Stable isotope ratios on planktonic foraminifer N. pachyderma of surface sediments from the Arctic Ocean (Table 1)

Planktic foraminifers Neogloboquadrina pachyderma (sin.) from 87 eastern and central Arctic Ocean surface sediment samples were analyzed for stable oxygen and carbon isotope composition. Additional results from 52 stations were taken from the literature. The lateral distribution of delta18O (18O/16O) values in the Arctic Ocean reveals a pattern of roughly parallel, W-E stretching zones in the Eurasian Basin, each ~0.5 per mil wide on the delta18O scale. The low horizontal and vertical temperature variability in the Arctic halocline waters (0-100 m) suggests only little influence of temperature on the oxygen isotope distribution of N. pachyderma (sin.). The zone of maximum delta18O values of up to 3.8 per mil is situated in the southern Nansen Basin and relates to the tongue of saline (> 33%.) Atlantic waters entering the Arctic Ocean through the Fram Strait. delta18O values decrease both to the Barents Shelf and to the North Pole, in accordance with the decreasing salinities of the halocline waters. In the Nansen Basin, a strong N-S delta18O gradient is in contrast with a relatively low salinity change and suggests contributions from different freshwater sources, i.e. salinity reduction from sea ice meltwater in the south and from light isotope waters (meteoric precipitation and river-runoff) in the northern part of the basin. North of the Gakkel Ridge, delta18O and salinity gradients are in good accordance and suggest less influence of sea ice melting processes. The delta13C (13C/12C) values of N. pachyderma (sin.) from Arctic Ocean surface sediment samples are generally high (0.75-0.95 per mil). Lower values in the southern Eurasian Basin appear to be related to the intrusion of Atlantic waters. The high delta13C values are evidence for well ventilated surface waters. Because the perennial Arctic sea ice cover largely prevents atmosphere-ocean gas exchange, ventilation on the seasonally open shelves must be of major importance. Lack of delta13C gradients along the main routes of the ice drift from the Siberian shelves to the Fram Strait suggests that primary production (i.e. CO2 consumption) does probably not change the CO2 budget of the Arctic Ocean significantly.

Distribution of planktonic foraminifera in Quaternary sediments east of New Zealand

A series of cores from east of New Zealand have been examined to determine the paleoceanographic history of the late Quaternary in the SW Pacific using planktonic foraminiferal data. Distinct shifts of species can be seen between glacial and interglacial times especially south of Chatham Rise east of South Island. Foraminiferal fragmentation ratios and benthic/planktonic foraminiferal ratios both show increased dissolution during glacials, especially isotope stage 2 to the south of Chatham Rise. The present-day Subtropical Convergence appears to be tied to the Chatham Rise at 44°S, but during glacial times this rise separated cold water to the south from much warmer water to the north, with an associated strong thermal gradient across the rise. We estimate that this gradient could have presented as much as an 8°C temperature change across 4°C of latitude during the maximum of the last ice age. There is only weak evidence of the Younger Dryas cool event, but there is a clear climatic optimum between 8 and 6.4 ka with temperatures 1°-2°C higher than the present day. The marine changes compare well with vegetational changes on both South and North Island.

(Table A1) Diatom isotope measurements from ODP Hole 145-882A

In comparison to other sectors of the marine system, the palaeoceanography of the subarctic North Pacific Ocean is poorly constrained. New diatom isotope records of d13C, d18O, d30Si (d13Cdiatom, d18Odiatom, and d30Sidiatom) are presented alongside existing geochemical and isotope records to document changes in photic zone conditions, including nutrient supply and the efficiency of the soft-tissue biological pump, between Marine Isotope Stage (MIS) 4 and MIS 5e. Peaks in opal productivity in MIS 5b/c and MIS 5e are both associated with the breakdown of the regional halocline stratification and increased nutrient supply to the photic zone. Whereas the MIS 5e peak is associated with low rates of nutrient utilisation, the MIS 5b/c peak is associated with significantly higher rates of nutrient utilisation. Both peaks, together with other smaller increases in productivity in MIS 4 and 5a, culminate with a significant increase in freshwater input which strengthens/re-establishes the halocline and limits further upwelling of sub-surface waters to the photic zone. Whilst d30Sidiatom and previously published records of diatom d15N (d15Ndiatom) (Brunelle et al., 2007, 2010) show similar trends until the latter half of MIS 5a, the records become anti-correlated after this juncture and into MIS 4, suggesting a possible change in photic zone state such as may occur with a shift to iron or silicon limitation.

