Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Physical oceaongraphy and hydrochemistry measured on water bottle samples during METEOR cruise M84/3 in 2001

Here we report on data from an oceanographic cruise on the German research vessel Meteor covering large parts of the Mediterranean Sea during spring of 2011. The main objective of this cruise was to conduct measurements of physical, chemical and biological variables on a section across the Mediterranean Sea with the goal of producing a synoptic picture of the distribution of relevant physical and biogeochemical properties, in order to compare those to historic data sets. During the cruise, a comprehensive data set of relevant variables following the guide lines for repeat hydrography outlined by the GO-SHIP group (http://www.go-ship.org/) was collected. The measurements include salinity and temperature (CTD), an over-determined carbonate system, inorganic nutrients, oxygen, transient tracers (CFC-12, SF6), helium isotopes and tritium, and carbon isotopes. The cruise sampled all major basins of the Mediterranean Sea following roughly an east-to-west section from the coast of Lebanon through to the Strait of Gibraltar, and to the coast of Portugal. Also a south-to-north section from the Ionian Sea to the Adriatic Sea was carried out. Additionally, sampling in the Aegean, Adriatic and Tyrrhenian Seas were carried out. The sections roughly followed lines and positions that have been sampled previously during other programs, thus providing the opportunity for comparative investigations of the temporal development of various parameters.

Physical and chemical oceanography in the Arctic Ocean

Data from sections across the Eurasian Basin of the Arctic Ocean occupied by the German Research Vessel Polarstern in 1987 and by the Swedish icebreaker Oden in 1991 are used to derive information on the freshwater balance of the Arctic Ocean halocline and on the sources of the deep waters of the Nansen, Amundsen and Makarov basins. Salinity, d18O and mass balances allow separation of the river-runoff and the sea-ice meltwater fractions contained in the Arctic halocline. This provides the basis for tracking the river-runoff signal from the shelf seas across the central Arctic Ocean to Fram Strait. The halocline has to be divided into at least three lateral regimes: the southern Nansen Basin with net sea-ice melting, the northern Nansen Basin and Amundsen Basin with net sea-ice formation and increasing river-runoff fractions, and the Canadian Basin with minimum sea-ice meltwater and maximum river-runoff fractions and water of Pacific origin. In the Canadian Basin, silicate is used as a tracer to identify Pacific water entering through Bering Strait and an attempt is made to quantify its influence on the halocline waters of the Canadian Basin. For this purpose literature data from the CESAR and LOREX ice camps are used. Based on mass balances and depending on the value of precipitation over the area of the Arctic Ocean the average mean residence time of the river-runoff fraction contained in the Arctic Ocean halocline is determined to be about 14 or 11 years. Water column inventories of river-runoff and sea-ice meltwater are calculated for a section just north of Fram Strait and implications for the ice export rate through Fram Strait are discussed. Salinity, tritium, 3He and the d18O ratio of halocline waters sampled during the 1987 Polarstern cruise to the Nansen Basin are used to estimate the mean residence time of the river-runoff component in the halocline and on the shelves of the Arctic Ocean. These estimates are done by comparing ages of the halocline waters based on a combination of tracers yielding different time information: the tritium 'vintage' age which records the time that has passed since the river-runoff entered the shelf and the tritium/3He age which reflects the time since the shelf waters left the shelf. The difference between the ages determined by these two methods is about 3 to 6 years. Correction for the initial tritium/3He age of the shelf waters (about 0.5 to 1.5 years) yields a mean residence time of the river-runoff on the shelves of about 3.5 ± 2 years. Comparison of the 18O/16O ratios of shelf water, Atlantic water and the deep waters of the Arctic Ocean indicate that the sources of the deep and bottom waters of the Eurasian Basin are located in the Barents and Kara seas.

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.

Geochemistry of ODP Sites 121-758 and 121-757

Nd isotopes are useful tracers for paleoceanography due to the short Nd residence time in seawater and the large differences between the isotopic signatures of various geological reservoirs. Therefore, ?Nd variations reflect the geological history of individual oceanic basins. Using a differential dissolution technique, which extracts Nd isotopes of seawater trapped in MnO2 coatings and carbonates in marine sediment, we measured almost two hundred samples from ODP Sites 758 and 757 in the Northern Bay of Bengal covering the last 4 Ma. For the first time, we have shown a covariation between epsilon-Nd and d18O over at least the last 800 ka. We also show that from 4 Ma to 2.6 Ma, epsilon-Nd is almost constant and starts to fluctuate at 2.6 Ma when northern glaciations increased. From 2.6 Ma to 1 Ma the fluctuation period is close to 40 ka while from 1 Ma to present it is dominantly 100 ka. We attribute these findings to mixing between Himalayan river water (that ultimately originates as Indian summer monsoon rain) and normal Bay of Bengal seawater. Previous studies on seawater, using epsilon-Nd, d18O analyzed on planktonic foraminifera and sedimentary data, can be integrated into this model. A simple quantitative binary mixing model suggests that the summer monsoon rain was more intense during interglacial than glacial periods. During last glacial episode, the monsoon trajectory was deviated to the east. At a large scale, the Indian monsoon is fully controlled by the variations in Northern Hemisphere climate but with a complex response function to this forcing. Our study clearly establishes the large potential of Nd isotope data to evaluate the hydrological river regime during the Quaternary and its relationship with climate fluctuations, particularly when the sediment archive is sampled close to sediment sources.

