Biogeosciences (May 2008)
Reconstruction of the biogeochemistry and ecology of photoautotrophs based on the nitrogen and carbon isotopic compositions of vanadyl porphyrins from Miocene siliceous sediments
Abstract
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-<i>c</i><sub>1-3</sub>, whereas 8-nor-DPEP may have originated from chlorophylls-<i>a</i><sub>2</sub> or <i>b</i><sub>2</sub> or bacteriochlorophyll-<i>a</i>. 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 δ<sup>15</sup>N value for the entire photoautotrophic community is estimated to be –2 to +1‰ from the δ<sup>15</sup>N values of DPEP (–6.9 to –3.6‰; <i>n</i>=7), considering that the empirical isotopic relationships that the tetrapyrrole nuclei of chloropigments are depleted in <sup>15</sup>N by ~4.8‰ and enriched in <sup>13</sup>C by ~1.8‰ relative to the whole cells. This finding suggests that nitrogen utilized in the primary production was supplied mainly through N<sub>2</sub>-fixation by diazotrophic cyanobacteria. Based on the δ<sup>13</sup>C values of DPEP (–17.9 to –15.6‰; <i>n</i>=7), we estimated isotopic fractionation associated with photosynthetic carbon fixation to be 8–14‰. This range suggests the importance of β-carboxylation and/or active transport of the carbon substrate, indicating in turn the substantial contribution of diazotrophic cyanobacteria to primary production. Based on the δ<sup>15</sup>N values of 17-nor-DPEP (–7.4 to –2.4‰ <i>n</i>=7), the δ<sup>15</sup>N range of chlorophylls-<i>c</i>-producing algae was estimated to be –3 to +3‰. This relative depletion in sup>15</sup>N suggests that these algae mainly utilized nitrogen regenerated from diazotrophic cyanobacteria. Given that diatoms are likely to have constituted the chlorophylls-<i>c</i>-producing algae within the biogenic-silica-rich Onnagawa Formation, cyanobacteria-hosting diatoms may have been important contributors to primary production.
