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.

U-Th dating of marine sediments from the Bahamas slope

In order to understand the driving forces for Pleistocene climate change more fully we need to compare the timing of climate events with their possible forcing. In contrast to the last interglacial (marine isotope stage (MIS) 5) the timing of the penultimate interglacial (MIS 7) is poorly constrained. This study constrains its timing and structure by precise U-Th dating of high-resolution delta18O records from aragonite-rich Bahamian slope sediments of ODP Leg 166 (Sites 1008 and 1009). The major glacial-interglacial cycles in delta18O are distinct within these cores and some MIS 7 substages can be identified. These sediments are well suited for U-Th dating because they have uranium concentrations of up to 12 ppm and very low initial 230Th contributions with most samples showing 230Th/232Th activity ratio of >75. U and Th concentrations and isotope ratios were measured by thermal ionisation mass spectrometry and multiple collector inductively coupled plasma mass spectrometry, with the latter providing dramatically better precision. Twenty-nine of the 41 samples measured have a delta234U value close to modern seawater suggesting that they have experienced little diagenesis. Ages from 27 of the 41 samples were deemed reliable on the basis of both their U and their Th isotope ratios. Ages generally increase with depth, although we see a repeated section of stratigraphy in one core. Extrapolation of constant sedimentation rate through each substage suggests that the peak of MIS 7e lasted from ~237 to 228 ka and that 7c began at 215 ka. This timing is consistent with existing low precision radiometric dates from speleothem deposits. The beginning of both these substages appears to be slightly later than in orbitally tuned timescales. The end of MIS 7 is complex, but also appears to be somewhat later than is suggested by orbitally tuned timescales, although this event is not particularly well defined in these cores.

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.

(Table 2) Uranium and thorium isotopic composition, activity ratios and ages of bivalvia shells in sediment core GIK14350, northern Germany

A new chemical procedure for cleaning marine carbonates was applied to remove detritus as well as metaloxide contaminations of marine shells from Eemian deposits and adjoining succession of a sediment core from Dagebüll, Schleswig- Holstein. Hence, one can significantly reduce the contamination with detrital uranium and thorium. Thermal ionisation mass spectrometry was applied to determine the uranium and thorium activities used for 230Th/U dating of these shells. At least ten samples of marine bivalves of five different core sections were analysed. Samples located below a five meter thick clay layer at 19-24 m yielded an average age of 132±18 ka. Shells located above the clays at 15-20 m depth were strongly influenced by percolating groundwaters of an open system. Therefore, a reliable dating of these samples was not possible.