Rare earth elements (REEs) have been analysed from fossil vertebrate microremains (thelodont scales) from the Vesiku Bone Bed, Saaremaa, Estonia, using in situ microsampling by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Well-preserved scales of three species of the genus Thelodus (T. carinatus, T. laevis and Thelodus sp.) show very uniform REE patterns with slightly lower overall REE concentrations in enameloid than in dentine, with enrichment in middle REEs, depletion in heavy REEs and pronounced negative europium anomaly, but no cerium anomaly. The results of this study suggest a similar diagenetic history and possibly contemporaneous habitats for all three Thelodus species, as well as possible suboxic to anoxic conditions of the bottom and pore waters during the formation of the Vesiku Bone Bed.
Bau, M. & Dulski, P. 1996. Distribution of yttrium and rare-earth elements in the Penge and Kuruman iron-formations, Transvaal Supergroup, South Africa. Precambrian Research, 79, 37–55.
http://dx.doi.org/10.1016/0301-9268(95)00087-9
Blom, H., Märss, T. & Miller, G. 2002. Silurian and lowermost Devonian birkenoid anaspids from the northern hemisphere. Transactions of the Royal Society of Edinburgh: Earth Sciences, 92, 263–323.
Bright, C. A., Cruse, A. M., Lyons, T. W., Mac Leod, K. G., Glascock, M. D. & Ethington, R. L. 2009. Seawater rare-earth element patterns preserved in apatite of Pennsylvanian conodonts? Geochimica et Cosmochimica Acta, 73, 1609–1624.
http://dx.doi.org/10.1016/j.gca.2008.12.014
Herwartz, D., Tütken, T., Münker, C., Jochum, K. P., Stoll, B. & Sander, P. M. 2011. Timescales and mechanisms of REE and Hf uptake in fossil bones. Geochimica et Cosmochimica Acta, 75, 82–105.
http://dx.doi.org/10.1016/j.gca.2010.09.036
Ederfield, H. & Pagett, R. 1986. Rare earth elements in ichthyoliths: variations with redox conditions and depositional environment. Science of the Total Environment, 49, 175–197.
http://dx.doi.org/10.1016/0048-9697(86)90239-1
Kemp, R. A. & Trueman, C. N. 2003. Rare earth elements in Solnhofen biogenic apatite: geochemical clues to the palaeoenvironment. Sedimentary Geology, 155, 109–127.
http://dx.doi.org/10.1016/S0037-0738(02)00163-X
Kocsis, L., Trueman, C. N. & Palmer, M. R. 2010. Protracted diagenetic alteration of REE contents in fossil bioapatite: direct evidence from Lu–Hf isotope systematics. Geochimica et Cosmochimica Acta, 74, 6077–6092.
http://dx.doi.org/10.1016/j.gca.2010.08.007
Kohn, M. J., Schoeninger, M. J. & Barker, W. W. 1999. Altered states: effects of diagenesis on fossil tooth chemistry. Geochimica et Cosmochimica Acta, 63, 2737–2747.
http://dx.doi.org/10.1016/S0016-7037(99)00208-2
Lécuyer, C., Reynard, B. & Grandjean, P. 2004. Rare earth element evolution of Phanerozoic seawater recorded in biogenic apatites. Chemical Geology, 204, 64–102.
http://dx.doi.org/10.1016/j.chemgeo.2003.11.003
Männik, P. 2014. The Silurian System of Estonia. In 4th Annual Meeting of IGCP 591, Estonia, 10–19 June 2014, Abstracts and Field Guide (Bauert, H., Hints, O., Meidla, T. & Männik, P., eds), pp. 123–128. University of Tartu, Tartu.
Märss, T. 1986. Silurian vertebrates of Estonia and West Latvia. Fossilia Baltica, 1, 1–104.
Märss, T. 2003. Paralogania from the Rootsiküla (Wenlock) and Paadla (Ludlow) stages of Estonia. Proceedings of the Estonian Academy of Sciences, Geology, 52, 98–112.
Märss, T. 2005. Thelodont Oeselia mosaica gen. et sp. nov. from the Wenlock and Ludlow of the East Baltic. Proceedings of the Estonian Academy of Sciences, Geology, 54, 181–190.