Modeling the sensitivity of precipitation oxygen isotopes to the Last Glacial Maximum boundary conditions: A study using Community Atmosphere Model (CAM3.0)

To understand the validity of d18O proxy records as indicators of past temperature change, a series of experiments was conducted using an atmospheric general circulation model fitted with water isotope tracers (Community Atmosphere Model version 3.0, IsoCAM). A pre-industrial simulation was performed as the control experiment, as well as a simulation with all the boundary conditions set to Last Glacial Maximum (LGM) values. Results from the pre-industrial and LGM simulations were compared to experiments in which the influence of individual boundary conditions (greenhouse gases, ice sheet albedo and topography, sea surface temperature (SST), and orbital parameters) were changed each at a time to assess their individual impact. The experiments were designed in order to analyze the spatial variations of the oxygen isotopic composition of precipitation (d18Oprecip) in response to individual climate factors. The change in topography (due to the change in land ice cover) played a significant role in reducing the surface temperature and d18Oprecip over North America. Exposed shelf areas and the ice sheet albedo reduced the Northern Hemisphere surface temperature and d18Oprecip further. A global mean cooling of 4.1 °C was simulated with combined LGM boundary conditions compared to the control simulation, which was in agreement with previous experiments using the fully coupled Community Climate System Model (CCSM3). Large reductions in d18Oprecip over the LGM ice sheets were strongly linked to the temperature decrease over them. The SST and ice sheet topography changes were responsible for most of the changes in the climate and hence the d18Oprecip distribution among the simulations.

Analysis of the iron oxide assemblages in the ANDRILL AND-1B drill core, Ross Sea, Antarctica

The AND-1B drill core recovered a 13.57 million year Miocene through Pleistocene record from beneath the McMurdo Ice Shelf in Antarctica (77.9°S, 167.1°E). Varying sedimentary facies in the 1285 m core indicate glacial-interglacial cyclicity with the proximity of ice at the site ranging from grounding of ice in 917 m of water to ice free marine conditions. Broader interpretation of climatic conditions of the wider Ross Sea Embayment is deduced from provenance studies. Here we present an analysis of the iron oxide assemblages in the AND-1B core and interpret their variability with respect to wider paleoclimatic conditions. The core is naturally divided into an upper and lower succession by an expanded 170 m thick volcanic interval between 590 and 760 m. Above 590 m the Plio-Pleistocene glacial cycles are diatom rich and below 760 m late Miocene glacial cycles are terrigenous. Electron microscopy and rock magnetic parameters confirm the subdivision with biogenic silica diluting the terrigenous input (fine pseudo-single domain and stable single domain titanomagnetite from the McMurdo Volcanic Group with a variety of textures and compositions) above 590 m. Below 760 m, the Miocene section consists of coarse-grained ilmenite and multidomain magnetite derived from Transantarctic Mountain lithologies. This may reflect ice flow patterns and the absence of McMurdo Volcanic Group volcanic centers or indicate that volcanic centers had not yet grown to a significant size. The combined rock magnetic and electron microscopy signatures of magnetic minerals serve as provenance tracers in both ice proximal and distal sedimentary units, aiding in the study of ice sheet extent and dynamics, and the identification of ice rafted debris sources and dispersal patterns in the Ross Sea sector of Antarctica.

