Nd and Sr isotopic composition of Cretaceous MORB

Chemical and isotopic (Nd and Sr) compositions have been determined for 12 Cretaceous basaltic samples (108 Ma old) from Holes 417D and 418A of Legs 51,52 and 53. We have found that: (1) The chemical compositions are typical of MORB. They do not vary systematically with the stratigraphic positions of the analyzed samples; thus, the chemical evolution is independent of the eruption sequence that occurred at this Cretaceous ridge. (2) REE patterns for all rocks are characterized by a strong LREE depletion with (La/Sm)N = 0.38-0.50; no significant Eu anomalies are found; HREE are nearly flat or slightly depleted towards Yb-Lu and have 12-18 * chondritic abundances. Combining the results of previous studies, it suggests that no significant temporal and spatial variation in magma chemistry (especially for LIL elements) has occurred in the 'normal' ridge segments over the last 150 Ma. (3) lsotopically, 143Nd/144Nd ratios vary from 0.513026 to 0.513154, corresponding to epsilon-Nd(0) = +7.5 to +10, and they fall in the typical range of MORB. However, these rocks have unexpectedly high 87Sr/86Sr ratios (0.70355-0.70470) which are attributed to the result of seawater-rock interaction. (4) The Nd model ages (Tin), ranging from 1.53 to 2.47 (average 2.06) AE, suggest that the upper mantle source(s) underwent a large scale chemical differentiation leading to LREE and other LIL element depletion about 2 AE ago, assuming a simple two-stage model. More realistically, the variation in Tm(Nd) or epsilon-Nd could be derived from mixing of heterogeneous mantle sources that were a consequence of continuous mantle differentiation and continental formation. (5) Because of the low mg values (0.52-0.63), the analyzed basaltic rocks do not represent primary liquids of mantle melting. The variation in La/Sm ratios and TiO2 are not compatible with a model in which all rocks are genetically related by a simple fractional crystallization. Rather, it is proposed that the basaltic rocks might have been derived from some heterogeneous upper mantle source with or without later magmatic mixing, and followed by some shallow-level fraetionations.

Isotopic composition of igneous rocks from DSDP Site 462

The tholeiitic basalts and microdolerites that comprise the Cretaceous igneous complex in the Nauru Basin in the western equatorial Pacific have moderate ranges in initial 87Sr/86Sr (0.70347 - 0.70356), initial 143Nd/144Nd (0.51278 - 0.51287), and measured 206Pb/204Pb (18.52 - 19.15), 207Pb/204Pb (15.48 - 15.66) and 208Pb/204Pb (38.28 - 38.81). These isotopic ratios overlap with those of both oceanic island basalts (OIB) and South Atlantic and Indian mid-ocean ridge basalts (MORB). However, the petrography, mineralogy, and bulk rock chemistry of the igneous complex are more similar to MORB than to OIB. Also, the rare earth element contents of Nauru Basin igneous rocks are uniformly depleted in light elements (La/Sm(ch) < 1) indicative of a mantle source compositionally similar to that of MORB. These results suggest that the igneous complex is the top of the original ocean crust in the Nauru Basin, and that the notion that the crust must be 15 to 35 m.y. older based on simple extrapolation and identification of the M-sequence magnetic lineations (Larson et al., 1981, doi:10.2973/dsdp.proc.61.1981; Moberly et al., 1985, doi:10.2973/dsdp.proc.81.1984) may be invalid because of a more complicated tectonic setting. The igneous complex most probably was extruded from an ocean ridge system located near the anomalously hot, volcanically active, and isotopically distinct region in the south central Pacific which has been in existence since c. 120 Ma.

Geochemical and isotopic composition of pore fluids of ODP Hole 131-808C

At the Western Nankai Trough subduction zone at ODP Site 808, chemical concentration and isotopic ratio depth profiles of D, O, Sr, and He do not support fluid flow along the décollement nor at the frontal thrust. They do, however, support continuous or periodic lateral fluid flow: (1) at the base of the Shikoku Basin volcanic-rich sediment member, situated ~140 m above the décollement, and particularly (2) below the décollement. The latter must have been rather vigorous, as it was capable of transporting clay minerals over great distances. The fluid at ~140 m above the décollement is characterized by lower than seawater concentrations of Cl- (>=18% seawater dilution). It is 18O-rich and D-poor and has a non-radiogenic, oceanic, or volcanic arc Sr isotopic signature. It originates from "volcanic" clay diagenesis. The fluid below the décollement has also less Cl- than seawater (>20% dilution), is more enriched in 18O and depleted in D than fluid, but its Sr isotopic signature is radiogenic, continentalterrigenous. The source of this fluid is located arcward, is deep-seated, where illitization of the subducted clay minerals, a mixture of terrigenous and volcanic clays, occurs. The 3He/4He ratio below the décollement points to an ~25% mantle contribution. The nature of the physical and chemical discontinuities across the décollement suggests it is overpressured and is forming a leaky "dynamic seal" for fluid flow. In contrast with the situation at Barbados and Peru, where the major tectonic features are mineralized, here, although the complex is extremely fractured and faulted, mineralized macroscopic veins, fractures, and faults are absent. Instead, mineralized microstructures are widespread, indicating a diffuse mode of dewatering.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Isotopic and micropaleontological record of sediments of the Baffin Bay

