Re-OS and Pb isotope ratios of sediments from Saanich Inlet, Western Canada

Re-Os and Pb-Pb isotopic analysis of reduced varved sediments cored in the deeper basin of Saanich Inlet (B.C.) are presented. From core top to 61 cm down-core, spanning approximately the last 100 yrs of sedimentation, 187Os/188Os ratio and Os concentration respectively increase from ~0.8 to ~0.9 and from 55 to 60 ppt, whereas Re concentration decreases from 3600 to 2600 ppt. Re correlates with Corg (R2=0.6) throughout the entire section, whereas Os follows Re and Corg trends deeper down-core, suggesting a decoupling of a Re- and Os-geochemistry during burial and/or very early diagenesis. No systematic compositional differences are observed between seasonal laminae. 204Pb-normalized lead isotope ratios increase from sediment surface down to 7 cm down-core, then decrease steadily to pre-industrial levels at ~50 cm down-core. This pattern illustrates the contamination from leaded gasoline until the recent past. The measured Pb isotopic ratios point primarily toward gasoline related atmospheric lead from the USA. The osmium isotopic values measured are significantly lower than those of modern seawater-Os. In comparison with other anoxic environments, the osmium content of Saanich Inlet sediments is low, and its Os isotopic composition suggests significant inputs from unradiogenic sources (detrital and/or dissolved). Ultramafic lithologies in the watershed of the Fraser River are suspected to contribute to sedimentary inputs as well as to the input of dissolved unradiogenic osmium in the water of Saanich Inlet. The presence of some unradiogenic Os from anthropogenic contamination cannot be discounted near the core top, but since deeper, pre-anthropogenic levels also yielded unradiogenic Os results, one is led to conclude that the overall low 187Os/188Os ratios result from natural geochemical processes. Thus, the bulk sediment of Saanich Inlet does not appear to record 187Os/188Os composition of the marine end-member of the only slightly below normal salinity, fjord water. The low seawater-derived Os content of the sediment, coupled with unradiogenic Os inputs from local sources, explains the overall low isotopic values observed. As a consequence, such near-shore anoxic sediments are unlikely to record changes in the past ocean Os isotopic composition.

Geochemistry of North Atlantic Igneous Province basalts

New Sr-Nd-Pb-Hf data require the existence of at least four mantle components in the genesis of basalts from the the North Atlantic Igneous Province (NAIP): (1) one (or more likely a small range of) enriched component(s) within the Iceland plume, (2) a depleted component within the Iceland plume (distinct from the shallow N-MORB source), (3) a depleted sheath surrounding the plume and (4) shallow N-MORB source mantle. These components have been available since the major phase of igneous activity associated with plume head impact during Paleogene times. In Hf-Nd isotope space, samples from Iceland, DSDP Leg 49 (Sites 407, 408 and 409), ODP Legs 152 and 163 (southeast Greenland margin), the Reykjanes Ridge, Kolbeinsey Ridge and DSDP Leg 38 (Site 348) define fields that are oblique to the main ocean island basalt array and extend toward a component with higher 176Hf/177Hf than the N-MORB source available prior to arrival of the plume, as indicated by the compositions of Cretaceous basalts from Goban Spur (~95 Ma). Aside from Goban Spur, only basalts from Hatton Bank on the oceanward side of the Rockall Plateau (DSDP Leg 81) lie consistently within the field of N-MORB, which indicates that the compositional influence of the plume did not reach this far south and east ~55 Ma ago. Thus, Hf-Nd isotope systematics are consistent with previous studies which indicate that shallow MORB-source mantle does not represent the depleted component within the Iceland plume (Thirlwall, J. Geol. Soc. London 152 (1995) 991-996; Hards et al., J. Geol. Soc. London 152 (1995) 1003-1009; Fitton et al., 1997 doi:10.1016/S0012-821X(97)00170-2). They also indicate that the depleted component is a long-lived and intrinsic feature of the Iceland plume, generated during an ancient melting event in which a mineral (such as garnet) with a high Lu/Hf was a residual phase. Collectively, these data suggest a model for the Iceland plume in which a heterogeneous core, derived from the lower mantle, consists of 'enriched' streaks or blobs dispersed in a more depleted matrix. A distinguishing feature of both the enriched and depleted components is high Nb/Y for a given Zr/Y (i.e. positive DeltaNb), but the enriched component has higher Sr and Pb isotope ratios, combined with lower epsilon-Nd and epsilon-Hf. This heterogeneous core is surrounded by a sheath of depleted material, similar to the depleted component of the Iceland plume in its epsilon-Nd and epsilon-Hf, but with lower 87Sr/86Sr, 208Pb/204Pb and negative DeltaNb; this material was probably entrained from near the 670 km discontinuity when the plume stalled at the boundary between the upper and lower mantle. The plume sheath displaced more normal MORB asthenosphere (distinguished by its lower epsilon-Hf for a given epsilon-Nd or Zr/Nb ratio), which existed in the North Atlantic prior to plume impact. Preliminary data on MORBs from near the Azores plume suggest that much of the North Atlantic may be 'polluted' not only by enriched plume material but also by depleted material similar to the Iceland plume sheath. If this hypothesis is correct, it may provide a general explanation for some of the compositional diversity and variations in inferred depth of melting (Klein and Langmuir, 1987 doi:10.1029/JB092iB08p08089) along the MAR in the North Atlantic.