Geochemistry and radiogenic isotope ratios of the volcanic sequences from Izu-Bonin Arc, Japan

New radiogenic isotope and trace element data are presented for the volcanic sequences along 600 km of the active Izu-Bonin arc, the Oligocene Izu arc, and their associated rift basins. As with many intra-oceanic island arcs, the Pliocene-Recent Izu-Bonin frontal-arc lavas are highly depleted in Zr, Nb and the rare-earth elements relative to typical mid-ocean ridge basalt (MORB), indicating that the mantle wedge source has undergone a previous episode of melting. Ratios between these elements (such as Nb/Zr and La/Sm), as well as 143Nd/144Nd, do not vary significantly along the length of the frontal-arc. These parameters suggest that each of the arc volcanoes is derived from similar melt fractions of the mantle wedge. However, Ba/Zr, Ba/Rb and 87Sr/86Sr increase along the frontal-arc to the north. This leads us to propose that a variable enrichment in Ba and radiogenic Sr is superimposed on the mantle wedge. Sr-Nd and Pb-Nd isotope variation indicate that both Sr and Pb become more radiogenic after fluid addition. However, Pb isotope ratios do not correlate with increases in Pb concentration or ratios such as Ba/Zr and Nb/Pb. In other words, the Pb isotopic composition of the arc lavas appears to be independent of the amount of Pb introduced by subduction fluids into the mantle source. This buffering of Pb isotopes along the frontal-arc means that the isotopic composition of the lavas is indistinguishable from that of the fluid. Isotopic mixing models presented for the arc are only illustrative of the many plausible combinations of components and quantities. Despite this, we are able to determine that the mantle wedge has isotopic characteristics similar to Indian Ocean MORB, and that the subduction-fluid solute is primarily derived from subducted oceanic basalt with a <2% contribution from subducted sediment. Lavas in the Oligocene Izu arc and fore-arc basin were derived from a mantle wedge of similar composition to the active arc. Despite levels of Pb enrichment comparable to those of the modern arc, the Pb isotopes of the Oligocene volcanics indicate a lower sediment input into the melting region.

(Table 1) N-isotope record of planktonc foraminifera of sediment core MD02-2550C2

Constraining variations in marine N2-fixation over glacial-interglacial timescales is crucial for determining the role of the marine nitrogen cycle in modifying ocean productivity and climate, yet paleo-records from N2-fixation regions are sparse. Here we present new nitrogen isotope (d15N) records of bulk sediment and foraminifera test-bound (FB) nitrogen extending back to the last ice age from the oligotrophic Gulf of Mexico (GOM). Previous studies indicate a substantial terrestrial input during the last ice age and early deglacial, for which we attempt to correct the bulk sediment d15N using its observed relationship with the C/N ratio. Both corrected bulk and FB-d15N reveal a substantial glacial-to-Holocene decrease of d15N toward Holocene values of around 2.5 per mil, similar to observations from the Caribbean. This d15N change is most likely due to a glacial-to-Holocene increase in regional N2-fixation. A deglacial peak in the FB-d15N of thermocline dwelling foraminifera Orbulina universa probably reflects a whole ocean increase in the d15N of nitrate during deglaciation. The d15N of the surface dwelling foraminifera Globigerinoides ruber and the corrected bulk d15N show little sign of this deglacial peak, both decreasing from last glacial values much earlier than does the d15N of O. universa; this may indicate that G. ruber and bulk N reflect the euphotic zone signal of an early local increase in N2-fixation. Our results add to the evidence that, during the last ice age, the larger iron input from dust did not lead to enhanced N2-fixation in this region. Rather, the glacial-to-Holocene decrease in d15N is best explained by a response of N2-fixation within the Atlantic to the deglacial increase in global ocean denitrification.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

