Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.

Sea surface temperature record of ODP Site 202-1233

We present the first high-resolution alkenone-derived sea surface temperature (SST) reconstruction in the southeast Pacific (Ocean Drilling Program Site 1233) covering the major part of the last glacial period and the Holocene. The record shows a clear millennial-scale pattern that is very similar to climate fluctuations observed in Antarctic ice cores, suggesting that the Southern Hemisphere high-latitude climate changes extended into the midlatitudes, involving simultaneous changes in air temperatures over Antarctica, sea ice extent, extension of the Antarctic Circumpolar Current, and westerly atmospheric circulation. A comparison to other midlatitude surface ocean records suggests that this "Antarctic" millennial-scale pattern was probably a hemisphere-wide phenomenon. In addition, we performed SST gradient reconstructions over the complete latitudinal range of the Pacific Eastern Boundary Current System for different time intervals during the last 70 kyr. The main results suggest an equatorward displaced subtropical gyre circulation during marine isotope stages 2 and 4.

Miocene planktonic foraminifera of ODP Hole 130-806B

We document the waxing and waning of a "proto-warm pool" in the western equatorial Pacific (WEP) based on a study of multi-species planktic foraminiferal isotope ratios and census data spanning the 13.2-5.8 Ma interval at ODP Site 806. We hypothesize that the presence or absence of a proto-warm pool in the WEP, caused by the progressive tectonic constriction of the Indonesian Seaway and modulated by sea level fluctuations, created El Niño/La Niña-like alternations of hydrographic conditions across the equatorial Pacific during the late Miocene. This hypothesis is supported by the general antithetical relationship observed between carbonate productivity and preservation in the western and eastern equatorial Pacific, which we propose is caused by these alternating ocean-climate states. Warming of thermocline and surface waters, as well as a major change in planktic foraminferal assemblages record a two-step phase of proto-warm pool development ~11.6-10 Ma, which coincides with Miocene isotope events Mi5 and Mi6, and sea-level low stands. We suggest that these changes in the biota and structure of the upper water column in the WEP mark the initiation of a more modern equatorial current system, including the development of the Equatorial Undercurrent (EUC), as La Niña-like conditions became established across the tropical Pacific. This situation sustained carbonate and silica productivity in the eastern equatorial Pacific (EEP) at a time when carbonate preservation sharply declined in the Caribbean. Proto-warm pool weakening after ~10 Ma may have contributed to the nadir of a similar "carbonate crash" in the EEP. Cooling of the thermocline and increased abundances of thermocline taxa herald the decay of the proto-warm pool and higher productivity in the WEP, particularly ~ 9.0-8.8 Ma coincident with a major perturbation in tropical nannofossil assemblages. We suggest that this interval of increased productivity records El Niño-like conditions across the tropical Pacific and the initial phase of the widespread "biogenic bloom". Resurgence of a later proto-warm pool in the WEP ~6.5-6.1 Ma may have spurred renewed La Niña-like conditions, which contributed to a strong late phase of the "biogenic bloom" in the EEP.

Middle Eocene to late Oligocene calcareous nannofossils of ODP Hole 120-748B

A major deterioration in global climate occurred through the Eocene-Oligocene time interval, characterized by long-term cooling in both terrestrial and marine environments. During this long-term cooling trend, however, recent studies have documented several short-lived warming and cooling phases. In order to further investigate high-latitude climate during these events, we developed a high-resolution calcareous nannofossil record from ODP Site 748 Hole B for the interval spanning the late middle Eocene to the late Oligocene (~42 to 26 Ma). The primary goals of this study were to construct a detailed biostratigraphic record and to use nannofossil assemblage variations to interpret short-term changes in surface-water temperature and nutrient conditions. The principal nannofossil assemblage variations are identified using a temperate-warm-water taxa index (Twwt), from which three warming and five cooling events are identified within the middle Eocene to the earliest Oligocene interval. Among these climatic trends, the cooling event at ~39 Ma (Cooling Event B) is recorded here for the first time. Variations in fine-fraction d18O values at Site 748 are associated with changes in the Twwt index, supporting the idea that significant short-term variability in surface-water conditions occurred in the Kerguelen Plateau area during the middle and late Eocene. Furthermore, ODP Site 748 calcareous nannofossil paleoecology confirms the utility of these microfossils for biostratigraphic, paleoclimatic, and paleoceanographic reconstructions at Southern Ocean sites during the Paleogene.

