of recycled NH4+ , 2012, Proceedings of the National Academy of Sciences.

[45]  T. Steuber,et al.  Climate-controlled mass extinctions, facies, and sea-level changes around the Devonian–Carboniferous boundary in the eastern Anti-Atlas (SE Morocco) , 2011 .

[46]  C. Spötl Long-term performance of the Gasbench isotope ratio mass spectrometry system for the stable isotope analysis of carbonate microsamples. , 2011, Rapid communications in mass spectrometry : RCM.

[47]  R. Amils,et al.  Association between catastrophic paleovegetation changes during Devonian–Carboniferous boundary and the formation of giant massive sulfide deposits , 2010 .

[48]  Paul G Falkowski,et al.  The Evolution and Future of Earth’s Nitrogen Cycle , 2010, Science.

[49]  T. Algeo,et al.  Land plant evolution and weathering rate changes in the Devonian , 2010 .

[50]  D. Canfield,et al.  High isotope fractionations during sulfate reduction in a low-sulfate euxinic ocean analog , 2010 .

[51]  B. Ward,et al.  Denitrification as the dominant nitrogen loss process in the Arabian Sea , 2009, Nature.

[52]  M. Joachimski,et al.  Devonian climate and reef evolution: Insights from oxygen isotopes in apatite , 2009 .

[53]  L. Stal,et al.  Nitrogen isotopic fractionation associated with growth on dinitrogen gas and nitrate by cyanobacteria , 2009 .

[54]  R. Bustin,et al.  Investigating the use of sedimentary geochemical proxies for paleoenvironment interpretation of thermally mature organic-rich strata: Examples from the Devonian–Mississippian shales, Western Canadian Sedimentary Basin , 2009 .

[55]  Chen Xu,et al.  Paired δ13Ccarb and δ13Corg records of Upper Ordovician (Sandbian–Katian) carbonates in North America and China: Implications for paleoceanographic change , 2008 .

[56]  J. Hower,et al.  Changes in ocean denitrification during Late Carboniferous glacial–interglacial cycles , 2008 .

[57]  D. Canfield,et al.  Production of 15N-depleted biomass during cyanobacterial N2-fixation at high Fe concentrations , 2008 .

[58]  A. Bekker,et al.  Fractionation between inorganic and organic carbon during the Lomagundi (2.22–2.1 Ga) carbon isotope excursion , 2008 .

[59]  T. Steuber,et al.  Environmental change during the Late Famennian and Early Tournaisian (Late Devonian–Early Carboniferous): implications from stable isotopes and conodont biofacies in southern Europe , 2008 .

[60]  B. Cramer,et al.  Early Silurian paired δ13Ccarb and δ13Corg analyses from the Midcontinent of North America: Implications for paleoceanography and paleoclimate , 2007 .

[61]  T. Lyons,et al.  Hydrographic conditions of the Devono–Carboniferous North American Seaway inferred from sedimentary Mo–TOC relationships , 2007 .

[62]  Hong-zhen Feng,et al.  Carbon isotope variation through the Neoproterozoic Doushantuo and Dengying Formations, South China: Implications for chemostratigraphy and paleoenvironmental change , 2007 .

[63]  M. Benoît,et al.  Geological and land use control on δ34S and δ18O of river dissolved sulfate: The Moselle river basin, France , 2007 .

[64]  L. Marynowski,et al.  Water column euxinia and wildfire evidence during deposition of the Upper Famennian Hangenberg event horizon from the Holy Cross Mountains (central Poland) , 2007, Geological Magazine.

[65]  Yiefei Jia Nitrogen isotope fractionations during progressive metamorphism: A case study from the Paleozoic Cooma metasedimentary complex, southeastern Australia , 2006 .

[66]  T. Steuber,et al.  Geochemical evidence for major environmental change at the Devonian¿Carboniferous boundary in the Carnic Alps and the Rhenish Massif , 2006 .