Stable isotope, UK'37, SST, chlorin, alkenone and TOC data of sediment cores GIK17927-2 and GIK17928-3

Upwelling intensity in the South China Sea has changed over glacial-interglacial cycles in response to orbital-scale changes in the East Asian Monsoon. Here, we evaluate new multi-proxy records of two sediment cores from the north-eastern South China Sea to uncover millennial-scale changes in winter monsoondriven upwelling over glacial Terminations I and II. On the basis of U/Th-based speleothem chronology, we compare these changes with sediment records of summer monsoondriven upwelling east of South Vietnam. Ocean upwelling is traced by reduced (UK'37-based) temperature and increased nutrient and productivity estimates of sea surface water (d13C on planktic foraminifera, accumulation rates of alkenones, chlorins, and total organic carbon). Accordingly, strong winter upwelling occurred north-west of Luzon (Philippines) during late Marine Isotope Stage 6.2, Heinrich (HS) and Greenland stadials (GS) HS-11, GS-26, GS-25, HS-1, and the Younger Dryas. During these stadials, summer upwelling decreased off South Vietnam and sea surface salinity reached a maximum suggesting a drop in monsoon rains, concurrent with speleothem records of aridity in China. In harmony with a stadial-to-interstadial see-saw pattern, winter upwelling off Luzon in turn was weak during interstadials, in particular those of glacial Terminations I and II, when summer upwelling culminated east of South Vietnam. Most likely, this upwelling terminated widespread deep-water stratification, coeval with the deglacial rise in atmospheric CO2. Yet, a synchronous maximum in precipitation fostered estuarine overturning circulation in the South China Sea, in particular as long as the Borneo Strait was closed when sea level dropped below -40 m.

Stable carbon and oxygen isotope rates of Maastrichtian ODP samples from Shatsky Rise

We present new isotopic and micropaleontological data from a depth transect on Shatsky Rise that record the response of the tropical Pacific to global biotic and oceanographic shifts during the mid-Maastrichtian. Results reveal a coupling between the upper ocean, characterized by a weak thermocline and low to intermediate productivity, and intermediate waters. During the earliest Maastrichtian, oxygen and neodymium isotope data suggest a significant contribution of relatively warm intermediate water from the North Pacific. Isotopic shifts through the early Maastrichtian suggest that this warmer water mass was gradually replaced by cooler waters originating in the Southern Ocean. Although the cooler water mass remained dominant through the remainder of the Maastrichtian, it was displaced intermittently at shallow intermediate depths by North Pacific intermediate water. The globally recognized "mid-Maastrichtian event" ~69 Ma, manifested by the brief appearance of abundant inoceramid bivalves over shallow portions of Shatsky Rise, is characterized by an abrupt increase (~2°-3°C) in sea surface temperatures, a greater flux of organic matter out of the surface ocean, and warmer (~4°C) intermediate waters. Results implicate simultaneous changes in surface waters and the sources/distribution patterns of intermediate water masses as an underlying cause for widespread biotic and oceanographic changes during mid-Maastrichtian time.

(Table 1) Nd isotope ratios of ODP Leg 208 samples

We present new Nd isotope records from Walvis Ridge Ocean Drilling Program (ODP) sites 1262-1264 (southeastern Atlantic) spanning the past 24 Ma to investigate the Neogene evolution of Atlantic thermohaline circulation. The new data indicate that deepwater epsilon-Nd(t) values from ODP Site 1262 decrease from -11.0 at 10.6 Ma to -12.5 by 7.3 Ma. This decrease parallels the Nd isotope trends contained in Fe-Mn crust records from the northwestern Atlantic; however, the shift at ODP Site 1262 (4755 m water depth) occurred up to ~6 Ma earlier than the corresponding changes in crust records from the Atlantic and earlier than any Atlantic site shallower than 2700 m paleowater depth. Recent interpretations of the rapid decrease in Fe-Mn crust Nd epsilon-Nd(t)ss values invoke changes in weathering inputs to the Labrador Sea region rather than a fundamental change in deepwater convection in the Labrador Sea. However, the new evidence for significant depth stratification of the Nd isotope signal in the southeastern Atlantic between 10.6 and 7.3 Ma suggests that the onset of deepwater convection in the Labrador Sea may have played a role in the deepwater decrease in Nd isotopic composition. Climatic conditions during the middle to late Miocene likely favored an increase in the importance of glacially induced mechanical weathering, while at the same time promoting deep convection in the Labrador Sea.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