Stable carbon isotope ratios and the formation of dolomite in ODP Leg 175 sites

We examine the link between organic matter degradation, anaerobic methane oxidation (AMO), and sulfate depletion and explore how these processes potentially influence dolomitization. We determined rates and depths of AMO and dolomite formation for a variety of organic-rich sites along the west African Margin using data from Ocean Drilling Program (ODP) Leg 175. Rates of AMO are calculated from the diffusive fluxes of CH4 and SO4, and rates of dolomite formation are calculated from the diffusive flux of Mg. We find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming, indicating that the diffusive fluxes of Mg and Ca are not limiting. Based upon the calculated log IAP values, log K(sp) values for dolomite were found to narrowly range between -16.1 and -16.4. Dolomite formation is controlled in part by competition between AMO and methanogenesis, which controls the speciation of dissolved CO2. AMO increases the concentration of CO3[2-] through sulfate reduction, favoring dolomite formation, while methanogenesis increases the pCO2 of the pore waters, inhibiting dolomite formation. By regulating the pCO2 and alkalinity, methanogenesis and AMO can regulate the formation of dolomite in organic-rich marine sediments. In addition to providing a mechanistic link between AMO and dolomite formation, our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming.

Major element concentrations in spinel, olivine and pyroxene from peridotites of ODP Hole 210-1277 of the Newfoundland margin

Serpentinized spinel peridotites of the Newfoundland margin drilled during ODP Leg 210 at Site 1277 have preserved, relic mineral compositions similar to the most depleted abyssal peridotites worldwide and different from those of the conjugate Iberian margin. The samples are derived from mass flows containing clasts of peridotite and gabbro and from in-situ basement, and are mostly mylonitic cpx-poor spinel harzburgites with Cr-rich spinels (Cr#0.35-0.66). Melting of the Newfoundland mantle occurred in the spinel peridotite field and probably exceeded the cpx-out phase boundary for some samples. Using proposed spinel peridotite melting models and experimentally derived phase diagrams, the Newfoundland harzburgites can be modeled as a residue after extraction of 14 to 20-25% melting. Basalts that are interleaved with mass flow deposits on top of the peridotite basement resemble normal to transitional mid-ocean ridge basalt. This, together with the unusually high Cr# of some spinel harzburgites suggest that the formation of basalts and partial melting of the underlying peridotite are not cogenetic. Among mantle samples some of the Newfoundland harzburgites approach mineral compositions of the Bay of island ophiolite and ophiolites from Japan that represent peridotites formed in an arc-setting. Thus, the peridotites drilled at Site 1277 may represent inherited (Caledonian or older) subarc mantle that was exhumed close to the ocean floor during the rifting evolution of the Atlantic. Compared to the spinel harzburgites from Newfoundland, the peridotites from the conjugate Iberian margin are, on average, less depleted and provide evidence for local equilibration in the plagioclase stability field. This can either be explained by an inherited, primary, Ca-richer composition of the Iberia peridotite, or, alternatively, by local melt impregnation and stagnation during continental rifting, and thus refertilizing previously depleted (arc-related) peridotite.

