'Roxolany Tephra' (Ukraine) – New Evidence for an Origin From
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Journal of Quaternary Science Page 4 of 38 1 2 3 1 The ‘Roxolany Tephra’ (Ukraine) – new evidence for an origin from Ciomadul volcano, 4 5 2 East Carpathians 6 7 3 Sabine Wulf1,2*, Stanisław Fedorowicz3, Daniel Veres4, Maria Łanczont5, Dávid Karátson6, 8 4 Ralf Gertisser7, Marc Bormann8, Enikö Magyari9, Oona Appelt10, Ulrich Hambach11, Petro F. 9 5 Gozhyk12 10 11 6 1 Senckenberg Research Institute and Natural History Museum, BIK-F, TSP6 Evolution and Climate, 12 7 Senckenberganlage 25, D-60325 Frankfurt a.M., Germany 13 8 2 Institute for Geosciences, University of Heidelberg, Im Neuenheimer Feld 234, D-69120 Heidelberg, 14 9 Germany 3 15 10 University of Gdańsk, Institute of Geography, Department of Quaternary Geomorphology and 11 Geology, ul. Bażyńskiego 4, 80-950 Gdańsk, Poland 16 4 17 12 Romanian Academy Institute of Speleology "Emil Racovita", Clinicilor 5, 400006 ClujNapoca, 18 13 Romania 14 5 Department of Geoecology and Palaeogeography, Maria Curie-Skłodowska University, Al. Kraśnicka 19 15 2 cd, 20-718 Lublin, Poland 20 16 6 Eötvös University, Department of Physical Geography, H-1117 Budapest, Pázmány s. 1/C, Hungary 21 17 7 School of Physical and Geographical Sciences, Keele University, Keele ST5 5BG, United Kingdom 22 18 8 University of Cologne, Institute of Geography Education, Gronewaldstr. 2, D-50931 Cologne, Germany 23 19 9 Eötvös University, MTA-MTM-ELTE Research Group for Paleontology, Pázmány s. 1/C, H-1117 Budapest, 24 20 Hungary 25 21 10 Helmholtz Centre Potsdam, GFZ German Research Centre for Geosciences, Section 4.3 Chemistry 26 22 and Physics of Earth Materials, Telegrafenberg, D-14473 Potsdam, Germany 11 27 23 BayCEER & Chair of Geomorphology, University of Bayreuth, D-95440 Bayreuth, Germany 12 28 24 Institute of Geological Sciences, National Academy of Sciences of Ukraine, Gonchara 55B, 01 601 Kyiv, 29 25 Ukraine 30 26 31 32 27 * Corresponding author: [email protected] (S.Wulf), facsimile +49-(0)6221- 33 34 28 545503 35 36 29 Keywords: Tephra; Roxolany loess; Ukraine; Ciomadul; Lake St. Ana. 37 38 39 30 Abstract 40 41 31 We present major element glass data and correlations of the ‘Roxolany Tephra’ – a so far 42 43 32 geochemically unconstrained volcanic ash layer previously described in last glacial (MIS2) 44 45 33 loess deposits of the Roxolany loess-palaeosoil complex in the SW Ukraine. This 46 34 exceptionally well preserved, 2-3 cm thick tephra layer is characterised by a rhyolitic glass 47 48 35 composition that is comparable to that of proximal tephra units from Ciomadul volcano in the 49 50 36 East Carpathians, central Romania. The chemistry particularly matches that of the final LSPA 51 37 pyroclastic fall unit of St. Ana crater that is radiocarbon dated in the proximal Mohoş coring 52 53 38 site (MOH-2) at 29.6±0.62 cal ka BP. The age of the tephra correlative is well in agreement 54 55 39 with the newest radiocarbon and OSL age constraints from overlying palaeosoils and tephra- 56 40 embedding loess of the Roxolany sequence, respectively, which place the tephra between ca. 57 58 41 33 and 24 cal ka BP, and thus confirm the long-debated chronostratigraphy of this important 59 60 http://mc.manuscriptcentral.com/jqs 1 Page 5 of 38 Journal of Quaternary Science 1 2 3 42 environmental archive. The occurrence of a distal Ciomadul tephra ca. 350 km east of its 4 5 43 source indicates a great potential of further tephra and cryptotephra findings from this 6 44 volcanic complex in the south-eastern Mediterranean and Black Sea region. 7 8 45 9 10 46 1. Introduction 11 47 The loess-palaeosoil complex near the village of Roxolany in the SW Ukraine (Fig. 1) 12 13 48 provides an almost complete Pleistocene terrestrial sedimentary record and is therefore the 14 15 49 most representative sequence for the reconstruction of long-term palaeoclimatic and 16 50 environmental changes in the Northern Black Sea region. The ca. 48 m thick Roxolany loess- 17 18 51 palaeosoil sequence was first studied by P. Gozhik with his research team (Putievoditel, 1976; 19 20 52 Gozhik et al ., 1995), demonstrating its potential for palaeoenvironmental reconstruction on 21 53 the basis of granulometric, mineralogical, palaeomagnetic, palaeontological (molluscs, 22 23 54 mammal fauna) analyses as well as radiocarbon and Thermoluminescence (TL) dating. 24 25 55 Within these first studies, the authors suggested the Brunhes/Matuyama magnetic reversal (ca. 26 56 780 ka) in the lower part of the profile. Later, Tsatskin et al . (1998) provided a detailed 27 28 57 description, proposing a revised stratigraphic interpretation of the loess-palaeosoil horizons 29 30 58 and palaeomagnetic data, and their correlation with the marine oxygen isotope stages (MIS). 