Stable isotopic composition of Poritres lutea from New Caledonia

A 335 year stable isotope record from a New Caledonia coral (22°S, 166°E) helps fill a large gap in historical climate reconstructions. Although the long-term coral s18O-based sea surface temperature (SST) trend is one of warming, there are notable decadal fluctuations, especially in the early 18th and early 19th centuries. Mean annual SSTs between 1658 and 1900 are estimated to be ~0.3°C lower than the 20th century average, with interdecadal excursions of 0.5°-0.8°C. Time series analyses of the coral isotope record reveals significant concentrations of variance in the El Niño band; an inderdecadal spectral peak is present, but its robustness requires additional statistical evaluation. A secular but irregular decrease in coral d13C values begins in the mid-1800s and may reflect the anthropogenic perturbation of the carbon reservoir. These and other results indicate that the New Caledonia coral isotope record is a valuable source of information on southwest Pacific climate history.

Stable oxygen isotope ratios of diatoms and relative species abundances in ODP Site 145-882

Recent research has increasingly advocated a role for the North Pacific Ocean in modulating global climatic changes over both the last glacial cycle and further back into the geological record. Here a diatom d18O record is presented from Ocean Drilling Program Site 882 over the Pliocene/Quaternary boundary from 2.73 Ma to 2.52 Ma (MIS G6-MIS 99). Large changes in d18Odiatom of c. 4 per mil from 2.73 Ma onwards are documented to occur on a timeframe broadly coinciding with glacial-interglacial cycles. These changes are primarily attributed to large scale inputs of meltwater from glacials surrounding the North Pacific Basin and the Bering Sea. Despite these inputs and associated change in surface water salinity, on the basis of existing opal and UK37 temperature data and new modelled water column densities, no evidence exists to suggests a removal of the halocline stratification or a resumption of the high productivity system similar to that which prevailed prior to 2.73 Ma. The permanence of the halocline suggests that the region played a key role in driving global climatic changes over the early glacial-interglacial cycles that followed the onset of major Northern Hemisphere Glaciation by inhibiting deep water upwelling and ventilation of CO2 to the atmosphere.

Stable carbon and oxygen isotope ratios of foraminifera from Cretaceous and Paleocene sediments

Detailed analysis of over 200 samples of uppermost Cretaceous and Paleocene sediments from Atlantic Ocean DSDP Sites 384, 86, 95, 152, 144, 20C, 21, 356, 357, and 329 provides new information on the temperature stratification of Paleocene planktonic foraminifera, the temperature and carbon isotopic changes across the Cretaceous/Tertiary boundary, and the fluctuating temperature and carbon isotopic records through the Paleocene ~64.5-54 m.y.). There was a significant temperature rise across the Cretaceous/Tertiary boundary both at the surface and in deep waters of the Atlantic Ocean. This temperature rise occurred before the basal Tertiary 'Globigerina' eugubina Zone, so that in the oldest Paleocene sample yet analyzed from the deep sea (Site 356) temperatures are already three degrees higher at the bottom and at the surface than in the Cretaceous. The temperature rise across the boundaryis more pronounced on the bottom and in samples from higher latitudes. Accompanying the temperature rise across the boundary there is a significant shift in the carbon isotope profile. In the basal Paleocene the foraminifera of the surface zone demonstrate very negative carbon isotope values (unlike in the Cretaceous of today's ocean), while deeper dwelling species have more positive values which then decrease to the bottom. The unusual carbon isotope gradients persist through the first three million years of the Paleocene until towards the top of planktonic foraminiferal Zone P.1 (G. trinidadensis Zone) the foraminifera record a profile more positive at the surface and decreasing towards the bottom (as in today's ocean). During the Paleocene there are two noteworthy rises in surface water temperature; the first around 62-61 m.y. (G. trinidadensis Zone), and the second near the base of the Globorotalia angulata Zone, 60-59 m.y. At this time surface temperatures at low to mid latitudes reached values near 25°C, while at mid-latitude Site 384 temperature highs near 22°C were registered. At a sample spacing of around one per million years, we have only produced some of the detail of these temperature fluctuations. The later Paleocene is generally cooler and there do not seem to be any large variations either through time or latitude. Middle-latitude sites average temperatures near 15°C at the surface, while high lower latitude site temperatures range near 18°C. The most salient feature of the bottom temperature record (based on multispecific samples) through the Paleocene is its lack of fluctuations. There is an overall temperature range of 5°C at these intermediate depth sites (paleodepth estimates between 1500 and 3000 m). Higher values near 13°C accompany the surface temperature peaks around 62 and 60 m.y., while low values near 8°C occur in Zone P.2 (61-60 m.y.). We detected no change in bottom temperature across the paleocene/Eocene boundary in the few samples studied so far. While there are several fluctuations in the carbon isotope values through the early Paleocene, the general trend is one of increasingly positive values at the surface and at depth. This trend culminates in the late Paleocene (upper Zone P.4, about 56-57 m.y.) with a major excursion in the carbon isotope values. At low latitudes the range between the surface and the deepest planktonic foraminifera is a delta13C of 4 per mil as compared with a range of 2 per mil today. The carbon values drop off slightly, but remain strongly positive through the remainder of the Paleocene at most sites. Accompanying the carbon isotope excursion at Site 384 is a productivity increase and a proposed rise in the CCD.

