Twenty-six samples from two major altered volcanic ash beds, Kinnekulle and BII Bentonite of the Kuressaare core section (K-3), Saaremaa Island, were explored to record the geochemical and mineralogical heterogeneity of beds. Signs of ash transport fractionation, redeposition of volcanic ash and diagenetic redistribution of material are described and interpreted.
In authigenic mineralogy of the Kinnekulle Bentonite illite–smectite dominates with addition of K-feldspar at the margins. The BII Bentonite is composed of chlorite–smectite and illite–smectite. The stability of phenocryst compositions, including that of sanidine and biotite, indicates that both bentonites originate from a single eruption. The observed rather stable pyroclastic sanidine compositions in the cross section of bentonites confirm the reliability of sanidine-based fingerprinting of altered volcanic ash beds. Trace element distribution in bentonites and host rocks indicates that Zr, Ga, Rb, Nb, Ti and Th stayed largely immobile during volcanic ash alteration and reflect primary ash composition. However, some redistribution of Nb and Ti as well as Y has probably occurred near the contacts of bentonite with the host rock. More scattered grain size distribution and immobile element patterns of the Kinnekulle Bentonite support the idea that the primary ash bed had a heterogeneous composition and it was one of the biggest bentonites of the Phanerozoic and most likely records an extended volcanic event. Significant geochemical variations, including a high S content, near the upper and lower contacts of the Kinnekulle Bentonite and elevated Ca and P in host rocks of both bentonites suggest that the studied large ash-falls caused notable perturbations in shallow marine and early post-sedimentary environment.
Altaner, S. P., Hower, J. & Whitney, G. 1984. Model for K-bentonite formation – evidence from zoned K-bentonites in the disturbed belt, Montana. Geology, 12, 412–415.
http://dx.doi.org/10.1130/0091-7613(1984)12<412:MFKFEF>2.0.CO;2
Batchelor, R. A. 2009. Geochemical “Golden Spike” for Lower Palaeozoic metabentonites. Earth and Environmental Science Transactions of the Royal Society of Edinburgh, 99, 177–187.
http://dx.doi.org/10.1017/S1755691009007087
Batchelor, R. A. 2014. Geochemistry of Upper Ordovician metabentonites and their cognate apatite microphenocrysts from Norway and Sweden. GFF, 136, 387–397.
http://dx.doi.org/10.1080/11035897.2013.854272
Bergström, S. M., Huff, W. D., Kolata, D. R. & Bauert, H. 1995. Nomenclature, stratigraphy, chemical fingerprinting, and areal distribution of some Middle Ordovician K-bentonites in Baltoscandia. Geologiska Föreningens i Stockholm Förhandlingar (GFF), 117, 1–13.
http://dx.doi.org/10.1080/11035899509546191
Bergström, S. M., Huff, W. D., Kolata, D. R., Yost, D. A. & Hart, C. 1997. A unique Middle Ordovician K-bentonite bed succession at Röstånga, S. Sweden. GFF, 119, 231–244.
http://dx.doi.org/10.1080/11035899709546481
Brusewitz, A. M. 1988. Asymmetric zonation of a thick Ordovician K-bentonite bed at Kinnekulle, Sweden. Clays and Clay Minerals, 36, 349–353.
http://dx.doi.org/10.1346/CCMN.1988.0360409
Dahlqvist, P., Calner, M., Kallaste, T., Kiipli, T. & Siir, S. 2012. Geochemical variations within the mid-Silurian Grötlingbo Bentonite (Gotland, Sweden): discriminating between magmatic composition, ash transport fractionation and diagenetic effects. GFF, 134, 273–282.
http://dx.doi.org/10.1080/11035897.2012.759147
Duggen, S., Olgun, N., Croot, P., Hoffmann, L., Dietze, H., Delmelle, P. & Teschner, C. 2010. The role of airborne volcanic ash for the surface ocean biogeochemical iron-cycle. Biogeosciences, 7, 827–844.
http://dx.doi.org/10.5194/bg-7-827-2010
Filippelli, G. M. 2002. The global phosphorus cycle. In Phosphates: Geochemical, Geobiological, and Materials Importance (Kohn, M., Rakovan, J. & Hughes, J., eds), Mineralogy & Geochemistry, 48, 391–425.
