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Marine C, S and N Biogeochemical Processes in the Redox-Stratified Early Cambrian Yangtze Oceanc

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Marine C, S and N Biogeochemical Processes in the Redox-Stratified Early Cambrian Yangtze Oceanc research-article10.1144/jgs2014-054Marine C, S and N biogeochemical processes in the redox-stratified early Cambrian Yangtze oceanC. Cai, L. Xiang, Y. Yuan, X. He, X. Chu, Y. Chen &, C. XuXXX10.1144/jgs2014-054C. Cai et al.Biogeochemical processes in Early Cambrian 20152014-054 Downloaded from http://jgs.lyellcollection.org/ at Chinese Academy of Sciences on May 5, 2015 Research article Journal of the Geological Society Published online April 8, 2015 doi:10.1144/jgs2014-054 | Vol. 172 | 2015 | pp. 390 –406 Marine C, S and N biogeochemical processes in the redox-stratified early Cambrian Yangtze ocean C. Cai1*, L. Xiang2, Y. Yuan1, X. He3, X. Chu1, Y. Chen1 & C. Xu1 1 Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China 2 State Key Laboratory of Paleobiology and Stratigraphy, Nanjing Institute of Geology and Palaeontology, Nanjing 210008, China 3 Hangzhou Research Institute of Geology, PetroChina, Hangzhou 310023, China * Correspondence: [email protected] Abstract: The temporal change of redox conditions of the Yangtze ocean has been revealed by investigating the Ediacaran– Cambrian transition section at Zhalagou, South China. During the earliest Cambrian, cherts and shales were deposited under an anoxic and ferruginous bottom water with significantly increasing total organic carbon and P contents, and negative shift in kerogen δ13C values in the lowest part of the section. Euxinic bottom water conditions occurred during the earliest Cam- brian Stage 2, with the surface water dominated by N2 utilization by cyanobacteria or sulphur bacteria leading to negative kerogen δ15N values. During Stage 3, dissolved oxygen and sulphate concentrations were significantly increased, and thus the oxidized surface water and the redox transition zone overlying a euxinic bottom water may have been expanded, resulting in an increase in kerogen δ15N increasing to 2–4‰, a decrease in pyrite δ34S decreasing to as low as –24.6‰ and differences in δ34S values between kerogen and pyrite as high as 37‰. This period coincided with the abrupt appearance of large-body metazoans. Thus, the expanding oxic surface water may have reinforced the evolution of animals or vice versa. Interestingly, kerogen δ34S values show negative relationships to FePy/FeHR ratios and pyrite sulphur contents, indicating that they can be used to reflect redox conditions, with the lightest values being obtained from euxinic environments. Received 23 May 2014; revised 12 December 2014; accepted 13 December 2014 Dramatic biota evolution occurred during the Early Cambrian with anoxic and sulphidic conditions during Stage 2 in the inner shelf the disappearance of late Ediacaran soft-bodied biota and the and slope environments as recorded in the Shatan and Songtao sec- occurrence of the Cambrian explosion. During the Early Cam- tions (Goldberg et al. 2007; Guo et al. 2007; Xu et al. 2012). This brian, small shell fossils, sponges and arthropods, and trilobites sulphidic water column did not extend to the deeper lower slope and other metazoan fossils appeared, and the abundance and diver- and basin environment as found in the Tianping and Lijiatuo sec- sity of fossils were then rapidly increased. Redox conditions for tions (Cai et al. 2012; Wang et al. 2012a). the Early Cambrian Yangtze ocean are crucial to understand these However, Fe speciation measurements do not focus on the changes. Oxygen has been considered as the most likely extrinsic surface water, where the N cycle is most active. Consequently, the factor for the evolution of large, metabolically active animals N cycle in ocean chemistry must be evaluated directly (Busigny (Knoll & Carroll 1999); thus increasing oxidization of deep ocean et al. 2013; Godfrey et al. 2013). In sedimentary rocks, nitrogen is + has been considered to lead to the evolution of large-body metazo- mostly preserved as organic nitrogen and as fixed NH4 substitut- ans (Wang et al. 2012a) although the oxidization may not neces- ing for K+ in phyllosilicates. Nitrogen isotopes can provide a sarily result from an increase in atmospheric oxygen (Lenton et al. record of specific biosignatures and are sensitive to environmental 2014). redox changes during Earth history (Beaumont & Robert 1999; The global C, S, Fe, N and P cycles are intimately linked Godfrey & Falkowski 2009; Busigny et al. 2013; Cremonese et al. through biotic and abiotic processes, which are controlled by 2013, 2014; Godfrey et al. 2013; Thomazo & Papineau 2013). The marine redox and finally by atmospheric oxygen concentration nitrogen cycle for the late Archaean ocean has been proposed to (Berner 1989; Algeo & Ingall 2007). Carbon, S, Fe and N specia- include N2 fixation, denitrification, nitrification and anammox and + tion, and chemical and isotopic compositions have been shown to NH4 assimilation into organic matter (Fig. 1). It is considered that have great potential for palaeoenvironmental and biogeochemical the ‘normal’ or oxygenated marine sedimentary N