Strontium isotopic composition of interstitial waters from DSDP sites 25-245 and 38-336

Measurements of 87Sr/86Sr ratios of interstitial waters from leg 25, site 245 and leg 38, site 336 of the Deep Sea Drilling Project show that the enrichment of Sr[2+] with depth is caused both by the alteration of volcanic material and by the introduction of strontium derived from calcium carbonate. 87Sr/86 Sr ratios range from 0.70913 to 0.70794 at site 245 and from 0.70916 to 0.70694 at site 336. The low ratios compared with contemporaneous seawater reflect the release of Sr from a volcanic source having, according to material-balance calculations, a 87Sr/86 Sr ratio of about 0.7034 at site 336. At this site the source appears to be volcanic ash and not basaltic basement which acts as a sink for Sr[2+] during in situ low-temperature weathering. The volcanic contribution to the strontium enrichment in the basal interstitial waters varies from <10% at site 245 to >50% at site 336. The remaining Sr[2+] is derived from Sr-rich biogenic carbonate during diagenetic recrystallization to form Sr-poor calcite.

Strontium chemistry of anhydrite from DSDP/ODP Hole 504B

A unique record of the chemical evolution of seawater during hydrothermal recharge into oceanic crust is preserved by anhydrite from the volcanic sequences and sheeted dike complex in ODP Hole 504B. Chemical and isotopic analyses 87Sr/86Sr, delta18O, delta34S of anhydrite constrain the changing composition of fluids due to reaction with basalt. There is a general trend of decreasing 87Sr/86Sr of anhydrite, corresponding to the minor incorporation of basaltic strontium with depth in the volcanic rocks. 87Sr/86Sr ratios decrease rapidly with depth in the dikes to values identical to host basalt (0.7029). Sr/Ca ratios (<0.1 mmol/mol) suggest that recharge fluids have very low Sr concentrations and fluids evolve by first precipitating Sr-bearing phases before extensive exchange of Sr with the host basalt. There is a background trend of decreasing sulfate delta18O with depth from +12-13? in the lower volcanics to +7? in the lower sheeted dikes recording an increase in recharge fluid temperature from c. 150° to c. 250°C, and confirming the presence of sulfate in hydrothermal fluids at elevated temperatures. From the amount of anhydrite recovered from Hole 504B and the amount of seawater sulfur that has been reduced to sulfide, a minimum seawater recharge flux can be calculated. This value is 4-25 times lower than estimates of high-temperature fluid fluxes based on either thermal constraints or global chemical budgets and suggests that there is significant deficit of seawater-derived sulfur in the oceanic crust. Only a minor proportion of the seawater that percolates into the crust near the axis is heated to high temperatures and exits as black smoker-type fluids. A significant proportion of the axial heat loss must be advected at 200-250°C by sulfate-bearing hydrothermal solutions that egress diffusely from the crust. These fluids penetrate into the dikes and exchange both heat and chemical tracers without the extensive clogging of porosity by anhydrite precipitation, which would halt hydrothermal circulation for any reasonable fluid flux. The heating of the major proportion of hydrothermal fluids to only moderate temperatures (c. 250°C) reconciles estimates of hydrothermal fluxes derived from thermal models and global geochemical budgets. The flux of hydrothermal sulfate would be of a magnitude similar to the riverine input, and oxygen-isotopic exchange at 200-250°C between dissolved sulfate and recharge fluids during hydrothermal circulation provides a mechanism to continuously buffer seawater sulfate oxygen to the light isotopic composition observed.

Age determination of the rhyolites of the Lord Howe Rise in the Southwest Pacific Ocean

Drilling at site 207 (DSDP Leg 21), located on the broad summit of the Lord Howe Rise, bottomed in rhyolitic rocks. Sanidine concentrates from four samples of the rhyolite were dated by the 40Ar/39Ar total fusion method and conventional K-Ar method, and yielded concordant ages of 93.7 +/- 1.1 my, equivalent to the early part of the Upper Cretaceous. At this time the Lord Howe Rise, which has continental-type structure, is thought to have been emergent and adjacent to the eastern margin of the Australian-antarctic continent. Subsequent to 94 my ago and prior to deposition of Maastrichtian (70-65 myBP) marine sediments on top of the rhyolitic basement of the Lord Howe Rise, rifting occurred and the formation of the Tasman Basin began by sea-floor spreading with rotation of the Rise away from the margin of Australia. Subsidence of the Rise continued until Early Eocene (about 50 myBP), probably marking the end of sea-floor spreading in the Tasman Basin. These large scale movements relate to the breakup of this part of Gondwanaland in the Upper Cretaceous.

