(Table T1) Nd and Sr isotopic compositions, and Nd and Sm concentrations of glasses from ODP Leg 187 sites

The principal objective of Leg 187 was to locate the Indian/Pacific mantle boundary by sampling and analyzing 8- to 28-Ma seafloor basalts to the north of the Australian Antarctic Discordance (AAD). In this paper we present Sr and Nd isotopic data from basaltic glasses recovered from the 13 sites drilled during Leg 187. Our data show that the boundary region is characterized by a gradual east-west increase in 87Sr/86Sr, with a corresponding decrease in 143Nd/144Nd across a 150-km-wide zone located east and west of the 127°E Fracture Zone. The Sr-Nd isotopic composition of glasses therefore confirms the general conclusions derived by the Leg 187 shipboard scientific party in that the mantle boundary follows a west-pointing, V-shaped depth anomaly that stretches across the ocean floor from the Australian to the Antarctic continental margins. We document that two systematic trends of covariation between 87Sr/86Sr and 143Nd/144Nd can be distinguished, suggesting that the basalts sampled during Leg 187 formed through the interaction of three contrasting source components: (1) a component that lies within the broad spectrum of Indian-type mantle compositions, (2) a boundary component, and (3) a Pacific-type mantle component. The variations in elemental and isotopic compositions indicate that the boundary component represents a distinct mantle region that is associated with the boundary between the Pacific and the Indian mid-ocean-ridge basalt (MORB) sources rather than a dispersed mantle heterogeneity that was preferentially extracted in the boundary region. However, the origin of the boundary component remains an open question. The three components are not randomly intermixed. The Indian and the Pacific mantle sources both interacted with the boundary component, but they seem not to have interacted directly with each other. Large local variability in isotopic compositions of lavas from the mantle boundary region demonstrates that magma extraction processes were unable to homogenize the isotopic contrasts present in the mantle source in this region. Systematic variations in rare earth element (REE) concentrations across the depth anomaly cannot be explained solely by variations in source composition. The observed variations may be explained by an eastward increase and westward decrease in the degree of melting toward the mantle boundary region, compatible with a cooling of the Pacific mantle and a heating of the Indian mantle toward the mantle boundary.

Carbon and oxygen isotopic composition of benthic foraminifers from ODP Site 167-1014 and Hole 167-1020C

Benthic foraminiferal stable isotope data are presented for Sites 1014 (Tanner Basin, 1176 m) and 1020 (Gorda Ridge, 3040 m) to constrain past changes in Pacific deep- and intermediate-water nutrient chemistry associated with the onset of large-amplitude 100-k.y. climate cycles after ~900 ka. The Site 1014 data were based on analyses of separate species of Cibicidoides, whereas only Cibicidoides wuellerstorfi was used to generate the Site 1020 record. The present data span 380-920 and 620-950 ka at Sites 1014 and 1020, respectively.

TEX86 values and temperature estimation for sediment trap samples

The newly introduced temperature proxy, the tetraether index of archaeal lipids with 86 carbon atoms (TEX86), is based on the number of cyclopentane moieties in the glycerol dialkyl glycerol tetraether (GDGT) lipids of marine Crenarchaeota. The composition of sedimentary GDGTs used for TEX86 paleothermometry is thought to reflect sea surface temperature (SST). However, marine Crenarchaeota occur ubiquitously in the world oceans over the entire depth range and not just in surface waters. We analyzed the GDGT distribution in settling particulate organic matter collected in sediment traps from the northeastern Pacific Ocean and the Arabian Sea to investigate the seasonal and spatial distribution of the fluxes of crenarchaeotal GDGTs and the origin of the TEX86 signal transported to the sediment. In both settings the TEX86 measured at all trap deployment depths reflects SST. In the Arabian Sea, analysis of an annual time series showed that the SST estimate based on TEX86 in the shallowest trap at 500 m followed the in situ SST with a 1 to 3 week time delay, likely caused by the relatively low settling speed of sinking particles. This revealed that the GDGT signal that reaches deeper water is derived from the upper water column rather than in situ production of GDGTs. The GDGT temperature signal in deeper traps at 1500 m and 3000 m did not show a seasonal cyclicity observed in the 500 m trap but rather reflected the annual mean SST. This is probably due to a homogenization of the TEX86 SST signal carried by particles as they ultimately reach the interior of the ocean. Our data confirm the use of TEX86 as a temperature proxy of surface ocean waters.

