Journal of Alloys and Compounds 362 (2004) 99–106 Investigation of chemical composition of belemnite rostra by synchrotron-based X-ray microfluorescence and diffraction and electron microprobe Marek Florek a , Hwa Shik Youn b , Chul-Un Ro c , Hubert Wierzbowski d , János Osán e , Waldemar Kazimierczak f , Andrzej Kuczumow a,∗ a Department of Chemistry, Catholic University of Lublin, 20-718 Lublin, Poland b Pohang Accelerator Laboratory, Pohang 790-784, South Korea c Department of Chemistry, Hallym University, Chuncheon 200-702, South Korea d Institute of Geology, Polish Academy of Sciences, Warszawa, Poland e KFKI Atomic Energy Research Institute, Health and Environmental Physics, H-1525 Budapest, Hungary f Laboratory of Electron Microscopy, Catholic University of Lublin, 20-718 Lublin, Poland Received 28 June 2002 Abstract Rostra (bullet-shaped internal shells) of two species of belemnites: Belemnopsis sp. (from Bathonian Stage sediments ∼161–166 Ma ago) and Hibolites sp. (from Middle Oxfordian sediments ∼154–157 Ma) were investigated by the use of 1B2 microfluorescence beamline in Pohang Light Source in Korea. The cross-sections of the rostra showed an ordered structure of concentric growth laminae cut across by radial calcite crystals. The inner and outer parts of the cross-section differ in the size of calcite crystals, building the block. Very fine crystals existing in the inner parts of rostra are replaced by monocrystals in their external parts. Some compounds of metallic elements such as iron and zinc are present in the calcite matrices of belemnites. Their presence is especially pronounced in the zones separating particular growth rings. The concentrations of elements in calcite matrix were calibrated by atomic absorption method and the results for alkaline elements are: for Sr ∼1000 ppm for Oxfordian specimen and ∼3000 ppm for Bathonian; for Na, ∼2000 and ∼1400 ppm; for K, ∼160 and ∼100 ppm, respectively. The synchrotron-based investigations were complemented with the electron microprobe search for low-Z elements; using this method sodium, potassium, aluminum, silicon, chlorine and sulfur were detected in the matrix. The variability of molar Mg/Ca ratio follows the optical variability of the annual growth zones of the samples, suggesting that this ratio could be used as a palaeothermometer. Possibilities of both application of the elemental data for the estimation of palaeotemperatures, and cross-checking with the isotopic data are discussed. The substantial amounts of the excess carbon were detected in the samples. They are concluded to be potentially useful for the analysis of remnants of original biological matter. © 2003 Elsevier B.V. All rights reserved. Keywords: Belemnites; Crystal growth; Scanning electron microscopy; X-ray spectroscopies; Synchrotron radiation; Biomineralization 1. Introduction Extinct sea creatures called belemnites are common Juras- sic and Cretaceous fossils. They became extinct some 65 million years ago, leaving numerous traces of their exis- tence. As a rule, very characteristic fragments of their bodies, the so-called rostra are well preserved. Rostra were the pro- longed, bullet-shaped fragments of internal belemnite skele- ∗ Corresponding author. E-mail address: kuczon@kul.lublin.pl (A. Kuczumow). tons, built of low Mg calcite [1,2]. The crystals of such ma- terial are considered to be relatively resistant during lime- stone diagenetic alterations [3]. Nevertheless, diagenetic al- terations cannot be excluded, especially concerning the api- cal line and microfractures, since we should take into ac- count that the porosity of belemnite calcite is of the order 3–10% [1]. Together with the essential information on the ma- trix compound, some knowledge was collected about the chemical composition [4,5] and still more common in- formation about isotopic [6–9] composition of the rostra. Well-preserved belemnite rostra are often used for stable 0925-8388/$ – see front matter © 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0925-8388(03)00569-3