(Table 1) Description and tetrapyrrole-pigment yield at DSDP Leg 58 Holes

Nineteen core samples from the Shikoku Basin and the Daito Ridge and Basin province of the northwest Philippine Sea, obtained from DSDP Leg 58, were examined for products of chlorophyll diagenesis; we aimed at gaining a better understanding of the very early diagenetic history of sedimentary chlorophyll. We choose samples which, a priori, would allow isolation of tetrapyrrole pigments characteristic of (destructive) diagenesis modes. Studies of Japan Trench sediments (Louda et al., 1980; Baker and Louda, 1980) showed well the interplay of two main diagenesis schemes: anoxic preservation and oxic destruction. The results reported herein are a product of a preliminary investigation on sediments of scant organic matter content, which yielded limited tetrapyrrole pigment.

Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

(Table S1) Carbon and oxygen isotope values, and Mn and Sr concentrations of Early Jurassic sediments

For much of the Mesozoic record there has been an inconclusive debate on the possible global significance of isotopic proxies for environmental change and of sequence stratigraphic depositional sequences. We present a carbon and oxygen isotope and elemental record for part of the Early Jurassic based on marine benthic and nektobenthic molluscs and brachiopods from the shallow marine succession of the Cleveland Basin, UK. The invertebrate isotope record is supplemented with carbon isotope data from fossil wood, which samples atmospheric carbon. New data elucidate two major global carbon isotope events, a negative excursion of ~2 per mil at the Sinemurian-Pliensbachian boundary, and a positive excursion of ~2 per mil in the Late Pliensbachian. The Sinemurian-Pliensbachian boundary event is similar to the slightly younger Toarcian Oceanic Anoxic Event and is characterized by deposition of relatively deepwater organic-rich shale. The Late Pliensbachian strata by contrast are characterized by shallow marine deposition. Oxygen isotope data imply cooling locally for both events. However, because deeper water conditions characterize the Sinemurian-Pliensbachian boundary in the Cleveland Basin the temperature drop is likely of local significance; in contrast a cool Late Pliensbachian shallow seafloor agrees with previous inference of partial icehouse conditions. Both the large-scale, long-term and small-scale, short-duration isotopic cycles occurred in concert with relative sea level changes documented previously from sequence stratigraphy. Isotope events and the sea level cycles are concluded to reflect processes of global significance, supporting the idea of an Early Jurassic in which cyclic swings from icehouse to greenhouse and super greenhouse conditions occurred at timescales from 1 to 10 Ma.

(Table 1) Geochemistry of Sapropels of the Mediterranean Sea

Sapropels -organic-matter rich layers- are common in Neogene sediments of the eastern Mediterranean Sea. The formation of these layers has been attributed to climate-related increases in organic-matter production (Calvert et al., 1992, doi:10.1038/359223a0; Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X) and increased organic-matter preservation due to oxygen depletion in more stagnant bottom waters (Rossignol-Strick et al., 1982, doi:10.1038/295105a0; Rohling, 1994, doi:10.1016/0025-3227(94)90202-X). Here we report that eastern Mediterranean Pliocene sapropels (Emeis et al., 1996, doi:10.2973/odp.proc.ir.160.102.1996) contain molecular fossils of a compound (isorenieratene) known to be synthesized by photosynthetic green sulphur bacteria, suggesting that sulphidic (euxinic) -and therefore anoxic- conditions prevailed in the photic zone of the water column. These sapropels also have a high trace-metal content, which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column. The abundance and sulphur-isotope composition of pyrite are consistent with iron sulphide formation in the water column. We conclude that basin-wide water-column euxinia occurred over substantial periods during Pliocene sapropel formation in the eastern Mediterranean Sea, and that the ultimate degradation of the increased organic-matter production was strongly influential in generating and sustaining the euxinic conditions.

Lower Albian benthic foraminifera

The Early Albian Oceanic Anoxic Event 1b (OAE 1b) black shale is interrupted by one or more ventilation events that display significant changes in benthic and planktic populations. Within the OAE 1b sections studied, at ODP Site 1049, DSDP Site 545, and the Vocontian Basin, the benthic foraminiferal repopulation events last between ~500 and ~1,250 years and occur with a cyclicity of approximately 5.7 kyr. This period may represent an amplitude modulation of the precessional cycle. The OAE 1b sections from the marginal setting of the Vocontian Basin exhibit up to eight repopulation events. In contrast, there is only one repopulation event identified in the Atlantic OAE 1b sections from the Mazagan Plateau (DSDP 545) and Blake Nose (ODP 1049). Within the margin of dating uncertainties, this supraregional repopulation event occurred synchronously in the Vocontian Basin and the Atlantic Ocean. While the OAE 1b black shale formed under extremely warm and humid conditions, the repopulation events occurred during intervals of short-term cooling and reduced humidity at deep-water formation sites. The resulting increase in evaporation led to enhanced formation of low-latitude deep water, thus improving the ventilation of the sea floor.

(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.