Stable oxygen and carbon isotopes from ODP sites on Maud Rise and Kerguelen Plateau

Paleogene stable oxygen and carbon isotopes were measured in formainifera from ODP Sites 689 and 690 at Maud Rise in the Atlantic Ocean sector of the Southern Ocean, and from Sites 738, 744, 748 and 749 at the southern Kerguelen Plateau in the Indian Ocean sector. These data were compared with sedimentological data from the same sample set. Both benthic and planktic d18O values document a cooling trend beginning around 49.5 Ma at all sites. During the late middle Eocene planktic d18O values indicate a steepening latitudinal temperature gradient from 14°C at the northern sites towards 10°C at the southernmost sites. Terrigeneous sand grains of probably ice rafted origin and clay mineral assemblages point to the existence of a limited East Antarctic ice cap with some glaciers reaching sea level as early as middle Eocene time around 45.5 Ma. Between 45 and 40 Ma, average paleotemperatures were between 5° and 7°C in deep and intermediate water masses, while near-surface water masses ranged between 6° and 10°C. During the late Eocene, between 40 and 36 Ma, average temperatures further decreased to 4°-5°C in the deep and intermediate water masses and to 5°-8°C near the sea surface. Abruptly increasing d18O values at approximately 35.9 Ma exactly correlate with a sharp pulse in the deposition of ice-rafted material on the Kerguelen Plateau, a dramatic change in clay mineral composition, and an altered Southern Ocean circulation indicated by a differentiation of benthic d13C values between sites, increasing opal concentrations and decreasing carbonate contents. For planktic and benthic foraminifera this d18O increase ranges between 1.0 and 1.3 per mil, and between 0.9 and 1.4 per mil, respectively. We favour a hypothesis that explains most of the d18O shift at 35.9 Ma with a buildup of a continental East Antarctic ice sheet. Consequently, relatively warm Oligocene Antarctic surface water temperatures probably are explained by a temperate, wet-based nature of the ice sheet. This would also aid in the fast build-up of an ice sheet by enhancing the moisture transport on to the continent.

Record of pollen, silt and greyscale stack from the Eifel Laminated Sediment Archive (ELSA)

Investigating the processes that led to the end of the last interglacial period is relevant for understanding how our ongoing interglacial will end, which has been a matter of much debate. A recent ice core from Greenland demonstrates climate cooling from 122,000 years ago driven by orbitally controlled insolation, with glacial inception at 118,000 years ago. Here we present an annually resolved, layer-counted record of varve thickness, quartz grain size and pollen assemblages from a maar lake in the Eifel (Germany), which documents a late Eemian aridity pulse lasting 468 years with dust storms, aridity, bushfire and a decline of thermophilous trees at the time of glacial inception. We interpret the decrease in both precipitation and temperature as an indication of a close link of this extreme climate event to a sudden southward shift of the position of the North Atlantic drift, the ocean current that brings warm surface waters to the northern European region. The late Eemian aridity pulse occurred at a 65° N July insolation of 416 W/m**2, close to today's value of 428 W/m**2, and may therefore be relevant for the interpretation of present-day climate variability.

Stable isotope and geochemical record of ODP Hole 124-769A

Deep marine late Pleistocene sediments from Ocean Drilling Program Sulu Sea Site 769 contain a high-resolution record of paleoceanographic change in this strongly monsoonal climatic setting in the tropical western Pacific. Detailed time series of planktonic foraminifer (G.ruber; white variety) d18O, d13C, and bulk CaCO3 mass accumulation rate (MAR) were generated, spanning the last 750 k.y. Sedimentation rates in this portion of the record average 8.5 cm/k.y., and vary from 4 to 16 cm/k.y. Cross spectral analysis of the d18O and d13C time-series demonstrate that each contains increased variance at the primary orbital periodicities. The d18O record shows strong variability in the precessional-band and closely correlates with the SPECMAP d18O record and other high-resolution records. The dominance of a 23-k.y cycle in the d18O record agrees with other studies of the monsoon system in the Indian Ocean that have documented the importance of precessional insolation as a monsoon-forcing mechanism. In addition, d13C is strongly coherent, with d18O at a period of 41 k.y (obliquity), suggesting a connection between surface water CO2 chemistry in the Sulu Sea and high- latitude climatic change. The d18O and d13C time-series both contain increased spectral variance at a period of 30 k.y. Although the source of 30-k.y. variability is unknown, other studies have documented late Pleistocene Pacific Oceanographic variability with a period of 30 k.y. Major- and trace-metal analyses were performed on a second, less-detailed sample series to independently assess paleoproductivity changes and bottom-water conditions through time. Glacial periods are generally times of increased calcium carbonate and copper accumulation. The positive association between these independent indicators of paleoproductivity suggests an increase in productivity in the basin during most glacial episodes. Changing bottom-water redox conditions were also assessed using the geochemical data. Low concentrations of molybdenum throughout the record demonstrate that bottom waters at this site were never anoxic during the last 750 k.y. The bioturbated character of the sediments agrees with this interpretation.

