Sr/Ca, U/Ca, and stable isotope data and bimonthly records of Ogasawara coral core OGA-02-1

Instrumental climate observations provide robust records of global land and ocean temperatures during the twentieth century. Unlike for temperature, continuous salinity observations in the surface ocean are scarce prior to 1970, and the magnitude of salinity changes during the twentieth century is largely unknown. Surface ocean salinity is a major component in climate dynamics, as it influences ocean circulation and water mass formation. Here we present an annually resolved reconstruction of salinity variations in the surface waters of the western subtropical North Pacific Ocean since 1873, based on bimonthly records of d18O, Sr/Ca, and U/Ca in a coral from the Ogasawara Islands. The reconstruction indicates that an abrupt regime shift toward fresher surface ocean conditions occurred between 1905 and 1910. Observational atmospheric data suggest that the abrupt freshening was associated with a weakening of the winds that drive the Kuroshio Current system and the associated subtropical gyre circulation. We note that the abrupt early-twentieth-century freshening in the western subtropical North Pacific precedes abrupt climate change in the northern North Atlantic by a few years. The potential for abrupt regime shifts in surface ocean salinity should be considered in climate predictions for the coming decades.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

(Supplement Table S2) Results of 230Th/U-dating

We compared the suitability of two skeletal materials of the Atlantic brain coral Diploria strigosa for 230Th/U-dating: the commonly used bulk material comprising all skeletal elements and the denser theca wall material. Eight fossil corals of presumably Last Interglacial age from Bonaire, southern Caribbean Sea, were investigated, and several sub-samples were dated from each coral. For four corals, both the ages and the activity ratios of the bulk material and theca wall agree within uncertainty. Three corals show significantly older ages for their bulk material than for their theca wall material as well as substantially elevated 232Th content and (230Th/238U) ratios. The bulk material samples of another coral show younger ages and lower (230Th/238U) ratios than the corresponding theca wall samples. This coral also contains a considerable amount of 232Th. The application of the available open-system models developed to account for post-depositional diagenetic effects in corals shows that none of the models can successfully be applied to the Bonaire corals. The most likely explanation for this observation is that the assumptions of the models are not fulfilled by our data set. Comparison of the theca wall and bulk material data enables us to obtain information about the open-system processes that affected the corals. The corals showing apparently older ages for their bulk material were probably affected by contamination with a secondary (detrital) phase. The most likely source of the detrital material is carbonate sand. The higher (230Th/232Th) ratio of this material implies that detrital contamination would have a much stronger impact on the ages than a contaminant with a bulk Earth (230Th/232Th) ratio and that the threshold for the commonly applied 232Th reliability criterion would be much lower than the generally used value of 1 ng g^-1. The coral showing apparently younger ages for its bulk material was probably influenced by more than one diagenetic process. A potential scenario is a combination of detrital contamination and U addition by secondary pore infillings. Our results show that the dense theca wall material of D. strigosa is generally less affected by post-depositional open-system behaviour and better suited for 230Th/U-dating than the bulk material. This is also obvious from the fact that all ages of theca wall material reflect a Last Interglacial origin (~125 ka), whereas the bulk material samples are either substantially older or younger. However, for some corals, the 230Th/U-ages and activity ratios of the bulk material and the theca wall samples are similar. This shows that strictly reliable 230Th/U-ages can also be obtained from bulk material samples of exceptionally well-preserved corals. However, the bulk material samples more frequently show elevated activity ratios and ages than the corresponding theca wall samples. Our findings should be generally applicable to brain corals (Mussidae) that are found in tropical oceans worldwide and may enable reliable 230Th/U-dating of fossil corals with similar skeletal architecture, even if their bulk skeleton is altered by diagenesis. The 230Th/U-ages we consider reliable (120-130 ka), along with a recently published age of 118 ka, provide the first comprehensive dating of the elevated lower reef terrace at Bonaire (118-130 ka), which is in agreement in timing and duration with other Last Interglacial records.

