(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.

Isotope record of Nd-Sr-Pb in deep sea sediments from the Pacific (Table 2)

Pelagic clay of the east-central Pacific province is shown to be a mixture of three primary detrital components, reflecting continental source areas in Asia, North America, and Central and South America. Relative contributions from each source area are a function of geography, and this distribution appears to have remained constant over the past five million years, despite changing flux rates. A Q-mode factor analysis of downcore records for Pb, Sr, and Nd isotopes identified three factors that account for 98% of the total variance. These factors represent the radiogenic isotopic signatures of 1) late Cenozoic Asian dust, which dominates in the central North Pacific; 2) North American continental hemipelagic/eolian sources, restricted mainly to the easternmost North Pacific at ~30 °N latitude; and 3) Central and South American sources, restricted to areas east of ~100 °W longitude. South of the Intertropical Convergence Zone (~6 °N), the Asian dust signature diminishes abruptly. We conclude that late Cenozoic Asian dust sources can be isotopically differentiated downcore from both North American and South and Central American sources in the eastcentral Pacific. This approach has a utility for identifying changes in long-term Cenozoic atmospheric circulation patterns.

Isotope ratios of basalts from ODP Leg 115 holes (Table 1)

Strontium, neodymium, and lead isotope ratios are reported for 13 Leg 115 basalts as well as 3 basalts from Texaco drill hole SM-1 on the Mascarene Plateau. The 87Sr/86Sr ratios and eNd range from 0.70330 to 0.70439 and 5.5 to 7.4, respectively, although 87Sr/86Sr ratios higher than 0.70383 are found only in SM-1 basalts. The high 87Sr/86Sr values are thought to reflect seawater Sr in secondary phases, although all samples were strongly leached in HC1 before analysis. 206Pb/204Pb ratios range from 18.53 to 18.80, and sho high 207Pb/204Pb and 208Pb/204Pb ratios relative to 206Pb/204Pb ratios, typical of Indian Ocean mid-ocean ridge (MORB) and oceanic-island basalts (OIB). Isotopic compositions of Leg 115 basalts generally fall between fields for MORB and Reunion Island basalts, consistent with the conclusion drawn from geochronological studies that Deccan flood basalt volcanism, the Chagos-Laccadive Ridge, and the Mascarene Plateau are all products of the Reunion mantle plume. Isotopic compositions of magmas produced by this plume have varied systematically with time in the direction of less "depleted," less MORB-like isotopic signatures. This compositional change has been accompanied by a decrease in eruption rate. We interpret Deccan volcanism as the voluminous beginning of the plume. Reduced entrainment of asthenosphere following melting of the plume head resulted in less MORB-like isotope ratios in magmas and a decrease in eruptive activity with time.

Benthic foraminiferal stable isotope record from ODP Site 138-849 on the East Pacific Rise

Benthic foraminifer and delta13C data from Site 849, on the west flank of the East Pacific Rise (0°11 'N, 110°31'W; 3851 m), give relatively continuous records of deep Pacific Ocean stable isotope variations between 0 and 5 Ma. The mean sample spacing is 4 k.y. Most analyses are from Cibicides wuellerstorfi, but isotopic offsets relative to Uvigerina peregrina appear roughly constant. Because of its location west of the East Pacific Rise, Site 849 yields a suitable record of mean Pacific Ocean delta13C, which approximates a global oceanic signal. The ~100-k.y.-period climate cycle, which is prevalent in delta18O does not dominate the long-term delta13C record. For delta13C, variations in the ~400- and 41-k.y. periods are more important. Phase lags of delta13C relative to ice volume in the 41- and 23-k.y. bands are consistent with delta13C as a measure of organic biomass. A model-calculated exponential response time of 1-2 k.y. is appropriate for carbon stored in soils and shallow sediments responding to glacial-interglacial climate change. Oceanic delta13C leads ice volume slightly in the 100-k.y. band, and this suggests another process such as changes in continental weathering to modulate mean river delta13C at long periods. The delta13C record from Site 849 diverges from that of Site 677 in the Panama Basin mostly because of decay of 13C-depleted organic carbon in the relatively isolated Panama Basin. North Atlantic to Pacific delta13C differences calculated using published data from Sites 607 and 849 reveal variations in Pliocene deep water within the range of those of the late Quaternary. Maximum delta13C contrast between these sites, which presumably reflects maximum influx of high-delta13C northern source water into the deep North Atlantic Ocean, occurred between 1.3 and 2.1 Ma, well after the initiation of Northern Hemisphere glaciation. Export of high-delta13C North Atlantic Deep Water from the Atlantic to the circumpolar Antarctic, as recorded by published delta13C data from Subantarctic Site 704, appears unrelated to the North Atlantic-Pacific delta13C contrast. To account for this observation, we suggest that deep-water formation in the North Atlantic reflects northern source characteristics, whereas export of this water into the circumpolar Antarctic reflects Southern Hemisphere wind forcing. Neither process appears directly linked to ice-volume variations.

