Rare-earth elements and isotope ratios at DSDP Leg 82 Holes

We report 48 analyses of rare-earth elements (REE) and 15 143Nd/144Nd and 87Sr/86Sr analyses for basalts from the eight holes drilled during Leg 82. Discrete and distinct REE patterns and 143Nd/144Nd ratios characterize the eight holes, with little variation observed downhole except in Holes 561 and 558, thus suggesting dominantly long-term temporal and large-scale spatial variations in the mantle source of these basalts beneath the Mid-Atlantic Ridge over the last 35 Ma of its spreading activity. There is a good inverse correlation between 143Nd/144Nd and (La/Sm)EF with one exception in Hole 558 (approximately 35 Ma), the latter suggesting a recent (35 Ma) light REE depletion event, perhaps caused by dynamic or fractional melting. Short-term temporal and small-scale spatial mantle source variability is also evident in Hole 561 (approximately 18 Ma), which has rapid fluctuations in REE patterns and 143Nd/144Nd ratios (suggesting rapid transfer of magma from the time of melting) and is evidence contrary to the presence of a well-mixed magma chamber at this particular site and time. The mantle source variations noted can be interpreted within two extreme models. The first model invokes a convecting mantle depleted in large ion lithophile elements (LILE) and containing lumps (or veins) of LILE-enriched material of various shapes and sizes, passively and randomly distributed throughout. A second more restrictive model considers the interaction of fixed mantle plumes and the LILE-depleted asthenosphere flowing towards a migrating Mid- Atlantic Ridge (MAR) axis. With the exception of Hole 558 and the uncertainties of reconstructions of absolute plate movements in the region, the observed variations can be explained by two hot spots; the nearly ridge-centered Azores hot spot (plume) and another hot spot located beneath the African plate that may be affecting the source of basalts currently erupting at the MAR axis at 35°N and which, in the past, would have produced the New England chain of seamounts on the North American plate and (later) the Atlantis-Great Meteor chain on the African plate. Basalts erupted south of the Hayes Fracture Zone have not been affected by either of these two hot spots over the last 35 Ma and appear to have been continuously derived from the LILE-depleted source. Subaxial flow downridge from the Azores plume appears to have started 9 Ma, on the basis of the southward converging V-shaped time-transgressive ridges branching from the Pico and Corves Island, or not earlier than 16 Ma, on the basis of the geochemical results. Variations within Hole 558 remains unexplained by the latter model, unless we hypothesize a third hot spot.

Sedimentology and Nd isotope ratios of sediment core PS72/410-1

The freshwater budget of the Arctic Ocean is a key component governing the deep water formation in the North Atlantic and the global climate system. We analyzed the isotopic composition of neodymium (epsilon-Nd) in authigenic phases of marine sediments on the Mendeleev Ridge in the western Arctic Ocean spanning an estimated time interval from present to about 75 ka BP. This continuous record was used to reconstruct the epsilon-Nd of the polar deep water (PDW) and changes in freshwater sources to the PDW through time. Three deviations in epsilon-Nd from a long term average of -10.2 were identified at estimated 46-51, 35-39 and 13-21 ka BP. The estimated 46-51 ka BP event can be traced to bursting of ice-dammed lakes accompanying the collapse of the Barents-Kara Ice Sheet, which would have released radiogenic Nd to the eastern Arctic Ocean. The cyclonic surface circulation in the eastern Arctic Ocean must have been stronger than at present for the event to be recorded on the Mendeleev Ridge. For the 35-39 and 13-21 ka BP events, it is likely that the Laurentide Ice Sheet (LIS) supplied the unradiogenic freshwater. The configuration of the anticyclonic circulation in the western Arctic was probably similar to today or expanded eastward. Our simple mass balance calculations suggest that large amounts of freshwater were released but due to significant deep water formation within the Arctic Ocean, the effect on the formation of NADW was probably minor.

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.