31 59 The authors re-identified the Brunhes/Matuyama boundary in the middle part of the section in 32 33 60 loess unit L 6 at ca. 35 m depth of the Roxolany loess-palaeosoil complex, which now enabled 34 35 61 a solid correlation with other loess profiles in Europe and China (e.g. Tsatskin et al ., 2001; 36 62 Dodonov et al ., 2006; Gendler et al ., 2006; Faustov et al ., 2009). 37 38 39 63 Tsatskin et al . (1998) were the first to describe a macroscopic visible tephra (volcanic ash 40 64 fall) layer, the so-called ‘Roxolany Tephra’, within the initially proposed L loess unit 41 3 42 65 (corresponding to MIS 12, i.e. the period from 450 to 400 ka; Sartori, 2000). Tephras, in 43 44 66 general, are useful chronological and/or synchronisation markers in terrestrial and marine 45 67 palaeoenvironmental archives, if correlated via glass geochemical fingerprinting with known 46 47 68 and dated volcanic events (e.g. Lowe, 2011). Loess-palaeosoil complexes in the Middle and 48 49 69 Lower Danube Basin have proven the preservation of tephras in different stratigraphic 50 70 positions, although their chemical compositions, and thus their precise ages, were often poorly 51 52 71 constrained due to the strong alteration of volcanic glass shards under the prevailing humid to 53 54 72 semi-humid temperate climate (e.g. Horváth, 2001; Panaiotu et al ., 2001; Fitzsimmons et al ., 55 73 2013; Veres et al ., 2013; Marković et al ., 2015). Fedorowicz et al . (2012) provided a first 56 57 74 detailed description of the mineralogical components of the Roxolany Tephra and suggested a 58 59 60 http://mc.manuscriptcentral.com/jqs 2 Journal of Quaternary Science Page 6 of 38 1 2 3 75 possible genetic link with Carpathian volcanic activity. However, this assumption still lacked 4 5 76 the geochemical and chronological evidence from proximal and other distal tephra deposits. 6 77 Many years of comprehensive research focusing on Roxolany have brought up a number of 7 8 78 new, partially contradicting data in the chronostratigraphic diagnosis of the upper three loess 9 10 79 units (Fig. 2), and, implicitly, the timing of tephra deposition varied depending on such 11 80 interpretations (Putivnyk, 2000; Gozhik et al ., 2007; Boguckyi et al . [eds], 2013; Gozhik, 12 13 81 2013). According to the latest data, the ‘Roxolany Tephra’ is embedded within the Bug loess 14 15 82 (bg ) from the upper Pleniglacial of the Weichselian glaciation (MIS 2) (Gozhik et al ., 2007) 16 83 (Fig. 2). It is overlain by two palaeosoil layers of an interphase or interstadial rank, the 17 18 84 Prychornomorsk (pc) and the Dofinivka (df ) units, that have recently been radiocarbon dated 19 20 85 at ca. 23.0 cal ka BP and 34.0 cal ka BP, respectively (Fedorowicz et al ., 2012; Łanczont et 21 86 al ., 2015; this study Fig. 2, Table 1). The palaeosoil underlying the tephra-bearing bg loess, 22 23 87 the Vytachiv (vt ) unit, has been attributed to the middle Pleniglacial (MIS 3) and is AMS 24 25 88 radiocarbon dated between ca. 21.3 and 25.6 cal ka BP (Fedorowicz et al ., 2012; Łanczont et 26 89 al ., 2015; this study Fig. 2, Table 1). The vt unit developed on the Uday (ud ) loess, which is 27 28 90 correlated with MIS 4 (Fig. 2). Infrared optically-stimulated luminescence (IR-OSL) dates of 29 30 91 loess samples from ca. 9 m below the tephra revealed an age of 33.1±2.6 ka (Fedorowicz et 31 92 al ., 2012; this study Table 3), supporting both the radiocarbon-based chronology and the 32 33 93 stratigraphic scheme developed by Gozhik et al . (1995; 2007). Further attempts to directly 34 35 94 date phenocrysts of the Roxolany Tephra, however, led to unrealistic old ages of 50±3 Ma 36 95 (40 Ar/ 39 Ar; Tsatskin et al ., 1998; Sartori, 2000) and 11.83-14.54 Ma (K/Ar on amphibole and 37 38 96 biotite; Fedorowicz et al ., 2012). 39 40 97 In this study, we provide the first geochemical glass data of the ‘Roxolany Tephra’ and a solid 41 98 correlation scheme with its dated volcanic source in order to (1) clarify the younger 42 43 99 chronostratigraphy of the Roxolany loess-palaeosoil complex, and (2) extend the 44 45 100 tephrostratigraphic framework in south-eastern Europe with the principal aim at providing 46 101 means for comparing various records on a wider scale. 47 48 102 49 50 103 2. Samples and methods 51 104 2.1 Roxolany sampling site 52 53 105 The Roxolany outcrop is situated on the eastern bank of the Dniester estuary, about 40 km 54 55 106 southwest of Odessa and ca. 1.5 km northwest of the village of Roxolany (Ukrainian: 56 107 Roksolany), SW Ukraine (46 °10'N, 30 °27'E) (Fig.