Revised geomagnetic polarity timescale for the late Oligocene to early Miocene of ODP Site 177-1090

At Ocean Drilling Program (ODP) Site 1090 (subantarctic South Atlantic), benthic foraminiferal stable isotope data (from Cibicidoides and Oridorsalis) span the late Oligocene through early Miocene (~24-16 Ma) at a temporal resolution of ~5 ky. Over the same interval, a magnetic polarity stratigraphy can be unequivocally correlated to the geomagnetic polarity time scale (GPTS), thereby providing direct correlation of the isotope record to the GPTS. In an initial age model, we use the newly derived age of the Oligocene/Miocene (O/M) boundary of 23.0 Ma of Shackleton et al. (2000, doi:10.1130/0091-7613(2000)28<447:ACAFTO>2.0.CO;2), revised to the new astronomical calculation (La2003) of Laskar et al (2004, doi:10.1016/j.icarus.2004.04.005) to recalculate the spline ages of Cande and Kent (1995, doi:10.1029/94JB03098). We then tune the Site 1090 dekta18O record to obliquity using La2003. In this manner, we are able to refine the ages of polarity chrons C7n through C5Cn.1n. The new age model is consistent, within one obliquity cycle, with previously tuned ages for polarity chrons C7n through C6Bn from Shackleton et al. (2000) when rescaled to La2003. The results from Site 1090 provide independent evidence for the revised age of the Oligocene/Miocene boundary of 23.0 Ma. For early Miocene polarity chrons C6AAr through C5Cn, our obliquity-scale age model is the first to allow a direct calibration to the GPTS. The new ages are generally within one obliquity cycle of those obtained by rescaling the Cande and Kent (1995) interpolation using the new age of the O/M boundary (23.0 Ma) and the same middle Miocene control point (14.8 Ma) used by Cande and Kent (1995).

Geochemistry of volcanic glass from ODP holes 129-801C and 185-801C in the western Pacific

Major element chemistry of basalt from the southern East Pacific Rise (EPR) is different from that of the EPR at the time of the formation of the Pacific Plate at 170 Ma.Glass recovered from Jurassic age (170 Ma) Pacific ocean crust (Bartolini and Larson, 2001, doi:10.1130/0091-7613(2001)029<0735:PMATPS>2.0.CO;2) at Ocean Drilling Program Hole 801C records higher Fe8 (10.77 wt%) and marginally lower Na8 (2.21 wt%) compared to the modern EPR, suggesting deeper melting and a temperature of initial melting that was 60°C hotter than today.Trace element ratios such as La/Sm and Zr/Y, on the other hand, show remarkable similarities to the modern southern EPR, indicating that Site 801 was not generated on a hotspot-influenced ridge and that mantle composition has changed little in the Pacific over the past 170 Ma. Our results are consistent with the observation that mid-ocean ridge basalts (MORBs) older than 80 Ma were derived by higher temperature melting than are modern MORBs (Humler et al., 1999, doi:10.1016/S0012-821X(99)00218-6), which may have been a consequence of the Cretaceous superplume event in the Pacific.Site 801 predates the formation of Pacific oceanic plateaus and 801C basalt chemistry indicates that higher temperatures of mantle melting beneath Pacific ridges preceded the initiation of the superplume.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Paleomegnetic of basaltic sequenzes from DSDP Site 462 in the Nauru Basin

