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ACCEPTED MANUSCRIPT 1 Coupling of marine and continental oxygen isotope records 2 during the Eocene-Oligocene transition 3 4 Nathan D. Sheldon1*, Stephen T. Grimes 2, Jerry J. Hooker3, Margaret E. Collinson 4, 5 Melanie J. Bugler2, Michael T. Hren5, Gregory D, Price 2, Paul A. Sutton 2 6 7 * Corresponding author: [email protected] 8 9 1 Department of Earth and Environmental Sciences, University of Michigan, Ann 10 Arbor, MI 48109, USA. 11 2 School of Geography, Earth & Environmental Sciences, Plymouth University, Drake 12 Circus, Plymouth, Devon, PL4 8AA, UK. 3 13 Department of Earth Sciences, Natural History Museum, Cromwell Road, London, 14 SW7 5BD, UK. 15 4 Department of Earth Sciences, Royal Holloway University of London, Egham, 16 Surrey, TW20 0EX, UK. 17 5Department of Chemistry, University of Connecticut, Storrs, CT 06269, USA. 18 19 ABSTRACT 20 While marine records of the Eocene-Oligocene transition (EOT) indicate a generally 21 coherent response to global cooling and the growth of continental ice on Antarctica, 22 continental records indicate substantial spatial variability. Marine EOT records are 23 marked by a ~+1.1‰ foraminiferal δ18O shift, but continental records rarely record 24 the same geochemical signature, making both correlation and linking of causal 25 mechanisms between marine and continental records challenging. Here, a new high- 26 resolution continental δ18O record, derived from the freshwater gill-breathing 27 gastropod Viviparus lentus, is presented from the Hampshire Basin (UK). The Solent 28 Group records marine incursions and has an established magnetostratigraphy, 29 making it possible to correlate the succession directly with marine records. The V. 30 lentus δ18O record indicates a penecontemporaneous, higher magnitude shift 31 (>+1.4‰) than marine records, which reflects both cooling and a source moisture 32 compositional shift consistent with the growth of Antarctic ice. When combined with 33 “clumped” isotope measurements from the same succession, about half of the 34 isotopic shift can be attributed to cooling and about half to source moisture change, 35 proportions similar to marine foraminiferal records. Thus, the new record indicates 36 strong hydrological cycle connections between marine and marginal continental 37 environments during the EOT not observed in continental interior records. 38 39 Keywords: Eocene – Oligocene transition; oxygen isotopes; climate; Vivparus; 40 gastropod; continental; glaciation 41 1 ACCEPTED MANUSCRIPT 42 1. INTRODUCTION 43 The Eocene-Oligocene transition (EOT), onset at ~34 Ma ago, represents a 44 climatic regime change from "greenhouse" conditions to "icehouse" conditions. 45 Physical evidence (various; e.g., Davis et al., 2012) indicates the initiation of large- 46 scale Antarctic glaciation during the EOT, with permanent ice sheets formed on 47 Antarctica for the first time between 34.0 and 33.65 Ma peaking at the onset of an 48 oxygen isotopic event known as Oi-1 (Miller et al., 1991; Zachos et al., 1996, 2001; 49 Coxall et al., 2005; Pälike et al., 2006, supplement), which is a ~+1.1 shift that 50 reflects a combination of temperature and salinity/ice volume change (Zachos et al., 51 2008). Both benthic (Coxall et al., 2005; Coxall and Wilson, 2011) and planktonic 52 (Pearson et al., 2008) foraminifera record a coherent spatial and temporal isotopic 53 response, which implies global-scale changes to the Earth's oceans and global-scale 54 climatic cooling. 55 In contrast, continental records are spatially variable (Sheldon, 2009; Zanazzi 56 et al., 2015), with regional differences in the magnitude of temperature change (e.g., 57 Zanazzi et al., 2007 vs. Retallack, 2007), the magnitude of precipitation change 58 (Sheldon and Retallack, 2004; Abels et al., 2011), and even whether precipitation 59 increased or decreased (Sheldon et al., 2009). The widely recognized positive 60 isotope excursion seen in marine foraminiferal δ18O records of the EOT glaciation is 61 rarely found by terrestrial records (cf. Zanazzi et al., 2007; 2008), which instead often 62 show no discernible shift in δ18O (e.g., Sheldon et al., 2012) or a delayed shift relative 63 to marine records (Zanazzi et al., 2007). In addition, it can be difficult to link marine 64 and terrestrial records of the EOT for two reasons: 1) continental successions are 65 most often preserved in endorheic basins, far from marine incursions that would 66 make direct age comparison possible, and 2) oxygen isotope records from 2 ACCEPTED MANUSCRIPT 67 continental interiors can be complicated by a variety of non-temperature related 68 factors (e.g., changing circulation patterns, orographic effects) or may respond to 69 local, rather than global hydrologic cycle drivers (e.g., Sheldon et al., 2012). Thus, 70 sections in continental strata that span the EOT and which are well-calibrated to the 71 geomagnetic polarity timescale and to marine geochronology are rare. 72 The English Hampshire Basin Solent Group (Fig. 1) was deposited