Helium and oxygen isotope ratios of ODP Sites 193-1188 and 193-1189

Fluid mixing processes and thermal regimes within the Snowcap and Roman Ruins vent sites of the PACMANUS hydrothermal system, Papua New Guinea, were investigated using 3He/4He ratios from fluid inclusions within pyrite and anhydrite and the d18O signature of anhydrite. Depressed 3He/4He ratios of 0.2-6.91RA appear to be caused by significant atmospheric diffusive exchange, whilst He-Ne diffusive fractionation precludes correction using 20Ne. 40Ar/36Ar ratios of 295-310 are elevated above seawater, indicating the majority of argon is seawater derived but with a magmatic component. d18O anhydrite ratios are 6.5 per mil to 11 per mil for Snowcap and 6.4 per mil to 11.9 per mil for Roman Ruins. Using oxygen isotope fractionation factors for the anhydrite-water system, the temperatures calculated assuming isotopic equilibrium at depth are up to 100 °C cooler than fluid inclusion trapping temperatures. It is likely that anhydrite is precipitated rapidly, preventing d18O equilibration. By comparing new d18O values for anhydrite with corresponding published 87Sr/86Sr ratios, seawater is inferred to penetrate deep into the Snowcap system with little conductive heating. A simple fluid mixing model has been constructed whereby the differing venting styles can be explained by a plumbing system at depth which favors delivery of end-member hydrothermal fluid to the high temperature sites.

Sedimentology, age models and stable isotope ratios of sediment cores from the equatorial Pacific

Based on detailed reconstructions of global distribution patterns, both paleoproductivity and the benthic d13C record of CO2, which is dissolved in the deep ocean, strongly differed between the Last Glacial Maximum and the Holocene. With the onset of Termination I about 15,000 years ago, the new (export) production of low- and mid-latitude upwelling cells started to decline by more than 2-4 Gt carbon/year. This reduction is regarded as a main factor leading to both the simultaneous rise in atmospheric CO2 as recorded in ice cores and, with a slight delay of more than 1000 years, to a large-scale gradual CO2 depletion of the deep ocean by about 650 Gt C. This estimate is based on an average increase in benthic d13C by 0.4-0.5 per mil. The decrease in new production also matches a clear 13C depletion of organic matter, possibly recording an end of extreme nutrient utilization in upwelling cells. As shown by Sarnthein et al., [1987], the productivity reversal appears to be triggered by a rapid reduction in the strength of meridional trades, which in turn was linked via a shrinking extent of sea ice to a massive increase in high-latitude insolation, i.e., to orbital forcing as primary cause.