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.

Seawater carbonate chemistry and zooxanthellate coral Cladocora caespitosa boron isotopic and elemental systematics during experiments, 2011

Boron isotopic and elemental systematics are used to define the vital effects for the temperate shallow water Mediterranean coral Cladocora caespitosa. The corals are from a range of seawater pH conditions (pHT ~ 7.6 to ~ 8.1) and environmental settings: (1) naturally living colonies harvested from normal pH waters offshore Levanto, (2) colonies transplanted nearby a subsea volcanic vent system, and (3) corals cultured in aquaria exposed to high (700 µatm) and near present day (400 µatm) pCO2 levels. B/Ca compositions measured using laser ablation inductively coupled mass spectrometry (LA-ICPMS) show that boron uptake by C. caespitosa cultured at different pCO2 levels is independent of ambient seawater pH being mainly controlled by temperature-dependent calcification. In contrast, the boron isotope compositions (delta11Bcarb) of the full suite of corals determined by positive thermal ionisation mass spectrometry (PTIMS) shows a clear trend of decreasing delta11Bcarb (from 26.7 to 22.2 %o) with decreasing seawater pH, reflecting the strong pH dependence of the boron isotope system. The delta11Bcarb compositions together with measurements of ambient seawater parameters enable calibration of the boron pH proxy for C. caespitosa, by using a new approach that defines the relationship between ambient seawater pH (pHsw) and the internally controlled pH at the site of calcification (pHbiol). C. caespitosa exhibits a linear relationship between pHsw and the shift in pH due to physiological processes (deltapH = pHbiol - pHsw) giving the regression deltapHClad = 4.80 - 0.52* pHsw for this species. We further apply this method ("deltapH-pHsw") to calibrate tropical species of Porites, Acropora, and Stylophora reported in the literature. The temperate and tropical species calibrations are all linearly correlated (r2 > 0.9) and the biological fractionation component (deltapH) between species varies within ~ 0.2 pH units. Our "deltapH-pHsw" approach provides a robust and accurate tool to reconstruct palaeoseawater pHsw for both temperate and tropical corals, further validating the boron fractionation factor (alphaB3-B4 = 1.0272) determined experimentally by Klochko et al. (2006) and the boron isotope pH proxy, both of which have been the foci of considerable debate.

Pb concentrations, Pb isotopic composition, and amount of metalliferous components in pelagic sediments from the Pacific Ocean

The amount of lead annually transferred from oceanic crust to metalliferous sediments was estimated in order to test the hypothesis that a non-magmatic flux of lead causes the Pb surplus in the continental crust. A Pb surplus has been inferred from global crust-mantle lead mass balances derived from lead concentration correlations with other trace elements and from lead isotope systematics in oceanic basalts. DSDP/ODP data on the amount of metalliferous sediments in the Pacific Ocean and along a South Atlantic traverse are used to calculate the mean worldwide thickness of 3 (+/-1) m for purely metalliferous sediment componens. Lead isotope ratios of 39 metalliferous sediments from the Pacific define mixing lines between continent-derived (seawater) and mantle-derived (basaltic) lead, with the most metal-rich sediments usually having the most mantle-like Pb isotope composition. We used this isotope correlation and the Pb content of the 39 metalliferous sediments to derive an estimate of 130 (+/-70) µg/g for the concentration of mantle-derived lead in the purely metalliferous end-member. Mass balance calculations show that at least 12 (+/-8)% of the lead, annually transferred from upper mantle to oceanic crust at the ocean ridges, is leached out by hydrothermal processes and re-deposited in marine sediments. If all of the metalliferous lead is ultimately transferred to the continental crust during subduction, the annual flux of this lead from mantle to continental crust is 2.6 (+/-2.0) * 10**6 kg. Assuming this transfer rate to be proportional to the rate of oceanic plate production, one can fit the lead transfer to models of plate production rate variations through time. Integrating over 4 Ga, hydrothermal lead transfer to the continental crust accounts for a significant portion of the Pb surplus in the continental crust. It therefore appears to be one of the main reasons for the anomalous behavior of lead in the global crust-mantle system.