has a δ15N range reconstructions (Canfield et al. 1986, 2008; Canfield & Teske from +2 to +6‰, and is a product of equilibrium between nitrate 1996; Poulton & Canfield 2005; Godfrey & Falkowski 2009; assimilation, N2 fixation and denitrification. Under anoxic condi- Li et al. 2010; Godfrey et al. 2013). tions, nitrate is limited and thus dissolved atmospheric N2 is uti- Based on Fe speciation and Mo isotopic composition, the slope lized by diazotrophs in the water column; sedimentary organic to basin environment below storm wave base in south China dur- matter is expected to have an isotopic value averaging zero ing the earliest Cambrian (Fortunian) was considered as sulphidic (Beaumont & Robert 1999; Kuypers et al. 2004). The δ15N values (Canfield et al. 2008; Wille et al. 2008). However, the strata have can be negative in euxinic conditions (Cremonese et al. 2013) been considered to date to about 20 Ma after the Ediacaran– where chalcophiles such as Mo and Fe, which are essential to N2 Cambrian transition (Jiang et al. 2009). More recently, the earliest fixation (Anbar & Knoll 2002), may have been precipitated as sul- Cambrian lower slope to basin environment has been accepted as a phides. However, positive δ15N signatures have been reported redox stratified water column with a thin oxygenated (oxic or dys- from the Late Archaean ferruginous ocean (Busigny et al. 2013) oxic) upper layer overlying an anoxic and ferruginous lower layer and sulphidic Mesoproterozoic ocean in the Animikie Basin as supported by several geochemical proxies (Cai et al. 2012; (Godfrey et al., 2013), as well as fully oxic ocean (Cremonese Wang et al. 2012a). The underlying water chemistry changed to et al. 2013; Busigny et al. 2013), and thus may record very © 2015 The Author(s). Published by The Geological Society of London. All rights reserved. For permissions: http://www.geolsoc.org.uk/permissions. Publishing disclaimer: www.geolsoc.org.uk/pub_ethics Downloaded from http://jgs.lyellcollection.org/ at Chinese Academy of Sciences on May 5, 2015 Biogeochemical processes in Early Cambrian 391 phosphate from an anoxic basin has positive feedbacks on marine productivity (Algeo & Ingall 2007). The increase in primary pro- ductivity is expected to result in a decrease in selectivity of 12C and 13C, and thus to change the organic matter δ13C value. In the present study, we performed a series of analyses on Si, P and Ba elements, Fe speciation, S isotopes of pyrites, and C, S and N isotopes of organic matter (or kerogen) from cherts, shales and mudstones from the Lower Cambrian in the Zhalagou section, South China. The aims of this study were (1) to determine redox conditions of water in the palaeohigh around a deep basin during the Early Cambrian using multi-proxies, (2) to understand the nitrogen cycle in oxygenated surface water overlying anoxic and sulphidic or ferruginous water, and thus (3) to show whether δ15N values can be used to explain the N cycle without independent con- straints from other proxies; also, (4) to determine what controlled total organic carbon (TOC) or organic productivity, (5) to describe sulphur occurrence and show whether kerogen δ34S is related to redox conditions, and (6) to discuss the possible link of evolution Fig. 1. The biogeochemical nitrogen cycle (Godfrey & Falkowski of redox conditions to the Cambrian explosion. 2009). Geological setting different N biogeochemical cycles. For example, no extreme N limitation has been proposed to explain positive and stable The Zhalagou section is located about 5 km east of Sandu County δ15N values (c. 5.3‰ at inner shelf and c. 3.9‰ at outer shelf sites) in Guizhou Province, South China (Fig. 2). The Yangtze Block for sediments deposited under sulphidic conditions in the evolved from a rift basin to a passive continental margin basin dur- Mesoproterozoic redox-stratified water column in the Animikie ing the Ediacaran–Cambrian transition (Wang et al. 2003). Basin (Busigny et al. 2013). Thus, interpretation of the N isotopes Metazoans began to diversify and expand during the Early in terms of the N biogeochemical cycle requires independent con- Cambrian. The lowest part of the Cambrian was stratigraphically straints on the redox structure of the ocean using other proxies correlated using assemblages of small shelly fossils (Steiner et al. such as iron speciation and sulphur isotopes. 2007). Traditionally, the Cambrian System was divided into the Organic matter is expected to have δ15N values lower than bulk Early, Middle and Late Cambrian series. The Early Cambrian in – + – sediment if inorganic N (NO3 , NH4 , or NO2 ) is not fully con- the Yangtze Block was further subdivided into four stages: in sumed, or if N2 fixation is high relative to other forms of N assim- ascending order, the Meishucunian Stage, Qiongzhusian Stage, ilation. Thus, a roughly parallel changing trend was observed Canglangpuan Stage and Longwangmiaoan Stage (Yin 1996; (Kump et al. 2011). The δ15N values will be similar when produc- Xiang et al. 1999). Based on the small shelly fossils record, the tivity consumes all inorganic N (Godfrey & Falkowski 2009; Meishucunian Stage is subdivided into four biozones in shallow Godfrey et al.
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