Fisher, R. V. & Schmincke, H. U. 1984. Pyroclastic Rocks. Springer-Verlag, Berlin, Heidelberg, New York, Tokyo, 472 pp.
http://dx.doi.org/10.1007/978-3-642-74864-6
Fortey, R. A. & Cocks, L. R. M. 2005. Late Ordovician global warming – The Boda event. Geology, 33, 405–408.
http://dx.doi.org/10.1130/G21180.1
Grim, R. E. & Güven, N. 1978. Bentonites, geology, mineralogy, properties and uses. Developments in Sedimentology, 24, 1–256.
Hetherington, C. J., Nakrem, H. A. & Potel, S. 2011. Note on the composition and mineralogy of upper Silurian bentonites from the Ringerike District: implications for local and regional stratigraphic correlation and sedimentation. Norwegian Journal of Geology, 91, 181–192.
Hints, L., Männik, P., Hints, O. & Hints, R. 2008. Discovery of the Ordovician Kinnekulle K-bentonite at the Põõsaspea cliff, NW Estonia. Estonian Journal of Earth Sciences, 57, 192–196.
http://dx.doi.org/10.3176/earth.2008.3.07
Hints, O., Kallaste, T. & Kiipli, T. 1997. Mineralogy and micropalaeontology of the Kinnekulle altered volcanic ash bed (Ordovician) at Pääsküla, North Estonia. Proceedings of the Estonian Academy of Sciences, Geology, 46, 107–118.
Hints, O., Hints, L. & Meidla, T. 2003. Effects of the Ordovician Kinnekulle ash-fall recorded in northern Estonia. Bulletin of the Geological Society of Denmark, 50, 115–123.
Hints, R., Kirsimäe, K., Somelar, P., Kallaste, T. & Kiipli, T. 2006. Chloritization of Late Ordovician K-bentonites from the northern Baltic Palaeobasin – influence from source material or diagenetic environment? Sedimentary Geology, 191, 55–66.
http://dx.doi.org/10.1016/j.sedgeo.2006.01.004
Hints, R., Kirsimäe, K., Somelar, P., Kallaste, T. & Kiipli, T. 2008. Multiphase Silurian bentonites in the Baltic Palaeobasin. Sedimentary Geology, 209, 69–79.
http://dx.doi.org/10.1016/j.sedgeo.2008.06.009
Huff, W. D., Kolata, D. R., Bergström, S. M. & Zhang, Y.-S. 1996. Large-magnitude Middle Ordovician volcanic ash falls in North America and Europe: dimensions, emplacement and post-emplacement characteristics. Journal of Volcanology and Geothermal Research, 73, 285–301.
http://dx.doi.org/10.1016/0377-0273(96)00025-X
Huff, W. D., Bergström, S. M. & Kolata, D. R. 2010. Ordovician explosive volcanism. In The Ordovician Earth System (Finney, S. C. & Berry, W. B. N., eds), The Geological Society of America Special Paper, 466, 13–28.
Jones, M. T. & Gislason, S. R. 2008. Rapid releases of metal salts and nutrients following the deposition of volcanic ash into aqueous environments. Geochimica et Cosmochimica Acta, 72, 3661–3680.
http://dx.doi.org/10.1016/j.gca.2008.05.030
Kaljo, D., Grytsenko, V., Kallaste, T., Kiipli, T. & Martma, T. 2014. Upper Silurian stratigraphy of Podolia revisited: carbon isotopes, bentonites and biostratigraphy. GFF, 136, 136–141.
http://dx.doi.org/10.1080/11035897.2013.862850
Kallaste, T. & Kiipli, T. 2006. New correlations of Telychian (Silurian) bentonites in Estonia. Proceedings of the Estonian Academy of Sciences, Geology, 55, 241–251.
Kastner, M. 1971. Authigenic feldspars in carbonate rocks. American Mineralogist, 56, 1403–1442.