Composition and crystal parameters of carbonate-apatites from animal teeth and bones and from phosphate rocks of the ocean bottom

Samples of recent to Miocene fish and marine mammal bones from the bottom of the Atlantic and Pacific Oceans and Miocene Maikop deposits (Transcaspian region) are studied by X-ray diffraction technique combined with chemical and energy-dispersive analyses. Changes of lattice parameters and chemical composition of bioapatite during fossilization and diagenesis suggest that development of skeletal apatite proceeds from dahllite-type hydroxyapatite to francolite-type carbonate-fluorapatite. It is assumed that jump-type transition from dahllite to francolite during initial fossilization reflects replacement of biogeochemical reactions in living organisms, which are subject to nonlinear laws of nonequilibrium thermodynamics, by physicochemical processes according to the linear equilibrium thermodynamics.

(Table T1) Mineralogy of ODP Leg 199 and DSDP Hole 16-162 sediments - comparison of methods

During Ocean Drilling Program Leg 199 in the equatorial Pacific, visible and near-infrared spectroscopy (VNIS) was used to measure the reflectance spectra (350-2500 nm) of 1343 sediment samples. Reflectance spectra were also measured for a suite of 60 samples of known mineralogy, thereby providing a local ground-truth calibration of spectral features to percentages of calcite, opal, smectite, and illite. The associated algorithm was used to calculate mineral percentages from the 1343 spectra. Using multiple regression and VNIS mineralogy, multisensor track physical properties and light spectroscopy data were then converted into continuous high-resolution mineralogy logs.

Age models, sedimentology and geochemistry from sediment cores in Drake Passage throughflow

The Drake Passage (DP) is the major geographic constriction for the Antarctic Circumpolar Current (ACC) and exerts a strong control on the exchange of physical, chemical, and biological properties between the Atlantic, Pacific, and Indian Ocean basins. Resolving changes in the flow of circumpolar water masses through this gateway is, therefore, crucial for advancing our understanding of the Southern Ocean's role in global ocean and climate variability. Here, we reconstruct changes in DP throughflow dynamics over the past 65,000 y based on grain size and geochemical properties of sediment records from the southernmost continental margin of South America. Combined with published sediment records from the Scotia Sea, we argue for a considerable total reduction of DP transport and reveal an up to ~40% decrease in flow speed along the northernmost ACC pathway entering the DP during glacial times. Superimposed on this long-term decrease are high-amplitude, millennial-scale variations, which parallel Southern Ocean and Antarctic temperature patterns. The glacial intervals of strong weakening of the ACC entering the DP imply an enhanced export of northern ACC surface and intermediate waters into the South Pacific Gyre and reduced Pacific-Atlantic exchange through the DP ("cold water route"). We conclude that changes in DP throughflow play a critical role for the global meridional overturning circulation and interbasin exchange in the Southern Ocean, most likely regulated by variations in the westerly wind field and changes in Antarctic sea ice extent.

(Table 2) Geochemistry of K-feldspars and associated plagioclase phenocrysts and rims at DSDP Legs 69, 52, 51 and 19

Basalts from some holes of the Deep Sea Drilling Project contain secondary K-feldspar which forms pseudomorphs after calcic (>76% An) Plagioclase cores, whereas Plagioclase of rims and microlites (68-74% An) remains unaltered. In basalts of Hole 504B two such grains with relics of Plagioclase in the central parts of phenocysts were recovered. The composition of the Plagioclase rims and of non-replaced phenocrysts is An79-81; the composition of relics is An83. The An and Ab contents of the K-feldspar is higher than in K-feldspar from altered basalt in Hole 418A in the Atlantic Ocean near the Bermuda Rise. Replacement of plagioclases by K-feldspar evidently is caused by oxygen-rich nearbottom sea water penetrating into basalts. The temperature interval of K-feldspathization is probably in the range 30 to 80°C, more-calcic Plagioclase being replaced by K-feldspar at higher temperatures.