[67]  M. Joachimski,et al.  Carbon isotope stratigraphy of the Devonian of Central and Southern Europe , 2006 .

[68]  M. Böttcher,et al.  34S/32S and 18O/16O Fractionation During Sulfur Disproportionation by Desulfobulbus propionicus , 2005 .

[69]  Daizhao Chen,et al.  The Late Devonian Frasnian–Famennian (F/F) biotic crisis: Insights from δ13Ccarb, δ13Corg and 87Sr / 86Sr isotopic systematics , 2005 .

[70]  J. Kallmeyer,et al.  Geochemistry of Peruvian near-surface sediments , 2004 .

[71]  Linda C. Kah,et al.  Low marine sulphate and protracted oxygenation of the Proterozoic biosphere , 2004, Nature.

[72]  R. Berner A model for calcium, magnesium and sulfate in seawater over Phanerozoic time , 2004 .

[73]  B. Jørgensen,et al.  Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments , 2004 .

[74]  J. G. Kuenen,et al.  Anaerobic ammonium oxidation by anammox bacteria in the Black Sea , 2003, Nature.

[75]  S. Calvert,et al.  Nitrogen isotope and productivity variations along the northeast Pacific margin over the last 120 kyr: Surface and subsurface paleoceanography , 2002 .

[76]  A. Devol,et al.  A global marine‐fixed nitrogen isotopic budget: Implications for Holocene nitrogen cycling , 2002 .

[77]  A. J. Kaufman,et al.  The sulfur isotopic composition of Neoproterozoic seawater sulfate: implications for a snowball Earth? , 2002 .

[78]  M. Lehmann,et al.  Preservation of organic matter and alteration of its carbon and nitrogen isotope composition during simulated and in situ early sedimentary diagenesis , 2002 .

[79]  A. Jahren The biogeochemical consequences of the mid-Cretaceous superplume , 2002 .

[80]  D. Beerling,et al.  An atmospheric pCO2 reconstruction across the Cretaceous-Tertiary boundary from leaf megafossils , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[81]  G. Wefer,et al.  Early diagenesis of organic matter from sediments of the eastern subtropical Atlantic: evidence from stable nitrogen and carbon isotopes , 2001 .

[82]  R. Wilkin,et al.  Variations in pyrite texture, sulfur isotope composition, and iron systematics in the Black Sea: evidence for Late Pleistocene to Holocene excursions of the o , 2001 .

[83]  P. Hofmann,et al.  Carbon–sulfur–iron relationships and δ13C of organic matter for late Albian sedimentary rocks from the North Atlantic Ocean: paleoceanographic implications , 2000 .

[84]  A. J. Kaufman,et al.  THE ABUNDANCE OF 13C IN MARINE ORGANIC MATTER AND ISOTOPIC FRACTIONATION IN THE GLOBAL BIOGEOCHEMICAL CYCLE OF CARBON DURING THE PAST 800 MA , 1999 .

[85]  D. Sigman,et al.  Nitrogen isotopic variations in the Gulf of California since the Last Deglaciation: Response to global climate change , 1999 .

[86]  R. Bustin,et al.  Devonian-carboniferous Hangenberg mass extinction event, widespread organic-rich mudrock and anoxia: Causes and consequences , 1999 .

[87]  L. Codispoti,et al.  Nitrogen isotopic studies in the suboxic Arabian Sea , 1998, Journal of Earth System Science.

[88]  Thomas J. Algeo,et al.  Terrestrial-marine teleconnections in the Devonian: links between the evolution of land plants, weathering processes, and marine anoxic events , 1998 .

[89]  W. Liesack,et al.  Elemental Sulfur and Thiosulfate Disproportionation by Desulfocapsa sulfoexigens sp. nov., a New Anaerobic Bacterium Isolated from Marine Surface Sediment , 1998, Applied and Environmental Microbiology.

[90]  A. Devol,et al.  Isotopic fractionation of oxygen and nitrogen in coastal marine sediments , 1997 .