Separating ITCZ- and ENSO-related rainfall changes in the Galápagos over the last 3 kyr using D/H ratios of multiple lipid biomarkers

We present a 3000-yr rainfall reconstruction from the Galápagos Islands that is based on paired biomarker records from the sediment of El Junco Lake. Located in the eastern equatorial Pacific, the climate of the Galápagos Islands is governed by movements of the Intertropical Convergence Zone (ITCZ) and the El Niño-Southern Oscillation (ENSO). We use a novel method for reconstructing past ENSO- and ITCZ-related rainfall changes through analysis of molecular and isotopic biomarker records representing several types of plants and algae that grow under differing climatic conditions. We propose that ?D values of dinosterol, a sterol produced by dinoflagellates, record changes in mean rainfall in El Junco Lake, while dD values of C34 botryococcene, a hydrocarbon unique to the green alga Botryococcus braunii, record changes in rainfall associated with moderate-to-strong El Niño events. We use these proxies to infer changes in mean rainfall and El Niño-related rainfall over the past 3000 yr. During periods in which the inferred change in El Niño-related rainfall opposed the change in mean rainfall, we infer changes in the amount of ITCZ-related rainfall. Simulations with an idealized isotope hydrology model of El Junco Lake help illustrate the interpretation of these proxy reconstructions. Opposing changes in El Niño- and ITCZ-related rainfall appear to account for several of the largest inferred hydrologic changes in El Junco Lake. We propose that these reconstructions can be used to infer changes in frequency and/or intensity of El Niño events and changes in the position of the ITCZ in the eastern equatorial Pacific over the past 3000 yr. Comparison with El Junco Lake sediment grain size records indicates general agreement of inferred rainfall changes over the late Holocene.

Age model and Plio-Pleistocene benthic stable oxygen isotope ratios of ODP Site 184-1143 in the Sourh China Sea

Based on benthic foraminiferal delta18O from ODP Site 1143, a 5-Myr astronomical timescale for the West Pacific Plio-Pleistocene was established using an automatic orbital tuning method. The tuned Brunhes/Matuyama paleomagnetic polarity reversal age agrees well with the previously published age of 0.78 Ma. The tuned ages for several planktonic foraminifer bio-events also agree well with published dates, and new ages for some other bio-events in the South China Sea were also estimated. The benthic delta18O from Site 1143 is highly coherent with the Earth's orbit (ETP) both at the obliquity and precession bands for the last 5 Myr, and at the eccentricity band for the last 2 Myr. In general, the 41-kyr cycle was dominant through the Plio-Pleistocene although the 23-kyr cycle was also very strong. The 100-kyr cycle became dominant only during the last 1 Myr. A comparison of the benthic delta18O between the Atlantic (ODP 659) and the East and West Pacific (846 and 1143) reveals that the Atlantic-Pacific benthic oxygen isotope difference ratio (Delta delta18OAtl-Pac) displays an increasing trend in three time intervals: 3.6-2.7 Ma, 2.7-2.1 Ma and 1.5-0.25 Ma. Each of the intervals begins with a rapid negative shift in Delta delta18OAtl-Pac, followed by a long period with an increasing trend, corresponding to the growth of the Northern Hemisphere ice sheet. This means that all three intervals of ice sheet growth in the Northern Hemisphere were accompanied at the beginning by a rapid relative warming of deep water in the Atlantic as compared to that of the Pacific, followed by its gradual relative cooling. This general trend, superimposed on the frequent fluctuations with glacial cycles, should yield insights into the processes leading to the boreal glaciation. Cross-spectral analyses of the Delta delta18OAtl-Pac with the Earth's orbit suggests that after the initiation of Northern Hemisphere glaciation at about 2.5 Ma, obliquity rather than precession had become the dominant force controlling the vertical structure or thermohaline circulation in the paleo-ocean.

Lithium concentrations and isotope composition of basalt samples from ODP/DSDP Sites from Costa Rica Rift

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (delta7Li=6.6-20.8?) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (-0.8-2.1?) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from -1.7 to 7.9?, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because 6Li is preferentially retained in greenschist and amphibolite facies minerals. The delta7Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8*10**9 mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.

Chemical and isotopical analsyes of DSDP Hole 34-321 basalts

A blue-green smectite (iron-rich saponite) and green mica (celadonite) are the dominant sheet silicates in veins within the 10.5 m of basalt cored during DSDP Leg 34, Site 32l, in the Nazca plate. Oxygen isotopic analyses of these clays, and associated calcite, indicate a formation temperature of <25°C. Celadonite contains appreciable Fe2O3, K2O and SiO2, intermediate MgO, and very little Al2O3. Celadonite is commonly associated with goethite and hematite, which suggests that this phase formed by precipitation within a dominantly oxygenated environment of components leached from basalt and provided by seawater. A mass balance estimate indicates that celadonite formation can remove no more than 15% of the K annually transported to the oceans by rivers. In contrast, iron-rich saponite containing significant Al2O3 appears to have precipitated from a nonoxidizing, distinctly alkaline fluid containing a high Na/K ratio relative to unmodified seawater. Seawater-basalt interaction at low temperatures, resulting in the formation of celadonite and smectite may explain chemical gradients observed in interstitial waters of sediments overlying basalts.