Great Barrier Reef coral element/Ca and stable isotope data and U-Th ages from IODP Expedition 325

Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1-2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought.

Stable isotope analysis and temperature reconstruction data from DSDP Hole 94-609B and ODP Hole 162-984B

The Greenland ice sheet is accepted as a key factor controlling the Quaternary glacial scenario. However, the origin and mechanisms of major Arctic glaciation starting at 3.15 Ma and culminating at 2.74 Ma are still controversial. For this phase of intense cooling Ravelo et al. proposed a complex gradual forcing mechanism. In contrast, our new submillennial-scale paleoceanographic records from the Pliocene North Atlantic suggest a far more precise timing and forcing for the initiation of northern hemisphere glaciation (NHG), since it was linked to a 2-3 °C surface water warming during warm stages from 2.95 to 2.82 Ma. These records support previous models, claiming that the final closure of the Panama Isthmus (3.0- ~2.5 Ma induced an increased poleward salt and heat transport. Associated strengthening of North Atlantic Thermohaline Circulation and in turn, an intensified moisture supply to northern high latitudes resulted in the build-up of NHG, finally culminating in the great, irreversible climate crash at marine isotope stage G6 (2.74 Ma). In summary, there was a two-step threshold mechanism that marked the onset of NHG with glacial-to-interglacial cycles quasi-persistent until today.

Rb, Sr, Sm and Nd concentrations and isotopic composition of basalts from DSDP Leg 74 (Table 1)

Basement intersected in DSDP holes 525A, 528 and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid and lower northwest flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge (Rabinowitz and LaBrecque, 1979 doi:10.1029/JB084iB11p05973, Moore et al. (1983 doi:10.1130/0016-7606(1983)94<907:TWRTDS>2.0.CO;2). The basalts were erupted approximately 70 m.y. ago, an age equivalent to that of immediately adjacent oceanic crust in the Angola Basin and coraistent with formation at the paleo mid-ocean ridge (Moore et al., 1983). The basalt types vary from aphyric quartz tholeiites on the ridge crest to highly plagioclase phyric olivine tholeiites on the ridge flank. These show systematic differences in incompatible trace element and isotopic composition. Many element and isotope ratio pairs form systematic trends with the ridge crest basalts at one end and the highly phyric ridge flank basalts at the other. The low 143Nd/144Nd (0.51238), 206Pb/204Pb (17.54), 207Pb/204Pb (15.47), 208Pb/204Pb (38.14) and high 87Sr/86Sr (0.70512) ratios of the ridge crest basalts suggest derivation from an old Nd/Sm-, Rb/Sr- and Pb/U-enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset to significantly lower Nd and Pb isotopic ratios. The isotopic ratio trends may be extrapolated beyond the ridge flank basalts with higher 143Nd/144Nd (0.51270), 206Pb/204Pb (18.32), 207Pb/204Pb (15.52), 208Pb/204Pb (38.77) and lower 87Sr/86Sr (0.70417) ratios in the direction of increasingly Nd/Sm-, Rb/Sr- and Pb/U-depleted source compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing, as might result from the rise of a lower mantle plume through the upper mantle. Incompatible element and Pb isotopic systematics also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources. In our preferred petrogenetic model the Walvis Ridge basalts were derived by partial melting of mantle similar to an enriched (E-type) MORB source which had become heterogeneous on a small scale due to the introduction of small-volume melts and metasomatic fluids.

Strontium isotope ratios of pore waters and planktonic foraminifera from DSDP holes

A detailed record of the strontium-87 to strontium-86 ratio in seawater during the last 100 million years was determined by measuring this ratio in 137 well-preserved and well-dated fossil foraminifera samples. Sample preservation was evaluated from scanning electron microscopy studies, measured strontium-calcium ratios, and pore water strontium isotope ratios. The evolution of the strontium isotopic ratio in seawater offers a means to evaluate long-term changes in the global strontium isotope mass balance. Results show that the marine strontium isotope composition can be used for correlating and dating well-preserved authigenic marine sediments throughout much of the Cenozoic to a precision of +/- 1 million years. The strontium-87 to strontium-86 ratio in seawater increased sharply across the Cretaceous/Tertiary boundary, but this feature is not readily explained as strontium input from a bolide impact on land.