The voluminous volcanic eruptions in the Nauru Basin, Western Pacific, have long been regarded as important research targets for tectonic history of the Pacific Plate and for the widespread Cretaceous volcanic activity in the Western Pacific. The Nauru Basin volcanic rocks were recovered at Site 462 by Deep Sea Drilling Project (DSDP) Legs 61 and 89, where more than 600 m of lavas and sills were drilled, thereby making it the deepest penetration into crust of Cretaceous age in the Pacific Ocean. For paleomagnetism, this section represents a unique possibility for averaging out secular variation to obtain a reliable paleolatitude estimate. However, previous paleomagnetic studies have only been subjected to alternating field (AF) demagnetization on several core samples, thus, unable to provide comprehensive understanding on the paleolatitude of the basin. The work reported here aims to determine the Cretaceous paleomagnetic paleolatitude for the Pacific Plate and define the magnetostratigraphy for the basaltic sections drilled in the Nauru Basin. A total of 391 basaltic rock samples were carefully re-sampled from DSDP Sites 462 and 462A. Stepwise thermal and AF demagnetizations have isolated characteristic components in the majority of the samples. The most important findings from this study include: (1) Two normal and one reversed polarity intervals are identified in Site 462, and six normal and six reversed polarity intervals are found in Site 462A, although possible erroneous markings of the opposite azimuth for some reversed polarity cores during the DSDP coring cannot be completely ruled out. (2) Based on previous radiometric ages, the magnetostratigraphic correlations with the Geomagnetic Polarity Time Scale (GPTS) indicate that the lower-basaltic flow unit in Site 462A began to erupt at least before 130 Ma. No correlation is available for the upper-sill unit. (3) Paleosecular variation for the lower-flow unit has been sufficiently averaged out; whereas bias may exist for that of the upper-sill unit; (4) The calculated mean inclination of ~50° for the lower-flow unit yields a paleolatitude of 30.8°S for the Nauru Basin at the time of emplacement. This value is well to the north of suggested location in plate reconstruction models, suggesting that there has been a significant amount of apparent polar wander of the Nauru Basin and Pacific plate since 130 Ma. In addition, the paleolatitude for the Nauru Basin is ~7° further south and the basin's age is more than 10 my older than those of the Ontong Java Plateau (OJP), which suggest that the volcanic eruptions of the lower flows in the Nauru Basin are unlikely related to the emplacement of the Ontong Java Plateau.

B/Ca ratios of benthic foraminifera

We present modern B/Ca core-top calibrations for the epifaunal benthic foraminifer Nuttallides umbonifera and the infaunal Oridorsalis umbonatus to test whether B/Ca values in these species can be used for the reconstruction of paleo-D[[CO3]2-]. O. umbonatus originated in the Late Cretaceous and remains extant, whereas N. umbonifera originated in the Eocene and is the closest extant relative to Nuttallides truempyi, which ranges from the Late Cretaceous through the Eocene. We measured B/Ca in both species in 35 Holocene sediment samples from the Atlantic, Pacific and Southern Oceans. B/Ca values in epifaunal N. umbonifera (~ 85-175 µmol/mol) are consistently lower than values reported for epifaunal Cibicidoides (Cibicides) wuellerstorfi (130-250 µmol/mol), though the sensitivity of D[[CO3]2-] on B/Ca in N. umbonifera (1.23 ± 0.15) is similar to that in C. wuellerstorfi (1.14 ± 0.048). In addition, we show that B/Ca values of paired N. umbonifera and its extinct ancestor, N. truempyi, from Eocene cores are indistinguishable within error. In contrast, both the B/Ca (35-85 µmol/mol) and sensitivity to D[[CO3]2-] (0.29 ± 0.20) of core-top O. umbonatus are considerably lower (as in other infaunal species), and this offset extends into the Paleocene. Thus the B/Ca of N. umbonifera and its ancestor can be used to reconstruct bottom water D[[CO3]2?], whereas O. umbonatus B/Ca appears to be buffered by porewater [[CO3]2-] and suited for constraining long-term drift in seawater B/Ca.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Planktonic foraminifer assemblages and stable oxygen and carbon isotope record of sediment core MD07-3076Q

We report high-resolution planktonic foraminifer census counts and stable oxygen and carbon isotope measurements of the planktonic foraminifera G. bulloides and N. pachyderma s. from sediment core MD07-3076Q for the last deglaciation, the last glacial maximum and Marine Isotope Stage 3. These data provide insights into the marine cycling of carbon and frontal dynamics in the sub-Antarctic Atlantic during the last 68 ka.