(Appendix) Carbon and nitrogen isotope ratios of ODP Site 160-964

Nitrogen isotopes of chlorins, degradation products of chlorophyll, reflect the isotopic composition of nutrient N utilized by marine phytoplankton communities. Here we show that in sediments of the eastern Mediterranean Pleistocene and Holocene, values of d15N for chlorins and total nitrogen vary in concert, with a consistent offset of ~5 per mil reflecting the fractionation imparted during chlorophyll biosynthesis. Samples from the Integrated Ocean Drilling Program Sites 964 and 969 were analyzed at a sampling resolution of ~4-10 cm, clustered around sapropel events 2, 3, 4 and 5 (~100-170 ka). In low organic content sediments, chlorin values of ~0 per mil coincident with total nitrogen values of ~+ 5 per mil indicate that the latter reflects the original biomass and is not a consequence of diagenetic isotope enrichment. In sapropel horizons, the chlorin and total nitrogen values are 5 per mil more negative (~-5 per mil and ~ 0 per mil, respectively), resembling previously-reported, modern-day water-column particulates (~0 per mil). We suggest that nutrient conditions in the Eastern Mediterranean correspond to three scenarios and that the similarity between sapropel and modern-day bulk d15N is coincidental. Organic-poor marl sediments formed under oligotrophic conditions where surface productivity resulted from upwelling of Atlantic-sourced nitrate. Sapropels were characterized by enhanced diazotrophy that was likely fueled by increased riverine P fluxes to surface waters. Present-day conditions are dominated by anthropogenic N sources. These scenarios agree with a model of sapropel formation in which stratification caused by increased fresh-water inputs led to N fixation due to P:N nutrient imbalance. Enhanced production combined with stratification promoted and maintained anoxic deep waters, consequently increasing organic matter preservation. Such a model may be relevant to interpreting other episodes of intense organic matter deposition in past oceans.

Occurrence of hiatuses PH and NH 1 through NH 7 in DSDP holes

Miocene paleoceanographic evolution exhibits major changes resulting from the opening and closing of passages, the subsequent changes in oceanic circulation, and development of major Antarctic glaciation. The consequences and timing of these events can be observed in variations in the distribution of deep-sea hiatuses, sedimentation patterns, and biogeographic distribution of planktic organisms. The opening of the Drake Passage in the latest Oligocene to early Miocene (25-20 Ma) resulted in the establishment of the deep circumpolar current, which led to thermal isolation of Antarctica and increased global cooling. This development was associated with a major turnover in planktic organisms, resulting in the evolution of Neogene assemblages and the eventual extinction of Paleogene assemblages. The erosive patterns of two widespread hiatuses (PH, 23.0-22.5 Ma; and NH 1, 20-18 Ma) indicate that a deep circumequatorial circulation existed at this time, characterized by a broad band of carbonate-ooze deposition. Siliceous sedimentation was restricted to the North Atlantic and a narrow band around Antarctica. A major reorganization in deep-sea sedimentation and hiatus distribution patterns occurred near the early/middle Miocene boundary, apparently resulting from changes in oceanic circulation. Beginning at this time, deep-sea erosion occurred throughout the Caribbean (hiatus NH 2, 16-15 Ma), suggesting disruption of the deep circumequatorial circulation and northward deflection of deep currents, and/or intensification of the Gulf Stream. Sediment distribution patterns changed dramatically with the sudden appearance of siliceous-ooze deposition in the marginal and east equatorial North Pacific by 16.0 to 15.5 Ma, coincident with the decline of siliceous sedimentation in the North Atlantic. This silica switch may have been caused by the introduction of Norwegian Overflow Water into the North Atlantic acting as a barrier to outcropping of silica-rich Antarctic Bottom Water. The main aspects of the present oceanic circulation system and sediment distribution pattern were established by 13.5 to 12.5 Ma (hiatus NH 3), coincident with the establishment of a major East Antarctic ice cap. Antarctic glaciation resulted in a broadening belt of siliceous-ooze deposition around Antarctica, increased siliceous sedimentation in the marginal and east equatorial North Pacific and Indian Oceans, and further northward restriction of siliceous sediments in the North Atlantic. Periodic cool climatic events were accompanied by lower eustatic sea levels and widespread deep-sea erosion at 12 to 11 Ma (NH 4), 10 to 9 Ma (NH 5), 7.5 to 6.2 Ma (NH 6), and 5.2 to 4.7 Ma (NH 7).