in a coastal 73 floodplain environment. It has documented magnetostratigraphy, sequence 74 stratigraphy, mammalian and charophyte biostratigraphy, and brief calcareous 75 nannoplankton events (Hooker, 1987, 2010; Sille et al., 2004; Gale et al., 2006; 76 Hooker et al., 2009) that allow good calibration to marine records through the entire 77 late Eocene (Priabonian) and early Oligocene (Rupelian). The depositional rate of the 78 Solent Group strata is high, ranging from ca. 3–10 cm ky-1 (Hooker et al., 2009), 79 which facilitates high resolution sampling. The only significant hiatus is during the 80 glacial maximum following the Oi-1 event, caused by major sea-level fall. Hren et al. 81 (2013) recently published a “clumped isotope” paleotemperature reconstruction of the 82 EOT from the Solent Group based on the prosobranch gastropod Viviparus lentus 83 (Solander) where they found: 1) the magnitude of mean annual air temperature 84 change (~4–6° C) was comparable to North Atlantic sea surface temperature 85 changes, and 2) growing season temperatures for V. lentus were essentially constant 86 prior to the EOT, but dropped by nearly 10° C following Oi-1. An earlier climate study 87 of the Solent Group from the combined proxies of mammal tooth enamel, pulmonate 88 gastropod (Lymnaea longiscata Brongniart) shells, fish otoliths and charophyte 89 gyrogonites at six horizons (Grimes et al. 2005) also found little evidence for 90 variability in summer temperatures prior to the EOT. However, both of those previous 91 studies had limited data for the early Oligocene. 3 ACCEPTED MANUSCRIPT 92 To build upon these low resolution isotope-derived climate studies and to 93 provide greater data coverage for the early Oligocene, we have analyzed the δ18O 94 composition of shell carbonate of V. lentus at numerous horizons through three 95 million years (35.4–32.4Ma) of the Solent Group (Bugler, 2011). This new, denser 96 paleoclimatic record (with ca. 750 ky leading up to Oi-1 having a frequency interval of 97 ca. 35 ky) is then compared with marine oxygen isotope records and with 98 paleoclimatic records from other continental EOT sites (Fig. 2). 99 100 2. SAMPLE LOCATIONS AND METHODOLOGY 101 Six localities representing different parts of the late Eocene (Priabonian) to 102 earliest Oligocene (Rupelian) Solent Group stratigraphy of the Hampshire Basin (Fig. 103 1; Supplemental Data and Table S1) were examined. In total, 40 stratigraphic 104 horizons containing abundant shells of the freshwater prosobranch (gill-breathing) 105 gastropod V. lentus were sampled, including both complete and fragmentary, but 106 identifiable, shells. Modern Viviparus gastropods inhabit only clean, slowly moving or 107 stable water bodies, and their habitat tracks the availability of aquatic environments 108 (Boss, 1978). Fossil Viviparus gastropods have been used previously in studies of 109 both warming (Schmitz and Andreasson, 2001) and cooling (Hren et al., 2013) 110 Paleogene paleoclimate events, and modern Viviparus gastropod species reliably 111 record changing environmental conditions (Bugler, 2011). 112 Bulk sediment samples were air dried, disaggregated in warm water, and then 113 wet sieved using mesh sizes of 2 mm, 1 mm, and 250 µm. Each size fraction was 114 oven dried at 25 ºC. Between 7 and 15 randomly selected V. lentus fragments were 115 picked from the >2 mm size fraction, and cleaned in an ultrasonic bath. Each 116 individual fragment (n = 483) was crushed using an agate mortar and pestle. 4 ACCEPTED MANUSCRIPT 117 Between 0.30 mg and 0.50 mg of powder was placed into vials for isotope analysis. 118 The remainder was retained for repeat analyses and X-Ray Diffraction (XRD) in order 119 to check for any alteration of the original aragonite mineralogy. 120 To determine the preservation state of shells from individual horizons, powder 121 from 3 to 5 V. lentus fragments from each horizon was analyzed either at the 122 Plymouth University (PU) or at Royal Holloway, University of London (RHUL). At PU 123 the samples were analyzed by MJB, using a Phillips PW1792 X-ray diffractometer 124 (XRD) with High-Score Plus identification software. The V. lentus powder was aligned 125 along a metal plate, which was then placed into a sealed chamber within the XRD. A 126 Cu anode source was used with generator settings of 30kV and 40 nA. Expert High 127 Score was used to analyze the x-ray chromatography produced. At RHUL, samples 128 were analyzed courtesy of Dr. Dave Alderton using a Philips Analytical XRD PW3710 129 machine with PC-APD diffraction software. Samples were scanned between 20° to 130 50° (2θ) using a copper tube anode. 131 For isotope analysis the carbonate powders were reacted with 100% 132 phosphoric acid at 90 ºC for approximately 1 hour. The CO2 produced was analyzed 133 on an Isoprime Mass Spectrometer with a Gilson Multiflow carbonate auto-sampler at 134 Plymouth University. The results were calibrated against Vienna Pee Dee Belemnite 135 (VPDB) using the international standards NBS-19, IAEA -CO-8, and IAEA-CO-9.