Triennial skeletal stable oxygen isotope ratios of Diploria labyrinthiformis

The reconstruction of the climatic history during the past several hundred years requires a sufficient geographical coverage of combined climate proxy series. Especially in order to identify causal connections between the atmosphere and the ocean, inclusion of marine records into composite climate time series is of fundamental importance. We present two skeletal delta18O chronologies of coral skeletons of Diploria labyrinthiformis from Bermuda fore-reef sites covering periods in the nineteenth and twentieth centuries and compare them with instrumental temperature data. Both time series are demonstrated to display sea-surface temperature (SST) variability on inter-annual to decadal time scales. On the basis of a specific modern delta18O vs instrumental SST calibration we reconstruct a time series of SST anomalies between AD 1350 and 1630 covering periods during the Little Ice Age. The application of the coral delta18O vs temperature relationship leads to estimates of past SST variability which are comparable to the magnitude of modern variations. Parallel to delta18O chronologies we present time series of skeletal bulk density. Coral delta18O and skeletal density reveal a strong similarity during Little Ice Age, confirming the reliability of both proxy climate indicators. The past coral records, presented in this study, share features with a previously published climate proxy record from Bermuda and a composite time series of reconstructed Northern Hemisphere summer temperatures. The coral proxy data presented here represent a valuable contribution to elucidate northern Atlantic subtropical climate variation during the past several centuries.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.

Boron isotope ratios of samples from ODP Leg 125 sites at a serpentine seamount, Mariana forearc

Serpentinite clasts and muds erupted from Conical Seamount, Mariana forearc, show substantial enrichment in boron (B) and 11B (delta11B up to +15?) relative to mantle values. These elevated B isotope signatures result from chemical exchange with B-rich pore fluids that are upwelling through the seamount. If the trends of decreasing delta11B with slab depth shown by cross-arc magmatic suites in the Izu and Kurile arcs of the western Pacific are extended to shallow depths (~25 km), they intersect the inferred delta11B of the slab-derived fluids (+13x) at Conical Seamount. Simple mixtures of a B-rich fluid with a high delta11B and B-poor mantle with a low delta11B are insufficient to explain the combined forearc and arc data sets. The B isotope systematics of subduction-related rocks thus indicate that the fluids evolved from downgoing slabs are more enriched in 11B than the slab materials from which they originate. Progressively lower delta11B in arc lavas erupted above deep slabs reflects both the progressive depletion of 11B from the slab and progressively greater inputs of mantle-derived B. This suggests that the slab releases 11B-enriched fluids from the shallowest levels to depths greater than 200 km.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.

Boron concentrations and isotope ratios of authigenic carbonates from the Oregon margin

Boron contents and boron, carbon and oxygen stable isotopes were determined for authigenic carbonates recovered from Ocean Drilling Program Leg 146, Oregon margin. Carbonate precipitates are the most widespread authigenic phase in the shallow accretionary wedge and carry chemical information about long-term variations in pore fluid origin and flow paths in the Cascadia subduction zone. Drilling the first ridge (toe area including the frontal thrust) and the second ridge (or Hydrate Ridge) of the prism demonstrated different fluid regimes, with higher B contents in the authigenic precipitates at the toe. The delta11B of 18 authigenic precipitates analysed ranges from 13.9 per mil to as high as 39.8 per mil, extending the upper range of previously reported carbonate delta11B values considerably. When related to the delta11B ratio of their parent solutions, these data are characteristic of fluid-related processes in accretionary prisms. Together with delta13C and delta18O, delta11B ratios of the carbonate concretions, nodules and crusts allow one to distinguish between precipitation influenced by (i) seawater, (ii) fluid reservoirs at different depth levels within the accretionary prism and (iii) cage water from dissociated gas hydrates, the latter possibly indicating a fluctuation of the bottom simulating reflector during most recent Earth's history. From this first systematic boron study on authigenic precipitates from an accretionary prism it is suggested that B contents of such carbonate crusts and concretions exceed those reported for other marine carbonates. Given the abundance of such precipitates at convergent margins, they represent a significant B sink in geochemical cycling. Isotopic compositions of the parent fluids to the carbonates mirror B chemistry of modern pore waters from convergent margins. The precipitates carry information of different subduction-related fluid processes over a certain period of time, and hence are a crucial tracer in the investigation of palaeo-fluid flow.

Isotope ratios, IRD and planktonic foraminifera content during marine isotope stage 5 of sediment cores MD99-2303, MD99-2304 and MD95-2010

Variable climatic and oceanographic conditions characterized the last interglacial at high northern latitudes, probably related to changes in the strength of the Atlantic Meridional Overturning Circulation (AMOC). The magnitudes of these changes are comparable to the Holocene variability, and were thus significantly subdued compared to glacial climate changes. A thermal optimum occurred during the early part of the interglacial, followed by a period of reduced Atlantic inflow to the northernmost Nordic Seas. Subsequently, a new period with increased strength of the AMOC occurred. Significant amounts of Ice-Rafted Debris (IRD) were deposited in the northernmost Nordic Seas before any major change of the global ice volume. This implies an early onset of local ice sheet growth, probably the result of enhanced inflow of Atlantic water to the northernmost Nordic Seas contemporary with a Northern Hemisphere summer insolation minimum. Contrasting sea-land conditions provided large moisture fluxes towards land, giving rise to rapid, early glacial growth. Throughout the glacial part of Marine Isotope Stage (MIS) 5, millennial-scale cold events occurred along the axis of the warm water transport, from the subtropics all the way to the northernmost Nordic Seas. Correlation of IRD events from sites in the Fram Strait, on the Voring Plateau, and in the North Atlantic provides evidence that the major Northern Hemisphere ice sheets at times responded coherently to the same forcing. The widespread distribution of these events highlights the importance of the oceanic influence on the regional climate system.