Germanium content in marine sediments

In the geosphere, germanium (Ge) has a chemical behavior close to that of silicon (Si), and Ge commonly substitutes for Si (in small proportions) in silicates. Studying the evolution of the respective proportions of Ge and Si through time allows us to better constrain the global Si cycle. The marine inventory of Ge present as dissolved germanic acid is facing two main sinks known through the study of present sediments: 1) incorporation into diatom frustules and transfer to sediments by these "shuttles", 2) capture of Ge released to pore water through frustule dissolution by authigenic mineral phases forming within reducing sediments. Our goals are to determine whether such a bio-induced transfer of Ge is also achieved by radiolarian and whether Ge could be trapped directly from seawater into authigenic phases with no intervention of opal-secreting organisms (shuttles). To this end, we studied two Paleozoic radiolarite formations and geological formations dated of Devonian, Jurassic and Cretaceous, deposited under more or less drastic redox conditions. Our results show that the Ge/Si values observed for these radiolarites are close to (slightly above) those measured from modern diatoms and sponges. In addition, our results confirm what is observed with some present-day reducing sediments: the ancient sediments that underwent reducing depositional conditions are authigenically enriched in Ge. Furthermore, it is probable that at least a part of the authigenic Ge came directly from seawater. The recurrence and extent (through time and space) of anoxic conditions affecting sea bottoms have been quite important through the geological times; consequently, the capture of Ge by reducing sediments must have impacted Ge distribution and in turn, the evolution of the seawater Ge/Si ratio.

(Table 1) Bulk Fe isotope values and pyrite framboids sizes of Cenomanian-Turonian samples

Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space.

Geochemical analysis at ODP Site 207-1261 from the Demerara Rise in the western equatorial Atlantic

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (~15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ~15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H2S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ?90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ~15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS**- production.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Biostratigraphy and average linear sedimentation rate and accumulation rate of ODP Site 159-959 (Table 1)

Reconstructing the long-term evolution of organic sedimentation in the eastern Equatorial Atlantic (ODP Leg 159) provides information about the history of the climate/ocean system, sediment accumulation, and deposition of hydrocarbon-prone rocks. The recovery of a continuous, 1200 m long sequence at ODP Site 959 covering sediments from Albian (?) to the present day (about 120 Ma) makes this position a key location to study these aspects in a tropical oceanic setting. New high resolution carbon and pyrolysis records identify three main periods of enhanced organic carbon accumulation in the eastern tropical Atlantic, i.e. the late Cretaceous, the Eocene-Oligocene, and the Pliocene-Pleistocene. Formation of Upper Cretaceous black shales off West Africa was closely related to the tectonosedimentary evolution of the semi-isolated Deep Ivorian Basin north of the Côte d'Ivoire-Ghana Transform Margin. Their deposition was confined to certain intervals of the last two Cretaceous anoxic events, the early Turonian OAE2 and the Coniacian-Santonian OAE3. Organic geochemical characteristics of laminated Coniacian-Santonian shales reveal peak organic carbon concentrations of up to 17% and kerogen type I/II organic matter, which qualify them as excellent hydrocarbon source rocks, similar to those reported from other marginal and deep sea basins. A middle to late Eocene high productivity period occurred off equatorial West Africa. Porcellanites deposited during that interval show enhanced total organic carbon (TOC) accumulation and a good hydrocarbon potential associated with oil-prone kerogen. Deposition of these TOC-rich beds was likely related to a reversal in the deep-water circulation in the adjacent Sierra Leone Basin. Accordingly, outflow of old deep waters of Southern Ocean origin from the Sierra Leone Basin into the northern Gulf of Guinea favored upwelling of nutrient-enriched waters and simultaneously enhanced the preservation potential of sedimentary organic matter along the West African continental margin. A pronounced cyclicity in the carbon record of Oligocene-lower Miocene diatomite-chalk interbeds indicates orbital forcing of paleoceanographic conditions in the eastern Equatorial Atlantic since the Oligocene-Miocene transition. A similar control may date back to the early Oligocene but has to be confirmed by further studies. Latest Miocene-early Pliocene organic carbon deposition was closely linked to the evolution of the African trade winds, continental upwelling in the eastern Equatorial Atlantic, ocean chemistry and eustatic sea level fluctuations. Reduction in carbonate carbon preservation associated with enhanced carbon dissolution is recorded in the uppermost Miocene (5.82-5.2 Ma) section and suggests that the latest Miocene carbon record of Site 959 documents the influence of corrosive deep waters which formed in response to the Messinian Salinity Crisis. Furthermore, sea level-related displacement of higher productive areas towards the West African shelf edge is indicated at 5.65, 5.6, 5.55, 5.2, 4.8 Ma. In view of humid conditions in tropical Africa and a strong West African monsoonal system around the Miocene-Pliocene transition, the onset of pronounced TOC cycles at about 5.6 Ma marks the first establishment of upwelling cycles in the northern Gulf of Guinea. An amplification in organic carbon deposition at 3.3 Ma and 2.45 Ma links organic sedimentation in the tropical eastern Equatorial Atlantic to the main steps of northern hemisphere glaciation and testifies to the late Pliocene transition from humid to arid conditions in central and western African climate. Aridification of central Africa around 2.8 Ma is not clearly recorded at Site 959. However, decreased and highly fluctuating carbonate carbon concentrations are observed from 2.85 Ma on that may relate to enhanced terrigenous (eolian) dilution from Africa.

Geochemical analysis at ODP Site 207-1259 from the Demerara Rise in the western equatorial Atlantic

Organic carbon-rich shales deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 were drilled during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic variations in marine and detrital sediment contribution, depositional processes, and bottom water redox conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V, Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites was generally dominated by marine material (carbonate, organic matter, opal) although relationships of detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular, and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older Cenomanian-Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms controlling continental supply and ocean redox state were time-invariant and kept the western equatorial Atlantic margin widely anoxic over millions of years.