1 Tonian-Cryogenian boundary sections of Argyll, Scotland Fairchild, et al. Highlights • Robust Sr– and C- isotope stratigraphy despite greenschist facies metamorphism 13 • Islay carbonates have molar tooth structure and low positive δ C • Cryogenian base at 9 m below diamictite, above negative δ13C (Garvellach) anomaly • Ice-rafted deposits overlap with shoaling, evaporative carbonates on the Garvellach Islands • Simple late Tonian Neoproterozoic section, 1.5 km thick, on seabed off the Garvellachs Revised version Precambrian Research 2nd August 2017 2 Tonian-Cryogenian boundary sections of Argyll, Scotland Ian J. Fairchilda,1, Anthony M. Spencerb, Dilshad O. Alic, Ross P. Andersond, Roger Andertone, Ian Boomera, Dayton Dovef, Jonathan D. Evansa, Michael J. Hambreyg, John Howeh, Yusuke Sawakii, Graham A. Shieldsj, Alasdair Skeltonk, Maurice E. Tuckerl, Zhengrong Wangm, Ying Zhouj a School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham B15 2TT, UK b Madlavollveien 14, 4041 Hafrsfjord, Norway c Department of Earth Sciences, Royal Holloway University of London, Egham, Surrey TW20 0EX, UK d Department of Geology and Geophysics, Yale University, 210 Whitney Avenue, New Haven, Connecticut, 06511, USA e Kilmichael House Kilmichael Glassary, Lochgilphead, Argyll, PA31 8QA, UK f British Geological Survey, Murchison House, West Mains Rd, Edinburgh EH9 3LA, UK g Centre for Glaciology, Department of Geography and Earth Sciences, Aberystwyth University, Aberystwyth, Ceredigion SY23 3DB, UK h Scottish Association for Marine Science, Scottish Marine Institute, Oban PA37 1QA, UK I Department of Earth Science and Astronomy, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo, 153- 8902, Japan j Department of Earth Sciences, University College London, Gower Street, London WC1E 6BT, UK. k Department of Geological Sciences, Stockholm University, 106 91 Stockholm, Sweden l School of Earth Sciences, University of Bristol, Wills Memorial Building, Queen’s Road, Bristol, BS8 1RJ, UK m Department of Earth and Atmospheric Sciences, The City College of New York, CUNY, New York, New York, 10031, USA 1 Corresponding author at School of Geography, Earth and Environmental Sciences, University of Birmingham B15 2TT, UK. Tel: +441214144181. E-mail address: [email protected] (I.J.Fairchild) 3 ABSTRACT The Tonian-Cryogenian System boundary is to be defined at a GSSP (Global Boundary Stratigraphic Section and Point) beneath the first evidence of widespread glaciation. A candidate lies within the Dalradian Supergroup of Scotland and Ireland, which is least deformed and metamorphosed in Argyll, western Scotland. We present new stratigraphic profiles and interpretations from the Isle of Islay and the Garvellach Islands, update the chemostratigraphy of the Appin Group Tonian carbonates underlying the thick (ca. 1 km) glacigenic Port Askaig Formation (PAF) and demonstrate an environmental transition at the contact. The Appin Group forms a regionally extensive, >4 km-thick, succession of limestones, shales and sandstones deposited on a marine shelf. On Islay, the upper part of the lithostratigraphy has been clarified by measuring and correlating two sections containing distinctive stratigraphic levels including molar tooth structure, oolite, stromatolitic dolomite and intraclastic microbial mounds. Significantly deeper erosion at the unconformity at the base of the overlying PAF is demonstrated in 13 the southern section. Carbonate facies show a gradual decline in δ CVPDB from +5 to +2‰ upwards. In NE Garbh Eileach (Garvellach Islands), a continuously exposed section of Appin Group carbonates, 70 m thick, here designated the Garbh Eileach Formation (GEF), lies conformably beneath the PAF. The GEF and the GEF-PAF boundary relationships are re-described with new sedimentological logs, petrological and stable isotope data. Interstratified limestone and dolomicrosparite with δ13C of -4 to -7 ‰ (a feature named the Garvellach anomaly, replacing the term Islay anomaly) are overlain by dolomite in which the isotope signature becomes weakly positive (up to +1 ‰) upwards. Shallow subtidal conditions become peritidal upwards, with evidence of wave and storm activity. Gypsum pseudomorphs and subaerial exposure surfaces are common near the top of the GEF. The basal diamictite (D1) of the PAF is rich in carbonate clasts similar to slightly deeper-water parts of the underlying succession. D1 is typically several metres thick with interstratified sandstone and conglomerate, but dies out laterally. Scattered siliciclastic coarse sandstone to pebble conglomerate with dropstones associated with soft-sediment deformation is interbedded with carbonate below and above D1. Dolomite beds with derived intraclasts and gypsum pseudomorphs are found above D1 (or equivalent position, where D1 is absent). Published and new Sr isotope studies, including successive leach data, demonstrate primary Tonian 87Sr/86Sr values of 0.7066-0.7069 on Islay, decreasing to 0.7064-0.7066 in the younger GEF limestones on the Garvellachs, with 1700-2700 ppm Sr. Other typically Tonian characteristics of the carbonates are the Sr-rich nature of limestones, molar tooth structure, and dolomitized peritidal facies with evidence of aridity. Seabed surveys suggesting uniformly-dipping strata and shallow borehole core material illustrate the potential for extending the Tonian record offshore of the Garvellachs. 