(Table 1) U and Th isotope analyses of pyrite and anhydrite of ODP Site 158-957

Hydrothermal circulation at oceanic spreading ridges causes sea water to penetrate to depths of 2 to 3 km in the oceanic crust where it is heated to ~400 °C before venting at spectacular 'black smokers'. These hydrothermal systems exert a strong influence on ocean chemistry (Edmond et al., 1979, doi:10.1016/0012-821X(79)90061-X), yet their structure, longevity and magnitude remain largely unresolved (Elderfield and Schultz., 1996, doi:10.1146/annurev.earth.24.1.191). The active Transatlantic Geotraverse (TAG) deposit, at 26° N on the Mid-Atlantic Ridge, is one of the largest, oldest and most intensively studied of the massive sulphide mounds that accumulate beneath black-smoker fields. Here we report ages of sulphides and anhydrites from the recently drilled (Humphris et al., 1995, doi:10.1038/377713a0) TAG substrate structures -determined from 234U-230Th systematics analysed by thermal ionization mass spectrometry. The new precise ages combined with existing data (Lalou et al., 1993, doi:10.1029/92JB01898; 1998, doi:10.2973/odp.proc.sr.158.214.1998) show that the oldest material (11,000 to 37,000 years old) forms a layer across the centre of the deposit with younger material (2,300-7,800 years old) both above and below. This stratigraphy confirms that much of the sulphide and anhydrite are precipitated within the mound by mixing of entrained sea water with hydrothermal fluid (James and Elderfield, 1996, doi:10.1130/0091-7613(1996)024<1147:COOFFA>2.3.CO;2). The age distribution is consistent with episodic activity of the hydrothermal system recurring at intervals of up to 2,000 years.

(Table 1) Sr, Nd, and Pb isotopic composition of ODP Leg 129 basalts

Basaltic rocks recovered from three drill sites in the western Pacific during Ocean Drilling Program Leg 129 have fairly distinct Sr, Nd, and Pb isotopic compositions. The Cretaceous alkali olivine dolerites from Site 800 in the northern part of Pigafetta Basin have fairly low 87Sr/86Sri (0.70292-0.70320) and 143Nd/144Ndi (0.51277-0.51281) and high present-day Pb isotopic ratios (206Pb/204Pb = 20.53-21.45; 207Pb/204Pb = 15.70-15.77; 208Pb/204Pb = 40.02-40.68). The Middle Jurassic tholeiites from Site 801 in the southern part of the basin have low 87Sr/86Sri (0.70237-0.70248), high 143Nd/144Ndi (0.51298-0.51322), and moderate present-day Pb isotopic ratios (206Pb/204Pb = 18.20-19.12; 207Pb/204Pb = 15.47-15.60; 208Pb/204Pb = 37.56-38.18); isotopic compositions of the alkali olivine basalts overlying the tholeiites fall between those of the tholeiites and Site 800 dolerites. The Cretaceous tholeiites from Site 802 in the East Mariana Basin have high 87Sr/86Sri (0.70360-0.70372), fairly low 143Nd/144Ndi (0.51277-0.51280), and fairly low and homogeneous present-day Pb isotopic ratios (206Pb/204Pb = 18.37-18.39; 207Pb/204Pb = 15.49-15.51; 208Pb/204Pb = 38.34-38.39). Isotopic compositions of Site 801 tholeiites are indistinguishable from those of modern mid-ocean ridge basalts, consistent with the proposal that these tholeiites are a part of the oldest Pacific crust. The diverse isotopic compositions of the younger basalts appear to be the result of Jurassic Pacific plate migration over the geologically anomalous south-central Pacific region, wherein they acquired their distinct isotopic compositions. The anomalous region was volcanically more active during the Cretaceous than at present.

Geochemistry and oxygen and iron isotope ratios of mafic rocks

Recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes. The oxygen isotope ratios (d18O) of some ocean island basalts (OIB) span values both above and below that of unmetasomatised upper mantle (5.5 ± 0.4 per mil) and provide support for this hypothesis, as it is widely assumed that most variations in d18O are produced by near-surface low-temperature processes. Here we show a significant linear relationship between d18O and stable iron isotope ratios (d57Fe) in a suite of pristine eclogite xenoliths. The d18O values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values. The observed range and correlation between d18O and d57Fe is unlikely to be inherited from oceanic crust, as d57Fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with d18O. It is proposed that the correlated d57Fe and d18O variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out. Fractionation of Fe and O isotopes by removal of partial melt enriched in isotopically heavy Fe and O is supported by negative correlations between bulk sample d57Fe and Cr content and bulk sample and garnet d18O and Sc contents, as Cr and Sc are elements that become enriched in garnet- and pyroxene-bearing melt residues. Melt extraction could take place either during subduction, where the eclogites represent the residues of melted oceanic lithosphere, or could take place during long-term residence within the lithospheric mantle, in which case the protoliths of the eclogites could be of either crustal or mantle origin. This modification of both d57Fe and d18O by melting processes and specifically the production of low-d18O signatures in mafic rocks implies that some of the isotopically light d18O values observed in OIB and eclogite xenoliths may not necessarily reflect near-surface processes or components.