Märss, T. & Männik, P. 2013. Revision of Silurian vertebrate biozones and their correlation with the conodont succession. Estonian Journal of Earth Sciences, 62, 181–204.
http://dx.doi.org/10.3176/earth.2013.15
McLennan, S. M. 1989. Rare earth elements in sedimentary rocks; influence of provenance and sedimentary processes. Reviews in Mineralogy and Geochemistry, 21, 169–200.
Nestor, V. 1997. Silurian. In Geology and Mineral Resources of Estonia (Raukas, A. & Teedumäe, A., eds), pp. 99–104. Estonian Academy Publishers, Tallinn.
Ounis, A., Kocsis, L., Chaabani, F. & Pfeifer, H.-R. 2008. Rare earth elements and stable isotope geochemistry (δ13C and δ18O) of phosphorite deposits in the Gafsa Basin, Tunisia. Palaeogeography, Palaeoclimatology, Palaeoecology, 268, 1–18.
http://dx.doi.org/10.1016/j.palaeo.2008.07.005
Patrick, D., Martin, J. E., Parris, D. C. & Grandstaff, D. E. 2004. Palaeoenvironmental interpretations of rare earth element signatures in mosasaurs (reptilian) from the upper Cretaceous Pierre Shale, central South Dakota, USA. Palaeogeography, Palaeoclimatology, Palaeoecology, 212, 277–294.
http://dx.doi.org/10.1016/S0031-0182(04)00315-3
Reynard, B., Lécuyer, C. & Grandjean, P. 1999. Crystal-chemical controls on rare-earth element concentrations in fossil biogenic apatites and implications for paleoenvironmental reconstructions. Chemical Geology, 155, 233–241.
http://dx.doi.org/10.1016/S0009-2541(98)00169-7
Suarez, C. A., Macpherson, G. L., Gonzalez, L. A. & Grandstaff, D. E. 2010. Heterogeneous rare earth element (REE) patterns and concentrations in a fossil bone: implications for the use of REE in vertebrate taphonomy and fossilization history. Geochimica et Cosmochimica Acta, 74, 2970–2988.
http://dx.doi.org/10.1016/j.gca.2010.02.023
Trueman, C. N. & Tuross, N. 2002. Trace elements in recent and fossil bone apatite. Phosphates: geochemical, geobiological, and materials importance. Reviews in Mineralogy and Geochemistry, 48, 1–742.
http://dx.doi.org/10.2138/rmg.2002.48.13
Trueman, C. N., Benton, M. J. & Palmer, M. R. 2003. Geochemical taphonomy of shallow marine vertebrate assemblages. Palaeogeography, Palaeoclimatology, Palaeoecology, 197, 151–169.
http://dx.doi.org/10.1016/S0031-0182(03)00457-7
Trueman, C. N., Kocsis, L., Palmer, M. R. & Dewdney, C. 2011. Fractionation of rare earth elements within bone mineral: a natural cation exchange system. Palaeogeography, Palaeoclimatology, Palaeoecology, 310, 124–132.
http://dx.doi.org/10.1016/j.palaeo.2011.01.002
Tütken, T., Vennemann, T. W. & Pfretzschner, H.-U. 2008. Early diagenesis of bone and tooth apatite in fluvial and marine settings: constraints from combined oxygen isotope, nitrogen and REE analysis. Palaeogeography, Palaeoclimatology, Palaeoecology, 266, 254–268.
http://dx.doi.org/10.1016/j.palaeo.2008.03.037
Vennemann, T. W., Hegner, E., Cliff, G. & Benz, G. W. 2001. Isotopic composition of recent shark teeth as a proxy for environmental conditions. Geochimica et Cosmochimica Acta, 65, 1583–1599.
http://dx.doi.org/10.1016/S0016-7037(00)00629-3
Wright, J., Schrader, H. & Holster, W. T. 1987. Paleoredox variations in ancient oceans recorded by rare earth elements in fossil apatite. Geochimica et Cosmochimica Acta, 51, 631–644.
http://dx.doi.org/10.1016/0016-7037(87)90075-5