Nd, Sr and Pb isotopic composition of eolian dust deposited in the central North Pacific

The silicate fractions of recent pelagic sediments in the central north Pacific Ocean are dominated by eolian dust derived from central Asia. An 11 Myr sedimentary record at ODP Sites 885/886 at 44.7°N, 168.3°W allows the evaluation of how such dust and its sources have changed in response to late Cenozoic climate and tectonics. The extracted eolian fraction contains variable amounts (>70%) of clay minerals with subordinate quartz and plagioclase. Uniform Nd isotopic compositions (epsilon-Nd =38.6 to 310.5) and Sm/Nd ratios (0.170-0.192) for most of the 11 Myr record demonstrate a well-mixed provenance in the basins north of the Tibetan Plateau and the Gobi Desert that was a source of dust long before the oldest preserved Asian loess formed. epsilon-Nd values of up to 36.5 for samples 62.9 Ma indicate <=35 wt% admixture of a young, Kamchatka-like volcanic arc component. The coherence of Pb and Nd in the erosional cycle allows us to constrain the Pb isotopic composition of Asian loess devoid of anthropogenic contamination to 206Pb/204Pb =18.97 +/- 0.06, 207Pb/204Pb =15.67 +/- 0.02, 208Pb/204Pb =39.19 +/- 0.11. 87Sr/86Sr (0.711-0.721) and Rb/Sr ratios (0.39-1.1) vary with dust mineralogy and provide an age indication of ~250 Ma. 40Ar/39Ar ages of six dust samples are uniform around 200 Ma and match the K-Ar ages of modern dust deposited on Hawaii. These data reflect the weighted age average of illite formation. Changes from illite- smectite with significant kaolinite to illite- and chlorite-rich, kaolinite-free assemblages since the late Pliocene document changes in the intensity of chemical weathering in the source region. Such weathering evidently did not disturb the K-Ar systematics, and only induced scatter in the Rb-Sr data. We propose that when smectite forms at the expense of illite, K and Ar are quantitatively lost from what becomes smectite, but are quantitatively retained in adjacent illite layers. 40Ar/39Ar age data, therefore, are insensitive to smectite formation during chemical weathering but date the diagenetic growth of illite, the major K-bearing phase in the dust. Over the past 12 Myr, the dust flux to the north Pacific increased by more than an order of magnitude, documenting a substantial drying of central Asia. This climatic change, however, did not alter the ultimate source of the dust, and neoformational products of chemical weathering always remained subordinate to assemblages reworked by mechanical erosion in dust deposited in eastern Asia and the Pacific Ocean.

Rb-Sr isotope systematics and Sr/Ca-Ba/Ca ratios at DSDP Hole 89-462A

Four samples of Nauru Basin basalts (Cores 94 to 109 of Hole 462A, sub-bottom depth 1077-1209 m) have 87Sr/86Sr ratios in the range 0.7037 to 0.7038, which is distinctly higher than the ratios of N-type MORB. The Rb contents of the samples are depleted in comparison with those of MORB and ocean-island basalts. These chemical and isotopic characteristics are identical to those of the basalts previously drilled during Leg 61 (Cores 75 to 90 of Hole 462A), and are explained in terms of inhomogeneity of the source region in the mantle or later alteration effects. Sr/Ca-Ba/Ca systematics of 15 samples from Cores 462A-94 to 462A-109 and 14 samples from Cores 462A-75 to 462A-90 suggest that the Nauru Basin basalts are derived from a mantle peridotite by 20 to 30% partial melting with subsequent Plagioclase crystallization.

Nd, Sr and Sm isotopic composition and model ages of rocks from the Anginskaya and Talanchanskaya formations, Lake Baikal

