Biogeosciences www.biogeosciences.net 1726-4170 1726-4189 5 3 2008 10.5194/bg-5-797-2008 http://www.biogeosciences.net/5/797/2008/ http://www.biogeosciences.net/5/797/2008/bg-5-797-2008.html http://www.biogeosciences.net/5/797/2008/bg-5-797-2008.pdf 797 816 2008-05-15 Reconstruction of the biogeochemistry and ecology of photoautotrophs based on the nitrogen and carbon isotopic compositions of vanadyl porphyrins from Miocene siliceous sediments Y. Kashiyama chiro@jamstec.go.jp N. O. Ogawa M. Shiro R. Tada H. Kitazato N. Ohkouchi Department of Earth and Planetary Science, University of Tokyo, Tokyo, Japan Institute for Research on Earth Evolution, Japan Agency for Marine-Earth Science and Technology, Yokosuka, Japan X-ray Research Laboratory, Rigaku Co., Akishima, Japan We determined both the nitrogen and carbon isotopic compositions of various vanadyl alkylporphyrins isolated from siliceous marine sediments of the Onnagawa Formation (middle Miocene, northeastern Japan) to investigate the biogeochemistry and ecology of photoautotrophs living in the paleo-ocean. The distinctive isotopic signals support the interpretations of previous works that the origin of 17-nor-deoxophylloerythroetioporphyrin (DPEP) is chlorophylls-c1-3, whereas 8-nor-DPEP may have originated from chlorophylls-a2 or b2 or bacteriochlorophyll-a. Although DPEP and cycloheptanoDPEP are presumably derived from common precursory pigments, their isotopic compositions differed in the present study, suggesting that the latter represents a specific population within the photoautotrophic community. The average δ15N value for the entire photoautotrophic community is estimated to be –2 to +1&permil; from the δ15N values of DPEP (–6.9 to –3.6&permil;; n=7), considering that the empirical isotopic relationships that the tetrapyrrole nuclei of chloropigments are depleted in 15N by ~4.8&permil; and enriched in 13C by ~1.8&permil; relative to the whole cells. This finding suggests that nitrogen utilized in the primary production was supplied mainly through N2-fixation by diazotrophic cyanobacteria. Based on the δ13C values of DPEP (–17.9 to –15.6&permil;; n=7), we estimated isotopic fractionation associated with photosynthetic carbon fixation to be 8–14&permil;. 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