13 A candidate Tonian-Cryogenian GSSP is proposed on Garbh Eileach within the smooth δ C 13 profile at the cross-over to positive δ C signatures, 4 m below the first occurrence of ice-rafted sediment and 9 m below the first diamictite. Although lacking radiometric constraints or stratigraphically significant biotas or biomarkers, the Scottish succession has a thick and relatively complete sedimentary record of glaciation, coherent carbon and strontium chemostratigraphy, lateral continuity of outcrops and 100% exposure at the proposed boundary interval. Keywords: Neoproterozoic, limestone, glaciation, dolomite, carbon isotopes, strontium isotopes 4 1. Introduction and previous research A revolution in our understanding of the evolution of the Earth system during the Neoproterozoic Era has occurred in the last 20 years (Spence et al., 2016; Hoffman et al., 2017). Notably it has been confirmed that on two occasions ice sheets had a global distribution (hence the term panglaciation) and had synchronous onset and terminations. These are the early Cryogenian or Sturtian (717-660 Ma) and late Cryogenian or Marinoan (ca. 645 to 635 Ma) ice ages (Halverson and Shields-Zhou, 2011; Rooney et al., 2014, 2015). Such synchroneity was the basis for the definition of the boundary between Cryogenian and Ediacaran Systems at the base of the cap carbonate overlying Marinoan glacial deposits in South Australia (Knoll et al., 2006) with its associated negative carbon isotope anomaly. Attention has now turned to defining a basal Cryogenian boundary and the Cryogenian stratigraphic sub-commission seeks to do this beneath the oldest evidence of widespread glaciation, in the meantime adopting a numerical age of 720 Ma as an interim position (Shields-Zhou et al., 2016). Preservation of glacigenic diamictite in a region of low palaeolatitude would support the concept that the associated glaciation was widespread. A combination of stratigraphic approaches has been used in addition to geochronology. The record of 87Sr/86Sr in marine carbonates shows values climbing through the Neoproterozoic, except for a fall from around 0.707 to as low as 0.7064 just prior to Sturtian glaciation (Halverson et al., 2010; Cox et al., 2016). Also, a negative carbon isotope anomaly has been found in carbonates preceding glaciation in several geographic areas (Halverson and Shields-Zhou, 2011). Currently, a biostratigraphic contribution to the boundary definition is not feasible. The definition of the basal Ediacaran sediments was facilitated by the near-universal presence of a negative carbon isotope anomaly in a cap carbonate at the base of a major transgressive succession resulting from eustatic sea level rise at the end of glaciation. In contrast, the expected eustatic sea level fall creates difficulties in defining a basal Cryogenian boundary. Shields-Zhou et al. (2016) argued that in the case of a transitional boundary, underlying deposits are likely to represent deep-water deposition of siliciclastic facies in which chemostratigraphy is impractical. Conversely, where shallow-water carbonate facies are present, they are liable to truncation during eustatic sea-level fall. A potential resolution arises where the basin subsidence rate is high, permitting a transition from shallow-marine through coastal to non-marine environments during global eustatic regression. Ali et al. (2017, this volume) argued that the Dalradian glacigenic succession of the Port Askaig Formation (PAF) in western Scotland shows a relatively complete record of events. In September 2013, this region became the first potential location to be visited by the Cryogenian stratigraphic sub-commission to consider its suitability for a Tonian-Cryogenian boundary stratotype and GSSP (Global Boundary Stratigraphic Section and Point). The aim of this paper is to synthesize a wide range of stratigraphic, sedimentological and isotopic data, much of it previously unpublished or new, which confirms and amplifies the chemostratigraphy of the region and, critically, establishes an environmental transition at the onset of glaciation, in a region reconstructed