Assamblages and cluster analysis from DSDP Hole 22-214 of the eastern Indian Ocean

Multivariate analyses of latest Pliocene through Holocene benthic foraminifera from 61 samples from Deep-Sea Drilling Project (DSDP) Site 214, eastem Indian Ocean were carried out. The 46 highest ranked species were used in R-mode factor analysis which has enabled to the identification of three environmentally significant assemblages at Site 214. Assemblage 1 is characterized by Uvigerina hispido-costata, Osangularia culter , Gavelinopsis lobatulus, Cibicides wuellerstorfi and Karreriella baccata as principal species. This assemblage is inferred to reflect high-energy, well-oxygenated and probably low-organic carbon deep-sea environment at Site 214. Assemblage 2 is defined principally by Globocassidulina pacifica and U. proboscidea and is considered to indicate an organic carbon-rich environment which resulted from high surface productivity irrespective of dissolved oxygen content. Assemblage 3 is marked by Oridorsalis umbonatus, Textularia lythostrota, Hoeglundina elegans, Pyrgo murrhina, and Pullenia quinqueloba as principal species. This assemblage is inferred to indicate a low-organic carbon environment with high pore water oxygen concentration leading to better preservation of deep-sea sediments.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

Os and Re concentrations and Os isotope ratios for DSDP and ODP metalliferous sediments from the Pacific Ocean (Table 1)

We report new 187Os/186Os data and Re and Os concentrations in metalliferous sediments from the Pacific to construct a composite Os isotope seawater evolution curve over the past 80 m.y. Analyses of four samples of upper Cretaceous age yield 187Os/186Os values of between 3 and 6.5 and 187Re/186Os values below 55. Mass balance calculations indicate that the pronounced minimum of about 2 in the Os isotope ratio of seawater at the K-T boundary probably reflects the enormous input of cosmogenic material into the oceans by the K-T impactor(s). Following a rapid recovery to 187Os/186Os of 3.5 at 63 Ma, data for the early and middle part of the Cenozoic show an increase in 187Os/186Os to about 6 at 15 Ma. Variations in the isotopic composition of leachable Os from slowly accumulating metalliferous sediments show large fluctuations over short time spans. In contrast, analyses of rapidly accumulating metalliferous carbonates do not exhibit the large oscillations observed in the pelagic clay leach data. These results together with sediment leaching experiments indicate that dissolution of non-hydrogenous Os can occur during the hydrogen peroxide leach and demonstrate that Os data from pelagic clay leachates do not always reflect the Os isotopic composition of seawater. New data for the late Cenozoic further substantiate the rapid increase in the 187Os/186Os of seawater during the past 15 Ma. We interpret the correlation between the marine Sr and Os isotope records during this time period as evidence that weathering within the drainage basin of the Ganges-Brahmaputra river system is responsible for driving seawater Sr and Os toward more radiogenic isotopic compositions. The positive correlation between 87Sr/86Sr and U concentration, the covariation of U and Re concentrations, and the high dissolved Re, U and Sr concentrations found in the Ganges-Brahmaputra river waters supports this interpretation. Accelerating uplift of many orogens worldwide over the past 15 Ma, especially during the last 5 Ma, could have contributed to the rapid increase in 187Os/186Os from 6 to 8.5 over the past 15 Ma. Prior to 15 Ma the marine Sr and Os record are not tightly coupled. The heterogeneous distribution of different lithologies within eroding terrains may play an important role in decoupling the supplies of radiogenic Os and Sr to the oceans and account for the periods of decoupling of the marine Sr and Os isotope records.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and U</=0.005 ppm in the primitive rocks and up to 2 ppm Pb and 0.2 ppm U in the evolved. The range of isotopic compositions of the unleached rocks is: 87Sr/86Sr=0.70280-0.70299, average 0.70287+/-0.00005 (1 S.D., N=30 samples) (except one felsic vein with 87Sr/86Sr=0.7045), 143Nd/144Nd=0.51304-0.51314, average 0.51310+/-0.00002 (1 S.D., N=28), 206Pb/204Pb=17.43-18.55, 207Pb/204Pb=15.40-15.61 and 208Pb/204Pb=37.19-38.28. The range of Sr and the almost constant Nd isotopic composition resemble that found in the upper 500 m of Hole 735B, while Pb ranges to more radiogenic compositions. In general, there is a decrease in isotopic variation of Sr and Pb as well as ? (238U/204Pb), U and Pb with depth, with a trend towards relatively unradiogenic compositions. This correlates with a decrease in alteration and frequency of evolved rock-types in the core. Leached samples generally have less radiogenic Pb with values trending towards 206Pb/204Pb=17.35, 207Pb/204Pb=15.35 and 208Pb/204Pb=37.0, while their 87Sr/86Sr ratios deviate less systematically from unleached rocks and reach both higher, 0.70307, and lower values, 0.70276. Separated clinopyroxene has elevated 87Sr/86Sr up to 0.7035, while plagioclase generally has close to whole rock Sr. Leaching reduced 87Sr/86Sr in clinopyroxene and in two (out of nine) cases leached separates and whole rock display isotopic equilibrium. Relatively minor hydrothermal seawater alteration is thought to have increased 87Sr/86Sr in the rocks, while a secondary high temperature percolation of a mantle-derived agent is thought to be the cause for the trend towards radiogenic Pb. This material had intermediate 87Sr/86Sr and may have originated from non-MORB off axis mantle. The main primary igneous isotopic variation of the gabbros is suggested to have been derived from the MORB-mantle and is defined mainly by leached samples from both ODP Leg 176 and Leg 118 and can be explained by two-component mixing of an end-member with composition like Central Indian Ridge basalts and an end-member with composition unlike any MORB. The latter is characterized by very unradiogenic Pb, in particular 207Pb/204Pb, and may have an origin with affinity to old depleted mantle (DM). The isotopic composition of the magmas parental to the FeTi-oxide rich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