Kiipli, E., Kallaste, T. & Kiipli, T. 2004. Metabentonites of the Pirgu Stage (Ashgill, Upper Ordovician) of the East Baltic. In WOGOGOB-2004, 8th Meeting of the Working Group on the Ordovician Geology of Baltoscandia, May 13–18, Tallinn and Tartu, Estonia, Abstracts and Field Guidebook (Hints, O. & Ainsaar, L., eds), pp. 53–54. Institute of Geology, University of Tartu.
Kiipli, E., Kiipli, T., Kallaste, T. & Ainsaar, L. 2010. Distribution of phosphorus in the Middle and Upper Ordovician Baltoscandian carbonate palaeobasin. Estonian Journal of Earth Sciences, 59, 247–255.
http://dx.doi.org/10.3176/earth.2010.4.01
Kiipli, E., Kiipli, T., Kallaste, T. & Siir, S. 2012. Al2O3/TiO2 ratio of the clay fraction of Late Ordovician–Silurian carbonate rocks as an indicator of paleoclimate of the Fennoscandian Shield. Palaeogeography, Palaeoclimatology, Palaeoecology, 365–366, 312–320.
http://dx.doi.org/10.1016/j.palaeo.2012.10.001
Kiipli, T., Kallaste, T., Kiipli, E. & Orlova, K. 2006. Upper Ordovician volcanic ash beds. In Kerguta (565) Drill Core (Põldvere, A., ed.), Estonian Geological Sections, 7, 15–18.
Kiipli, T., Kiipli, E., Kallaste, T., Hints, R., Somelar, P. & Kirsimäe, K. 2007. Altered volcanic ash as an indicator of marine environment, reflecting pH and sedimentation rate – example from the Ordovician Kinnekulle bed of Baltoscandia. Clays and Clay Minerals, 55, 177–188.
http://dx.doi.org/10.1346/CCMN.2007.0550207
Kiipli, T., Jeppsson, L., Kallaste, T. & Söderlund, U. 2008a. Correlation of Silurian bentonites from Gotland and the East Baltic using sanidine phenocryst composition, and biostratigraphical consequences. Journal of the Geological Society, 165, 211–220.
http://dx.doi.org/10.1144/0016-76492006-095
Kiipli, T., Orlova, K., Kiipli, E. & Kallaste, T. 2008b. Use of immobile trace elements for the correlation of Telychian bentonites on Saaremaa Island, Estonia, and mapping of volcanic ash clouds. Estonian Journal of Earth Sciences, 57, 39–52.
http://dx.doi.org/10.3176/earth.2008.1.04
Kiipli, T., Kallaste, T. & Nestor, V. 2010a. Composition and correlation of volcanic ash beds of Silurian age from the eastern Baltic. Geological Magazine, 147, 895–909.
http://dx.doi.org/10.1017/S0016756810000294
Kiipli, T., Kallaste, T., Nestor, V. & Loydell, D. K. 2010b. Integrated Telychian (Silurian) K-bentonite chemostratigraphy and biostratigraphy in Estonia and Latvia. Lethaia, 43, 32–44.
http://dx.doi.org/10.1111/j.1502-3931.2009.00162.x
Kiipli, T., Radzevičius, S., Kallaste, T., Kiipli, E., Siir, S., Soesoo, A. & Voolma, M. 2012. The Geniai Tuff in the southern East Baltic area – a new correlation tool near the Aeronian/Telychian stage boundary, Llandovery, Silurian. Bulletin of Geosciences, 87, 695–704.
http://dx.doi.org/10.3140/bull.geosci.1313
Kiipli, T., Kallaste, T., Kiipli, E. & Radzevičius, S. 2013. Correlation of Silurian bentonites based on the immobile elements in the East Baltic and Scandinavia. GFF, 135, 152–161.
http://dx.doi.org/10.1080/11035897.2013.783104
Kiipli, T., Kallaste, T., Nielsen, A., Schovsbo, N. & Siir, S. 2014a. Geochemical discrimination of the Upper Ordovician Kinnekulle Bentonite in the Billegrav-2 drill core section, Bornholm, Denmark. Estonian Journal of Earth Sciences, 63, 264–270.