Oxygen and hydrogen isotope ratios of pore waters from ODP sites in the Mediterranean Sea

Pore fluids from two ODP sites at Eastern Mediterranean mud volcanoes have been analyzed for their Cl concentration and their delta18O and deltaD isotopic composition. The Cl data span a wide range of concentrations, from extremely depleted with respect to seawater (as low as 60 mM) at the crest of Milano dome (site 970) to strongly enriched (up to 5.4 M) at Napoli dome (site 971). Chloride enrichment is known to be due to dissolving Messinian evaporites, whereas the source of the low-Cl fluid is deduced from stable isotope data presented here. The isotopic composition of the endmember fluid is found to be +10? for delta18O and -32? for deltaD for low- as well as for high-Cl waters. From this signature it can be concluded that neither gas hydrates nor meteoric water play a significant role in the freshening of the pore water. Several other processes altering the delta18O/deltaD composition of pore waters are discussed and considered to be of only negligible influence. The process characterizing the isotopic composition of the fluid is found to be clay mineral dehydration (mainly smectite-illite transformation), corresponding to a depth range of 3.5-7 km and an elevated temperature of about 120-165°C. A quantitative estimate shows that this reaction is capable of producing the observed extreme Cl depletion.

Clay mineralogical assemblages, Sm-Nd concentrations, Sm and Nd isotopic ratios and oxygen isotope ratios, OIS number and the age model of ODP Site 105-646

We present 40 Sm-Nd isotope measurements of the clay-size (<2 µm) fractions of sediments from the Southern Greenland rise (ODP-646) that span the last 365 kyr. These data track changes in the relative supply of fine particles carried into the deep Labrador Sea by the Western Boundary Under Current (WBUC) back to the fourth glacial-interglacial cycles. Earlier studies revealed three general sources of particles to the core site: (i) Precambrian crustal material from Canada, Greenland, and/or Scandinavia (North American Shield - NAS), (ii) Palaeozoic or younger crustal material from East Greenland, NW Europe, and/or western Scandinavia (Young Crust - YC) and (iii) volcanic material from Iceland and the Mid-Atlantic Ridge (MAR). Clay-size fractions from glacial sediments have the lowest Nd isotopic ratios. Supplies of young crustal particles were similar during glacial oxygen isotope stages (OIS) 2, 6, and 10. In contrast the mean volcanic contributions decreased relative to old craton material from OIS 10 to OIS 6 and then from OIS 6 to OIS 2. The glacial OIS 8 interval displays a mean Sm/Nd ratio similar to those of interglacials OIS 1, 5, and 9. Compared with other interglacials, OIS 7 was marked by a higher YC contribution but a similar ~30% MAR supply. The overall NAS contribution dropped by a factor of 2 during each glacial/interglacial transition, with the MAR contribution broadly replacing it during interglacials. To decipher between higher supplies and/or dilution, particle fluxes from each end member were estimated. Glacial NAS fluxes were systematically higher than interglacial fluxes. During the time interval examined, fine particle supplies to the Labrador Sea were strongly controlled by proximal ice-margin erosion and thus echoed the glacial stage intensity. In contrast, the WBUC-carried MAR supplies from the eastern basins did not change significantly throughout the last 365 kyr, except for a marked increase in surface-sediments that suggests unique modern conditions. Distal WBUC-controlled inputs from the Northern and NE North Atlantic seem to have been less variable than proximal supplies linked with glacial erosion rate.

Uranium contents and isotope ratios of uranium and strontium in sediments, leachates and pore fluids from ODP Hole 162-984A

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the 234U/238U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%). The pore water 234U/238U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment 234U/238U activity ratios are close to 1.0. The 234U/238U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess 234U to the pore fluid by a-recoil injection of 234Th. The fraction of 238U decays that result in a-recoil injection of 234U to pore fluid is estimated to be 0.10 to 0.20 based on the 234U/238U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 0.0000004 to 0.000002 1/yr. There is significant down-hole variability in pore water 234U/238U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 1000 times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials. The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ~ 0.1 1/age for ages spanning 1000 to 500,000,000 yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.

Stable isotope ratios of foraminifera from ODP Hole 171B-1051B sediments

The primary aim of the this investigation was to examine the stability of subtropical sea-surface temperatures and reconstruct the surface-to-benthos thermal gradient. High-resolution stable isotopic analyses (18O and 13C) were conducted on late middle Eocene planktonic and benthic foraminifers recovered from Hole 1051B, Blake Nose, western North Atlantic. The sequence comprises a siliceous nannofossil and foraminifer ooze, with well-preserved calcareous microfossils. Isotopic examination was conducted on the mixed-layer dweller Morozovella spinulosa and the benthic foraminifer Nuttalides truempyi at this subtropical site.

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.