Dissolved Si isotope composition measured in water samples during METEOR cruises M77/3 and M77/4

Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (d30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50'W and 82°00'W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions d30Si(OH)4 (+2.2 per mil to +4.4 per mil) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 µmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 µmol/kg are characterized by a large range in d30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the d30Si(OH)4 signature in the subsurface water column. Deep water masses (>2000 m) in the study area show a mean d30Si(OH)4 of +1.2±0.2 per mil, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher d30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between d30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of d30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a consequence of the mixing of several end member water masses with distinct Si isotope signatures including Lower Circumpolar Deep Water (LCDW) and North Pacific Deep Water (NPDW).

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Adaptive variability to low-pH river discharges in Acartia tonsa and stress responses to high PCO2 conditions

Environmental transitions leading to spatial physical-chemical gradients are of ecological and evolutionary interest because they are able to induce variations in phenotypic plasticity. Thus, the adaptive variability to low-pH river discharges may drive divergent stress responses [ingestion rates (IR) and expression of stress-related genes such as Heat shock protein 70 (Hsp70) and Ferritin] in the neritic copepod Acartia tonsa facing changes in the marine chemistry associated to ocean acidification (OA). These responses were tested in copepod populations inhabiting two environments with contrasting carbonate system parameters (an estuarine versus coastal area) in the Southern Pacific Ocean, and assessing an in situ and 96-h experimental incubation under conditions of high pressure of CO2 (PCO2 1200 ppm). Adaptive variability was a determining factor in driving variability of copepods' responses. Thus, the food-rich but colder and corrosive estuary induced a traits trade-off expressed as depressed IR under in situ conditions. However, this experience allowed these copepods to tolerate further exposure to high PCO2 levels better, as their IRs were on average 43% higher than those of the coastal individuals. Indeed, expression of both the Hsp70 and Ferritin genes in coastal copepods was significantly higher after acclimation to high PCO2 conditions. Along with other recent evidence, our findings confirm that adaptation to local fluctuations in seawater pH seems to play a significant role in the response of planktonic populations to OA-associated conditions. Facing the environmental threat represented by the inter-play between multiple drivers of climate change, this biological feature should be examined in detail as a potential tool for risk mitigation policies in coastal management arrangements.

Oxygen-isotope composition, temperature and depth of formation of chert at DSDP Leg 62 Holes

We measured oxygen-isotope compositions of 16 siliceous rocks from Deep Sea Drilling Project Sites 463, 464, 465, and 466 (Leg 62). Samples are from deposits that range in age from about 40 to 103 m.y. and that occur at sub-bottom depths of 9 to 461 meters. Mean d18O values range from 28.4 to 36.8 per mil and 36.0 ± 0.3 per mil for quartz-rich and opal-CTrich rocks, respectively. d18O values in chert decrease with increasing sub-bottom depth; the slope of the d18O/depth curve is less steep for Site 464 than for the other sites which indicates that chert at Site 464 formed at higher temperatures than chert at Sites 463, 465, and 466. Temperatures of formation of cherts were 7 to 42°C, using the silica-water fractionation factor of Knauth and Epstein (1976), or 19 to 56°C, using the equation of Clayton et al. (1972). Temperatures in the sediment where the cherts now occur are lower than their isotopically determined temperatures of formation, which means that the cherts record an earlier history when temperatures in the sediment section were greater. Estimated sediment temperatures when the cherts formed are comparable to, but generally slightly lower than, those calculated from Knauth and Epstein's equation. The isotopic composition of cherts is more closely related to environment of formation (diagenetic environment) or paleogeothermal gradients, than to paleoclimates (bottom-water temperatures). Opal-CT-rich rocks may better record paleo-bottom-water temperature. In Leg 62 cherts, better crystallinity of quartz corresponds to lower d18O values; this implies progressively higher temperatures of equilibration between quartz and water during maturation of quartz. The interrelationship of d18O and crystallinity is noted also in continental-margin deposits such as the Monterey Formation - but for higher temperatures. The apparent temperature difference between open-ocean and continental-margin deposits can be explained by the dominant control of temperature on silica transformation in the rapidly deposited continental-margin deposits, whereas time, as well as temperature, has a strong influence on the transformations in open-ocean deposits. Comparisons between the chemistry and d18O values of cherts reveal two apparent trends: both boron and SiO2 increase as d18O increases. However, the correspondence between SiO2 and d18O is only apparent, because the two cherts lowest in SiO2 are also the most deeply buried, so the trend actually reflects depth of burial. The correspondence between boron and d18O supports the conclusion that boron is incorporated in the quartz crystal structure during precipitation