Chemical and isotopic compositions of sediments and some minerals from the Derugin Basin, Sea of Okhotsk

The paper reports specific mineralogical and geochemical characteristics of deposits from local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for presence of hydrogen sulfide in bottom waters. Deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U), but have higher Mn contents.

Tab. 1: Mean water loss by mosses and lichens at 40%

The loss of water in a desiccating atmosphere (c.40% r.h. at 10°C) and uptake of water from a saturated atmosphere (100% r.h. at 10°C) was recorded at intervals over periods of many hours or days in the dominant mosses and macroiichens occurring near the Australian Casey Station. Wilkes Land, continental Antarctica. While major differences exist in the water holding capacity and rates of water loss between mosses and lichens, the minimum levels attained after prolonged exposure to desiccating conditions are remarkably similar. By contrast, the volume of water absorbed from a saturated atmosphere is very similar in both groups of cryptogams. Morphological and anatomical characters are responsible for many of the differences, both between species, and within species exhibiting different growth features. Thus, significantly larger amounts of water are held by colonies of Bryum algens with a dense tomentum of rhizoids than those with sparse rhizoids; similarly, the rhizinate Umbilicaria aprina held a greater volume of water than the erhizinate U. decussata. The filamentous mat form of Alectoria mimiscula permits a much higher water content to be attained than in the coarser fruticose forms of Usnea sphacelata and U. antarctica. The dense shoot arrangement in Schistidium antarcticum accounts for the high water holding capacity in the hydric turf form whereas the less densely packed shoots and thicker cell walls of the xeric cushion form maintain a lower water content. The rate of water loss (as percentage dry weight) was much faster in the turf form of Schistidium and tomenlose form of Bryum, although this trend was reversed when expressed as percentage of the initial water content. Minimal water contents arc achieved by the lichens in desiccating conditions within 6-12 hours, whereas the mosses take several times longer. The water relations characteristics of these cryptogams are considered in the light of their distribution in the field and of their metabolic activity under prevailing Antarctic conditions.

(Table 1) Trace element and age analysis from the Porites coral from IODP Exp 310

Climate responses and changes in marine environments during the last deglaciation have been controversial and few paleoceanographic data are available from the tropical South Pacific, though this region is crucial in the investigations of ocean-atmosphere interactions. Integrated Ocean Drilling Program Expedition 310 was conducted to establish the time course of the postglacial sea-level rise at Tahiti in the South Pacific. A principal objective of this expedition was to examine the variation of marine environments during the last deglaciation. As fossil Porites coral is ideal for assessing past marine environments, we selected only Porites specimens from the many coral specimens retrieved, examined them by XRD, and dated them by the 14C method. In all, we obtained 17 pristine Porites specimens composed of only aragonite with ages from 15 to 9 ka. Then, we measured Mg/Ca, Ba/Ca, and U/Ca ratios and Cd contents as proxies for upwelling and sea surface temperature. Higher Ba/Ca ratios and Cd content together with lower reconstructed SSTs using U/Ca ratios in the coral specimens between 12.6 and 9.8 cal ka compared to around 15 cal ka suggest that upwelling and/or entrainment of subsurface water into mixed layer was enhanced around Tahiti during this period. This finding is consistent with previous reports and supports the idea that the South Pacific was characterized by La Niña-like conditions at least from 12.6 to 9.8 cal ka.