The oxygen and carbon isotopic compositions of the planktonic foraminifer, Neogloboquadrina pachyderma (sinistral), were determined at 20-cm intervals through the 'composite' top ~ 22 m of sediments at ODP Site 645 (Holes 645B, 645C, 645F, and 645G) and at 10-cm intervals through a 9-m piston core (85-027-016) collected during the Hudson site survey. Quantitative analyses of palynomorphs, notably dinocysts, and of planktonic foraminifers were performed. Organic and nitrogen contents and isotopic composition of nitrogen and carbon in organic matter also were determined. These data provide a high-resolution record of changes that occurred in surface-water masses during the last glacial cycle in Baffin Bay. The basin experienced low planktonic productivity during most of the late Pleistocene, either from dilution in surface water by meltwater discharges from the surrounding ice-sheet or from the presence of a relatively dense sea-ice cover. Peaks of meltwater discharge are indicated by d18O values as low as about 1.5 per mil, correlative d13C- d18O shifts, low concentration of planktonic foraminifers, high concentrations of glacially reworked pre-Quaternary palynomorphs, and low-salinity dinocyst assemblages. As a whole, d18O values ranging between 4.5 and 2.5 per mil allow the establishment of an 18O stratigraphy spanning isotopic stages 5 to 1. Because of the poor core recovery, the general paucity of microflora and microfauna, and the possible occurrence of slumping or debris flow at Site 645, further interpretation remains problematic.

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

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.

Microbial community, biomarker concentrations and their isotopic signature in sediment of Gullfaks and Tommeliten methane seeps in the Northern North Sea

Gullfaks is one of the four major Norwegian oil and gas fields, located in the northeastern edge of the North Sea Plateau. Tommeliten lies in the greater Ekofisk area in the central North Sea. During the cruises HE 208 and AL 267 several seep locations of the North Sea were visited. At the Heincke seep at Gullfaks, sediments were sampled in May 2004 (HE 208) using a video-guided multiple corer system (MUC; Octopus, Kiel). The samples were recovered from an area densely covered with bacterial mats where gas ebullition was observed. The coarse sands limited MUC penetration depth to maximal 30 centimeters and the highly permeable sands did not allow for a high-resolution, vertical subsampling because of pore water loss. The gas flare mapping and videographic observation at Tommeliten indicated an area of gas emission with a few small patches of bacterial mats with diameters <50 cm from most of which a single stream of gas bubbles emerged. The patches were spaced apart by 10-100 m. Sampling of sediments covered by bacterial mats was only possible with 3 small push cores (3.8 cm diameter) mounted to ROV Cherokee. These cores were sampled in 3 cm intervals. Lipid biomarker extraction from 10 -17 g wet sediment was carried out as described in detail elsewhere (Elvert et al., 2003; doi:10.1080/01490450303894). Briefly, defined concentrations of cholestane, nonadecanol and nonadecanolic acid with known delta 13C-values were added to the sediments prior to extraction as internal standards for the hydrocarbon, alcohol and fatty acid fraction, respectively. Total lipid extracts were obtained from the sediment by ultrasonification with organic solvents of decreasing polarity. Esterified fatty acids (FAs) were cleaved from the glycerol head group by saponification with methanolic KOH solution. From this mixture, the neutral fraction was extracted with hexane. After subsequent acidification, FAs were extracted with hexane. For analysis, FAs were methylated using BF3 in methanol yielding fatty acid methyl esters (FAMES). The fixation for total cell counts and CARD-FISH were performed on-board directly after sampling. For both methods, sediments were fixed in formaldehyde solution. After two hours, aliquots for CARD-FISH staining were washed with 1* PBS (10mmol/l sodium phosphate solution, 130mmol/l NaCl, adjusted to a pH of 7.2) and finally stored in a 1:1 PBS:ethanol solution at -20°C until further processing. Samples for total cell counts were stored in formalin at 4°C until analysis. For sandy samples, the total cell count/CARD-FISH protocol was optimized to separate sand particles from the cells. Cells were dislodged from sediment grains and brought into solution with the supernatant by sonicating each sample onice for 2 minutes at 50W. This procedure was repeated four times and supernatants were combined. The sediment samples were brought to a final dilution of 1:2000 to 1:4000 and filtered onto 0.2µm GTTP filters (Millipore, Eschbonn, Germany).

(Table 3) Li concentrations and isotopic compositions in foraminiferal shells, carbonate sediments, and associated pore waters from ODP Sites 131-806 and 138-851

An improved procedure for lithium isotope analysis using Li3PO4 as the ion source has been investigated for application to geological samples. The 7Li/6Li ratio is measured using double rhenium filament thermal ionization mass spectrometry in which isotopic fractionation is minimized at high temperatures. The method produces a stable, high intensity Li+ ion beam that allows measurement of nanogram quantities of lithium. This results in a reduction in sample size of up to 1000 times relative to that required for the established Li2BO2+ method while maintaining a comparable precision of better than 1? (1 sigma). Replicate analyses of the NBS L-SVEC Li2CO3 standard yielded a mean value of 12.1047+/-0.0043 (n=21), which is close to the reported absolute value of 12.02+/-0.03. Intercalibration with a wide range of geological samples shows excellent agreement between the Li3PO4 and Li2BO2+ techniques. Replicate analyses of seawater and a fresh submarine basalt display high precision results that agree with previous measurements. Taking advantage of the high ionization efficiency of the phosphate ion source, we have made the first measurements of the lithium concentration (by isotope dilution) and isotopic composition of calcareous foraminiferal tests and other marine carbonates. Preliminary results indicate that substantial lithium exchange occurs between carbonate sediments and their interstitial waters. In addition, a possible link between lithium paleoceanography and paleoclimate during the last 1000 ky may be derived from planktonic foraminiferal tests. This highly sensitive technique can be applied in the examination of low lithium reservoirs and thereby provide insight into some fundamental aspects of lithium geochemistry.