The paper presents data on the Nd-Sr systematics of magmatic rocks of the Khaidaiskii Series of the Anginskaya Formation in the Ol'khon region, western Baikal area, and rocks of the Talanchanskaya Formation on the eastern shore of Lake Baikal. Geochemical characteristics of these rocks are identical and testify to their arc provenance. At the same time, the epsilon(t)Nd of rocks of the Khaidaiskii Series in the Ol'khon area has positive values, and the data points of these rocks plot near the mantle succession line in the epsilon(t)Nd-87Sr/86Sr diagram, whereas the epsilon(t)Nd values of rocks of the Talanchanskaya Formation are negative, and the data points of these rocks fall into the fourth quadrant in the epsilon(t)Nd -87Sr/86Sr diagram. This testifies to a mantle genesis of the parental magmas of the Khaidaiskii Series and to the significant involvement of older crustal material in the generation of the melts that produced the orthorocks on the eastern shore of the lake. These conclusions are corroborated by model ages of magmatic rocks in the Ol'khon area (close to 1 Ga) and of rocks of the Talanchanskaya Formation (approximately 2 Ga). The comparison of our data with those obtained by other researchers on the Nd-Sr isotopic age of granulites of the Ol'khon Group and metavolcanics in various structural zones in the northern Baikal area suggests, with regard for the geochemistry of these rocks, the accretion of tectonic nappes that had different isotopic histories: some of them were derived from the mantle wedge and localized in the island arc itself (magmatic rocks of the Anginskaya Formation) or backarc spreading zone (mafic metamagmatic rocks of the Ol'khon Group), while others were partial melts derived, with the participation of crustal material, from sources of various age (metagraywackes in the backarc basin in the Ol'khon Group and the ensialic basement of the island arc in the Talanchanskaya Formation).

Chemical and isotopic compositions of sediments from DSDP Hole 21-204

The highly depleted intra-oceanic Tonga-Kermadec island arc forms an endmember of arc systems and a unique location in which to isolate the effects of the slab flux. High precision TIMS uranium, thorium, strontium, neodymium, and lead isotopes, along with complete major and trace element data, have been obtained on an extensive sample set comprising fifty-eight lavas along the arc as well as nineteen samples of the subducting sediments at DSDP site 204 just to the east of the Tonga-Kermadec trench. Ca/Ti and Al/Ti ratios extend from values appropriate to an N-MORB source in the southern Kermadecs to very high ratios in Tonga interpreted to reflect increasing degrees of depletion of the mantle wedge due to backarc basalt extraction. The isotope data emphasize the need for four components in the petrogenesis of the lavas: (1) the mantle wedge; (2) a component with elevated 207Pb/204Pb towards which the Kermadec and southern Tongan lavas extend; (3) a component characterised by high 206Pb/204Pb, Ta/Nd, and low 143Nd/144Nd observed only in the northernmost Tongan islands of Tafahi and Niuatoputapu; (4) a fluid component characterised by strong enrichments of Rb, Ba, U, K, Ph, and Sr, relative to Th, Zr, and the REE and producing large 238U excesses ((230Th/238U) = 0.8-0.5) in the more depleted lavas. The mantle wedge (Component 1) is isotopically similar to the source of the Lau BABB. Component 2 is average pelagic sediment on the downgoing Pacific plate as observed at DSDP sites 595/596 and in the upper sections of the sediment pile at DSDP site 204. Mass balance calculations indicate that less than 0.5% is recycled into the arc lavas; essentially all the subducted sediment is returned to the upper mantle (~0.03 km**3/yr). Exceptionally low concentrations of Ta and Nb relative to Th and the LREE requires that this sediment component is added as a partial melt which was in equilibrium with residual rutile or ilmenite. Component 3 is identified as volcaniclastics from the Louisville Ridge which comprise the lower 44 m of the sediment section intersected at DSDP site 204. These volcaniclastics are spatially restricted to the vicinity of the Louisville Ridge and provide a unique sediment tracer which can be used to show that it takes 4 Myr from the time of subduction to its first appearance in the arc lava signature. Component 4, the fluid contribution to the lava source is inferred to contribute ~1 ppm Rb, 10 ppm Ba, 0.02 ppm U, 600 ppm K, 0.2 ppm Ph, and 30 ppm Sr. It has 87Sr/86Sr = 0.7035 and 206Pb/204Pb = 18.5 and thus it is inferred to have been derived from dehydration of the subducting altered oceanic crust. U-Th isotope disequilibria reflect the time since fluid release from the subducting slab and a reference line through the lowest (230Th/232Th) lavas constrains this to be 30000-50000 yr. The U-Th and Th-Ra isotope systematics are decoupled, and it is suggested that Th-Ra isotope disequilibria record the time since partial melting and thus indicate rapid channelled magma ascent. Olivine gabbro xenoliths from Raoul are interpreted as cumulates to their host lavas with which they form zero age U-Th isochrons indicating that minimal time was spent in magma chambers. The subduction signature is not observed in lavas from the backarc island of Niuafo'ou. These were derived from partial melting of fertile peridotite at 130-160 km depth with melt rates around 0.0002 kg/m**3/yr.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.