[91]  R. Bustin,et al.  Demise of a Devonian-Carboniferous carbonate ramp by eutrophication , 1996 .

[92]  A. J. Kaufman,et al.  Neoproterozoic variations in the C-isotopic composition of seawater: stratigraphic and biogeochemical implications. , 1995, Precambrian research.

[93]  J. Leventhal Carbon-sulfur plots to show diagenetic and epigenetic sulfidation in sediments , 1995 .

[94]  M. Brasier,et al.  Sr and C isotopes in Lower Cambrian carbonates from the Siberian craton: A paleoenvironmental record during the ‘Cambrian explosion’ , 1994 .

[95]  M. Altabet,et al.  Sedimentary nitrogen isotopic ratio as a recorder for surface ocean nitrate utilization , 1994 .

[96]  K. Finster,et al.  Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese , 1993, Applied and environmental microbiology.

[97]  David L. Kirchman,et al.  Isotope fractionation associated with ammonium uptake by a marine bacterium , 1992 .

[98]  B. Wilkinson,et al.  Meteoric-burial Diagenesis of Middle Pennsylvanian Limestones in the Orogrande Basin, New Mexico: Water/Rock Interactions and Basin Geothermics , 1992 .

[99]  J. Hayes,et al.  Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels. , 1992, Global biogeochemical cycles.

[100]  G. Flajs,et al.  Decision on the Devonian-Carboniferous boundary stratotype , 1991 .

[101]  W. Dean,et al.  Iron-sulfur-carbon relationships in organic-carbon-rich sequences I: Cretaceous Western Interior seaway , 1989 .

[102]  M. Altabet Variations in nitrogen isotopic composition between sinking and suspended particles: implications for nitrogen cycling and particle transformation in the open ocean , 1988 .

[103]  R. K. Given,et al.  Isotopic Evidence for the Early Meteoric Diagenesis of the Reef Facies, Permian Reef Complex of West Texas and New Mexico , 1986 .

[104]  R. Berner,et al.  Pyrite formation in euxinic and semi-euxinic sediments , 1985 .

[105]  R. Berner Sedimentary pyrite formation: An update , 1984 .

[106]  G. Racki,et al.  Comparative carbon isotope chemostratigraphy of major Late Devonian biotic crises , 2020 .

[107]  H. Svensen,et al.  The effects of large igneous provinces on the global carbon and sulphur cycles , 2016 .

[108]  B. Cramer,et al.  Record of the Late Devonian Hangenberg global positive carbon-isotope excursion in an epeiric sea setting: Carbonate production, organic-carbon burial and paleoceanography during the late Famennian , 2008 .

[109]  M. Schoonen Mechanisms of sedimentary pyrite formation , 2004 .

[110]  W. Ziegler,et al.  Late Devonian sea-level changes, catastrophic events, and mass extinctions , 2002 .

[111]  D. Canfield Biogeochemistry of Sulfur Isotopes , 2001 .

[112]  J. Boudou,et al.  Isotope study on organic nitrogen of Westphalian anthracites from the Western Middle field of Pennsylvania (U.S.A.) and from the Bramsche Massif (Germany) , 1998 .

[113]  K. L. Hanson,et al.  Effect of Phytoplankton Cell Geometry on Carbon Isotopic Fractionation , 1998 .

[114]  M. Streel,et al.  Eustatic cycles around the Devonian-Carboniferous boundary and the sedimentary and fossil record in Sauerland (Federal Republic of Germany) , 1992 .

[115]  S. Wainright,et al.  Diatom sources of 13C-rich carbon in marine food webs , 1991 .

[116]  C. Clayton Effect of maturity on carbon isotope ratios of oils and condensates , 1991 .

[117]  M. Streel,et al.  Spore correlations between the Rhenish Slate Mountains and the Russian Platform near the Devonian-Carboniferous Boundary , 1984 .