Size variations of Discoaster multiradiatus across the Paleocene-Eocene thermal maximum

Size measurements of the calcareous nannofossil taxon Discoaster multiradiatus were carried out across the Paleocene-Eocene Thermal Maximum (PETM) in Ocean Drilling Program Holes 690B (Maud Rise, Weddell Sea) and 1209B (Shatsky Rise, Pacific Ocean). Morphometric investigations show that D. multiradiatus specimens are generally larger at ODP Site 1209 than at ODP Site 690. A limited increase in size of D. multiradiatus is recorded at ODP Site 1209, whereas significant enlargements characterize ODP Site 690. Preservation is comparable at both sites: nannofossils are moderately preserved with some evidence of etching/overgrowth in the PETM interval. Yet, D. multiradiatus variations do not correlate with preservation state and morphometric data most likely represent primary signals rather than diagenetic artifacts. There is a direct relationship between D. multiradiatus size and paleotemperatures: largest specimens are coeval with global warming associated with the PETM, inferred to result from excess atmospheric CO2 due to (partial) oxidation of massive quantities of methane. Size increases and largest specimens of D. multiradiatus occur at different stratigraphic levels within PETM at ODP Sites 690 and 1209. A marked shift in diameter size was observed at the onset and peak of the Carbon Isotopic Excursion (CIE) at ODP Site 690, but only at the end of CIE and initial recovery interval at ODP Site 1209. This diachroneity is puzzling, but indeed correlates well with reconstructed changes in surface and thermocline water masses temperature and salinity in the PETM interval at low and high latitudes. The presumed high concentrations of carbon dioxide seem to have not influenced the morphometry of D. multiradiatus. The major size increase of D. multiradiatus in the CIE of ODP Site 690 could represent the migration of larger-sized allochtonus specimens that moved from peri-equatorial/subtropical areas to higher latitudes during the warmest interval of the PETM, although no direct evidence of distinct populations/subpopulations has been obtained from the frequency diagrams. As a result, we infer that D. multiradiatus is a proxy of water masses stratification and might be used for deriving temperature-salinity-nutrient conditions in the mixed layer and thermocline and their dynamics.

Calcareous microfossil isotopes and Miocene datum events of ODP Holes 189-1170A and 189-1172A

Downcore oxygen and carbon stable isotope records of planktonic and benthic foraminifers and fine-fraction carbonate from the southern high latitudes provide critical paleohydrographic constraints on the evolution of the Southern Ocean climate. In particular, the potential effects of an intensified Antarctic Circumpolar Current on the thermal isolation and cooling of the southern high latitudes, production of cold deep waters, and, ultimately, accumulation of continental ice on Antarctica in the middle Miocene are matters of interest. Using sediment materials from Ocean Drilling Program Leg 189 Sites 1170 and 1172 off Tasmania, Ennyu and Arthur (2004, doi:10.1029/151GM13) established the surface- and deepwater stable isotope records in the Southern Ocean across the middle Miocene event of the east Antarctic ice sheet expansion and discussed the paleoclimate proxy records in terms of the thermal evolution of the southern high latitudes and its effect on deepwater circulation. This report provides data tables and other supporting information relevant to discussions presented in Ennyu and Arthur (2004, doi:10.1029/151GM13). Items included in this report are (1) the oxygen and carbon stable isotope data measured on the Miocene bulk fine-fraction (i.e., <63 µm, primarily polyspecific nannofossil assemblage) carbonate and planktonic and benthic foraminifers from Holes 1170A and 1172A and (2) the Miocene depth-age models for the two sites.