http://dx.doi.org/10.3176/earth.2014.29
Kiipli, T., Radzevičius, S. & Kallaste, T. 2014b. Silurian bentonites in Lithuania: correlations based on sanidine phenocryst composition and graptolite biozonation – interpretation of volcanic source regions. Estonian Journal of Earth Sciences, 63, 18–29.
http://dx.doi.org/10.3176/earth.2014.02
Kiipli, T., Soesoo, A. & Kallaste, T. 2014c. Geochemical evolution of Caledonian volcanism recorded in the sedimentary rocks of the eastern Baltic region. In New perspectives on the Caledonides of Scandinavia and Related areas (Corfu, F., Gasser, D. & Chew, D. M., eds), Geological Society Special Publications, 390, 177–192.
Kiipli, T., Dahlquist, P., Kallaste, T., Kiipli, E. & Nõlvak, J. 2015. Upper Katian (Ordovician) bentonites in the East Baltic, Scandinavia and Scotland: geochemical correlation and volcanic source interpretation. Geological Magazine,
http://dx.doi.org/10.1017/S001675681400051X
Kolata, D. R., Frost, J. K. & Huff, W. D. 1987. Chemical correlation of K-bentonite beds in the Middle Ordovician Decorah Subgroup, upper Mississippi Valley. Geology, 15, 208–211.
http://dx.doi.org/10.1130/0091-7613(1987)15<208:CCOKBI>2.0.CO;2
Laufeld, S. & Jeppsson, L. 1976. Silicification and bentonites in the Silurian of Gotland. GFF, 98, 31–44.
http://dx.doi.org/10.1080/11035897609454336
Männik, P., Põldvere, A., Nestor, V., Kallaste, T., Kiipli, T. & Martma, T. 2014. The Llandovery–Wenlock boundary interval in west-central continental Estonia: an example from the Suigu (S-3) core section. Estonian Journal of Earth Sciences, 63, 1–17.
http://dx.doi.org/10.3176/earth.2014.01
Perrier, V., Meidla, T., Tinn, O. & Ainsaar, L. 2012. Biotic response to explosive volcanism: ostracod recovery after Ordovician ash-falls. Palaeogeography, Palaeoclimatology, Palaeoecology, 365–366, 166–183.
http://dx.doi.org/10.1016/j.palaeo.2012.09.024
Põlma, L. 1967. On the transitional area between the northern and axial lithofacies zones of the East Baltic Ordovician. Proceedings of the Estonian Academy of Sciences, Chemistry, Geology, 16, 272–275 [in Russian].
Rampino, M. R., Self, S. & Stothers, R. B. 1988. Volcanic winters. Annual Review of Earth and Planetary Science, 16, 73–99.
http://dx.doi.org/10.1146/annurev.ea.16.050188.000445
Ray, D. C., Collings, A. V. J., Worton, G. J. & Jones, G. 2011. Upper Wenlock bentonites from Wren’s Nest Hill, Dudley: comparisons with prominent bentonites along Wenlock Edge, Shropshire, England. Geological Magazine, 148, 670–681.
http://dx.doi.org/10.1017/S0016756811000288
Somelar, P., Kirsimäe, K., Hints, R. & Kirs, J. 2010. Illitization of Early Paleozoic K-bentonites in the Baltic Basin: decoupling of burial- and fluid-driven processes. Clays and Clay Minerals, 58, 388–398.
http://dx.doi.org/10.1346/CCMN.2010.0580309
Torsvik, T. H. & Rehnström, E. F. 2003. The Tornquist Sea and Baltic Avalonia docking. Tectonophysics, 362, 67–82.
http://dx.doi.org/10.1016/S0040-1951(02)00631-5
Winchester, J. A. & Floyd, P. A. 1977. Geochemical discrimination of different magma series and their differentiation products using immobile elements. Chemical Geology, 20, 325–343.
http://dx.doi.org/10.1016/0009-2541(77)90057-2