No abstract

Four sections documenting the impact of the late Cenomanian oceanic anoxic event (OAE 2) were studied in basins with different paleoenvironmental regimes. Accumulation rates of phosphorus (P) bound to iron, organic matter, and authigenic phosphate are shown to rise and arrive at a distinct maximum at the onset of OAE 2, with an associated increase in δ 13C values. Accumulation rates of P return to preexcursion values in the interval where the δ 13 C record reaches its fi rst maximum. An offset in time between the maximum in P accumulation and peaks in organic carbon burial, hydrogen indices, and C org /P react molar ratios is explained by the evolution of OAE 2 in the following steps. (1) An increase in productivity increased the fl ux of organic matter and P into the sediments; the preservation of organic matter was low and its oxidation released P, which was predominantly mineralized. (2) Enhanced productivity and oxidation of organic matter created dysoxic bottom waters; the preservation potential for organic matter increased, whereas the sediment retention potential for P decreased. (3) The latter effect sustained high primary productivity, which led to an increase in the abundance of free oxygen in the ocean and atmosphere system. After the sequestration of CO 2 in the form of black shales, this oxygen helped push the ocean back into equilibrium, terminating black shale deposition and removing bioavailable P from the water column.

Studies of phosphorus (P) dynamics in surface sediments of lakes and coastal seas typically emphasize the role of coupled iron (Fe), sulfur (S) and P cycling for sediment P burial and release. Here, we show that anaerobic oxidation of methane (AOM) also may impact sediment P cycling in such systems. Using porewater and sediment profiles for sites in an oligotrophic coastal basin (Bothnian Sea), we provide evidence for the formation of Fe-bound P (possibly vivianite; Fe3(PO4)2 .8H2O) below the zone of AOM with sulfate. Here, dissolved Fe2+ released from oxides is no longer scavenged by sulfide and high concentrations of both dissolved Fe2+ (>1 mM) and PO4 in the porewater allow supersaturation with respect to vivianite to be reached. Besides formation of Fe(II)-P, preservation of Fe-oxide bound P likely also contributes to permanent burial of P in Bothnian Sea sediments. Preliminary budget calculations suggest that the burial of Fe-bound P allows these sediments to act as a major sink for P from the adjacent eutrophic Baltic Proper.

The upper Cenomanian pelagic sediments of Furlo in the northern Apennines, Italy, are characterized by a 1.5-m-thick organic-rich stratigraphic horizon called the Bonarelli Level, which represents the second major oceanic anoxic event in the Cretaceous (OAE 2). The Bonarelli Level is depleted in carbonates and consists essentially of biogenic quartz, phyllosilicates, and organic matter, with values of TOC reaching 18%. The age of the Furlo section is constrained by correlating its d 13 C curve with that of the well-dated Pueblo (USA) and Eastbourne (UK) sections. The presence of all the planktonic foraminiferid zones and details of the OAE 2 d 13 C excursion indicates a relatively continuous but reduced sedimentation rate across the Cenomanian/Turonian (C/T) boundary. Sediment and TOC mass accumulation rates have been calculated and suggest a sedimentation break in the upper Bonarelli Level. This may be an artifact of the diachronous FAD of the planktonic foraminiferid Helvetoglobotruncana helvetica and suggests that in some sections the d 13 C curve may provide more reliable age control for dating the C/T boundary. In order quantitatively to explain the carbon isotope curve and the measured TOC mass accumulation rate, a simple dynamic model of the isotope effects of organic versus inorganic carbon burial was developed. In order to verify the consistency of the model we correlated the modeled output of the Furlo section with that of the Manilva section, in southeast Spain. The modeling shows that increasing productivity only partially explains the measured d 13 C excursion and is not the only factor relevant to black shales deposition. Preservation may play a central role, especially in the later stages of OAE 2. Phosphorus and TOC accumulation patterns in the Bonarelli Level in both Furlo and Manilva suggest a similar process although other factors may also be involved.