Stable oxygen and carbon isotope record of benthic foraminifera in Pliocene sediments of the Californian margin

New benthic foraminiferal stable isotopic records of northeast Pacific intermediate water (ODP Site 1014, 1177 m) and mid-depth water (ODP Site 1018, 2476 m) were compared to isotopic records of deep water in the tropical Pacific (ODP Site 849, 3851 m) for the reconstruction of vertical profiles of nutrient and physical properties from the Early Pliocene to the Early Pleistocene (approx. 5-1.4 Ma). Our data indicate that, for the entire interval, there was enhanced north Pacific intermediate water ventilation relative to today, and a similar to modern circulation pattern with northward flowing Pacific Bottom Water (PBW) beneath its southward flowing return flow. However, the core of maximally aged return flow resided as deep as ~2500 m (as compared to ~1500 m today), probably due to the strengthened intermediate water flow. Less apparent aging of deep water along its path before 2.7 Ma indicates that thermohaline overturning may have been more rapid in the warm period of the Early Pliocene. In addition, prior to 2.7 Ma, foraminiferal oxygen isotopic values at mid-depth sites are higher than at deep sites (a reversed vertical gradient relative to today) in both the Atlantic and Pacific Oceans. We suggest that NADW was warmer and more saline than today and that it influenced mid-depth waters throughout the Atlantic and Pacific Oceans. Enhanced Pliocene formation of warmer/saltier intermediate water in the north Pacific, and deep water in the north Atlantic, may have been a result of higher than modern high/mid-latitude sea surface temperatures, evaporation, and salinity.

Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

Geochemistry of pore fluids and bulk solids of ODP Site 195-1200, South Chamorro Seamount

At the South Chamorro Seamount in the Mariana subduction zone, geochemical data of pore fluids recovered from Ocean Drilling Program Leg 195 Site 1200 indicate that these fluids evolved from dehydration of the underthrusting Pacific plate and upwelling of fluids to the surface through serpentinite mud volcanoes as cold springs at their summits. Physical conditions of the fluid source at 27 km were inferred to be at 100°-250°C and 0.8 GPa. The upwelling of fluid is more active near the spring in Holes 1200E and 1200A and becomes less so with increasing distance toward Hole 1200D. These pore fluids are depleted in Cl and Br, enriched in F (except in Hole 1200D) and B (up to 3500 µM), have low 11B (16-21), and have lower than seawater Br/Cl ratios. The mixing ratios between seawater and pore fluids is calculated to be ~2:1 at shallow depth. The F, Cl, and Br concentrations, together with B concentrations and B isotope ratios in the serpentinized igneous rocks and serpentine muds that include ultramafic clasts from Holes 1200A, 1200B, 1200D, 1200E, and 1200F, support the conclusion that the fluids involved in serpentinization originated from great depths; the dehydration of sediments and altered basalt at the top of the subducting Pacific plate released Cl, H2O, and B with enriched 10B. Calculation from B concentrations and upwelling rates indicate that B is efficiently recycled through this nonaccretionary subduction zone, as through others, and may contribute the critical missing B of the oceanic cycle.

Whole-rock oxygen and carbon isorope record across the Cretaceous/Tertiary boundary in ODP Hole 130-807C

Whole-rock d18O analyses of the Paleogene and Upper Cretaceous succession at Ocean Drilling Program Hole 807C suggest the presence of hiatuses between 876.95 and 894.47 mbsf and between 1138.82 and 1140.94 mbsf. The d13C data show a pronounced positive excursion between 1130 and 1180 mbsf that corresponds to the positive d13C values characteristic of the Paleocene. Despite the stratigraphic breaks in the section, the d18O data show a systematic increase between 1360 mbsf and the hiatus between 876.95 and 894.47 mbsf, which is consistent with previous suggestions of long-term climatic cooling through the Paleogene. The Cretaceous/Tertiary transition is apparently complete in this section and is of remarkable thickness. The expanded nature of this portion of the succession is probably the result of secondary depositional processes. High-resolution sampling across this boundary may reveal detailed structure of the d13C decline associated with the extinctions that mark the termination of the Cretaceous.

Flow rates, hydraulic conductivities and permeabilities of sediments from ODP Holes 190-1173A and 190-1174B

Understanding the role of fluids in active accretionary prisms requires quantitative knowledge of parameters such as permeability. We report here the results of permeability tests on four samples from Ocean Drilling Program Leg 190 at the Nankai Trough accretionary prism-two from Site 1173 and two from Site 1174. Volcanic ash is present in one of the samples; otherwise, the material is hemipelagic mud. A constant-rate-of-flow technique was used at various effective pressures and rates of flow. The permeability of the four samples ranges between 10**-15 and 10**-18 m**2, with the ash-bearing sample showing the highest values.