Geochemistry, sediment components, and paleoproductivity reconstruction for the Miocene to early Pliocene sediments

We reconstruct paleoproductivity at three sites in the Atlantic Ocean (Ocean Drilling Program Sites 982, 925, and 1088) to investigate the presence and extent of the late Miocene to early Pliocene 'biogenic bloom' from 9 to 3 Ma. Our approach involves construction of multiple records including benthic foraminiferal and CaCO3 accumulation rates, Uvigerina counts, dissolution proxies, and geochemical tracers for biogenic and detrital fluxes. This time interval also contains the so-called late Miocene carbon isotope shift, a well-known decrease in benthic foraminiferal d13C values. We find that the timing of paleoproductivity maxima differs among the three sites. At Site 982 (North Atlantic), benthic foraminifera and CaCO3 accumulation were both at a maximum at ~5 Ma, with smaller peaks at ~6 Ma. The paleoproductivity maximum was centered earlier (~6.6-6.0 Ma) in the tropical Atlantic (Site 925). In the South Atlantic (Site 1088), paleoproductivity increased even earlier, between 8.2 Ma and 6.2 Ma, and remained relatively high until ~5.4 Ma. We note that there is some overlap between the interval of maximum productivity between Sites 925 and 1088, as well as the minor productivity increase at Site 982. We conclude that the paleoproductivity results support hypotheses aiming to place the biogenic bloom into a global context of enhanced productivity. In addition, we find that at all three sites the d13C shift is accompanied by carbonate dissolution. This observation is consistent with published studies that have sought a relationship between the late Miocene carbon isotope shift and carbonate preservation.

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.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Geochemistry of lavas and dikes from the upper oceanic crust of Hess Deep Rift, eastern Pacific Ocean

Strontium isotopes are useful tracers of fluid-rock interaction in marine hydrothermal systems and provide a potential way to quantify the amount of seawater that passes through these systems. We have determined the whole-rock Sr-isotopic compositions of a section of upper oceanic crust that formed at the fast-spreading East Pacific Rise, now exposed at Hess Deep. This dataset provides the first detailed comparison for the much-studied Ocean Drilling Program (ODP) drill core from Site 504B. Whole-rock and mineral Sr concentrations indicate that Sr-exchange between hydrothermal fluids and the oceanic crust is complex, being dependent on the mineralogical reactions occurring; in particular, epidote formation takes up Sr from the fluid increasing the 87Sr/86Sr of the bulk-rock. Calculating the fluid-flux required to shift the Sr-isotopic composition of the Hess Deep sheeted-dike complex, using the approach of Bickle and Teagle (1992, doi:10.1016/0012-821X(92)90221-G) gives a fluid-flux similar to that determined for ODP Hole 504B. This suggests that the level of isotopic exchange observed in these two regions is probably typical for modern oceanic crust. Unfortunately, uncertainties in the modeling approach do not allow us to determine a fluid-flux that is directly comparable to fluxes calculated by other methods.

Detriral flux of sediment cores in the southeast Indian Ocean

Because of a close relationship between detrital flux variations and magnetic susceptibility (MS) flux (MS cm**3 of bulk sediment multiplied by the linear sedimentation rate) variations in the southeast Indian basin of the southern ocean, MS flux profiles have been used to examine the spatial and temporal detrital flux changes in this basin during the last climatic cycle. Results indicate a general increase in detrital material input during the coldest periods, suggesting a widespread phenomenon, at least on the basin scale. Mineralogical data, geochemical data, and 87Sr/86Sr isotopic ratios have been used to determine the origin and transport mechanisms responsible for increased detrital flux during glacial periods. Mineralogical and geochemical data show that these glacial 'highs' are due to increases in both Kerguelen-Crozet volcanic and Antarctic detrital inputs. The 87Sr/86Sr isotopic composition of the >45-µm fraction indicates that the Kerguelen-Crozet province contributes to at least 50% of the coarse particule input to the west. This contribution decreases eastward to reach less than 10%. These tracers clearly indicate that the Crozet-Kerguelen province was a major source region of detrital in the western part of the basin during glacial times. In contrast, material of Antarctic origin is well represented in the whole basin (fine and coarse fractions). Because of the minor amount of coarse particles in the sediments, volcanic particles from Kerguelen and crustal particles from Antarctica have most probably been transported by the Antarctic bottom water current and/or the Circumpolar deepwater current during glacial periods as is the case today. Nevertheless, the presence of coarse particles even in low amount suggests also a transport by ice rafting (sea-ice and icebergs), originated from both Kerguelen and Antarctic sources. However, the relative importance of both hydrographic and ice-rafting modes of transport cannot be identified accurately with our data. During low sea level stands (glacial maximum periods), increasing instability and erosion of the continental platform and shallow plateaus could have resulted in a more efficient transfer of crustal and volcano-detrital material to the Southeast Indian basin. At the same time, extension of the grounded ice shelves over the continental margins and increase in the erosion rate of the Antarctic ice sheet could have induced a greater input of ice rafted detritus (IRD) to southern ocean basins. Enhancement of the circumpolar deepwater current strength might have also carried a more important flux of detrital material from Kerguelen. However, an increase in the bottom water flow is not necessarily required.