In Livello Bonarelli black shale deposited during Cretaceous Oceanic Anoxic Event 2 (OAE-2, ca. 94 Ma), nitrogen isotopic compositions of bulk sediments are mostly in a narrow range from –2.7 to –0.7‰. We also determined molecular distribution and nitrogen isotopic compositions of geoporphyrins extracted from the black shale. The nitrogen isotopic compositions of C<sub>32</sub> Ni deoxophylloerythroetioporphyrin (DPEP) and total Ni porphyrins are –3.5 and –3.3‰, respectively, leading us to the estimation that the mean nitrogen isotopic composition of photoautotrophic cells were around +1‰ during the formation of Bonarelli black shale. This value is suggestive of N<sub>2</sub>-fixation, a dominant process for these photoautotrophs when assimilating nitrogen. Furthermore, Ni-chelated C<sub>32</sub> DPEP, derived mainly from chlorophyll <i>a</i> had the highest concentration. Based on this evidence, we conclude that diazotrophic cyanobacteria were major primary producers during that time. Cyanobacteria may be key photoautotrophs during the formation of black shale type sediments intermittently observed throughout the later half of the Earth's history, and hence may have played a crucial role in the evolution of geochemical cycles even in the later half of the Earth's history