Helium isotope ratios and sedimentation rate models of ODP holes

A continuous age model for the brief climate excursion at the Paleocene-Eocene boundary has been constructed by assuming a constant flux of extraterrestrial 3He (3He[ET]) to the seafloor. 3He[ET] measurements from ODP Site 690 provide quantitative evidence for the rapid onset (and short duration (<120 kyr) of global warming and of the associated disturbance to the Earth's surficial carbon budget at this time. These observations support astronomically calibrated age models indicating extremely rapid release of isotopically light carbon, possibly from seafloor methane hydrate, as the proximal cause of the event. However, the 3He[ET] technique indicates a previously unrecognized and extreme increase in sedimentation rate coincident with the return of climate proxies to pre-event values. The 3He[ET]-based age model thus suggests a far more rapid recovery from the climatic perturbation than previously proposed or predicted on the basis of the modern carbon cycle, and so may indicate additional or accelerated mechanisms of carbon removal from the ocean-atmosphere system during this period. 3He[ET] was also measured at ODP Site 1051 to test the validity of the Site 690 chronology. Comparison of these data sets seems to require removal of several tens of kyr of sediment within the climatic excursion at Site 1051, an observation consistent with sediment structures and previous age modeling efforts. The Site 1051 age model shows a ~30 kyr period in which climate proxies return toward pre-event values, after which they remain invariant for ~80 kyr. If this rise represents the recovery interval identified at Site 690, then the 3HeET-based age models of the two sites are in good agreement. However, alternative interpretations are possible, and work on less disrupted sites is required to evaluate the reliability of the proposed new chronology of the climate excursion. Regardless of these details, this work shows that the 3HeET technique can provide useful independent evidence for the development and testing of astronomically calibrated age models.

Radioisotopes and He accumulation in deep sea sediments of the Ontong Java Plateau

The accumulation of extraterrestrial 3He, a tracer for interplanetary dust particles (IDPs), in sediments from the Ontong Java Plateau (OJP; western equatorial Pacific Ocean) has been shown previously to exhibit a regular cyclicity during the late Pleistocene, with a period of ~100 ka. Those results have been interpreted to reflect periodic variability in the global accretion of IDPs that, in turn, has been linked to changes in the inclination of Earth's orbit with respect to the invariable plane of the solar system. Here we show that the accumulation in OJP sediments of authigenic 230Th, produced by radioactive decay of 234U in seawater, exhibits a 100-ka cyclicity similar in phase and amplitude to that evident in the 3He record. We interpret the similar patterns of 230Th and 3He accumulation to reflect a common origin within the ocean-climate system. Comparing spatial and temporal patterns of sediment accumulation against regional patterns of biological productivity and against the well-established pattern of CaCO3 dissolution in the deep Pacific Ocean leads to the further conclusion that a common 100-ka cycle in accumulation of biogenic, authigenic and extraterrestrial constituents in OJP sediments reflects the influence of climate-related changes in sediment focusing, rather than changes in the rate of production or supply of sedimentary constituents.

Annual 10Be concentrations from Lakes Tiefer See and Czechowskie AD1983-2009

Beryllium 10 concentrations (10Becon) were measured at annual resolution from varved sediment cores of Lakes Tiefer See (TSK) and Czechowskie (JC) for the period 1983-2009 (~solar cycles 22 and 23). Calibrating the 10Becon time-series against complementing proxy records from the same archive as well as local precipitation and neutron monitor data, reflecting solar forced changes in atmospheric radionuclide production, allowed (i) identifying the main depositional processes and (ii) evaluating the potential for solar activity reconstruction. 10Becon in TSK and JC sediments are significantly correlated to varying neutron monitor counts (TSK: r=0.5, p=0.05, n=16; JC: r=0.46, p=0.03, n=22). However, the further correlations with changes in organic carbon contents in TSK as well as varying organic carbon and detrital matter contents in JC point to catchment specific biases in the 10Becon time-series. In an attempt to correct for these biases multiple regression analysis was applied to extract an atmospheric 10Be production signal (10Be atmosphere). To increase the signal to noise ratio a 10Be composite record (10Be composite) was calculated from the TSK and JC 10Be atmosphere time-series. 10Becomposite is significantly correlated to variations in the neutron monitor record (r=0.49, p=0.01, n=27) and matches the expected amplitude changes in 10Be production between solar cycle minima and maxima. This calibration study on 10Be from two sites indicates the large potential but also, partly site-specific, limitations of 10Be in varved lake sediments for solar activity reconstruction.