Size-related isotopic trends in Maastrichtian planktic foraminifera of DSDP Core 44-390A (Appendix B)

Stable isotope analyses were performed on ontogenetic dissections of four taxa of low latitude Late Cretaceous planktonic foraminifera from DSDP Hole 390A. The species studied include Planoglobulina acervulinoides, Planoglobulina multicamerata, Pseudoguembelina palpebra, and Racemiguembelina fructicosa. Delta18O and delta13C data indicate a deeper surface water paleohabitat for P. multicamerata than the other three taxa, and ontogenetic increases in delta18O values suggest all these taxa underwent vertical migrations from shallow to deeper surface waters. Changes in delta13C values through ontogeny include sharp increases in delta13C composition in the juvenile size intervals, a decrease in the rate of delta13C change through intermediate size intervals, and reversals to a negative trend in delta13C values in terminal size intervals. The intermediate and terminal growth changes in delta13C signals are similar to ontogenetic trends observed in some extant and Paleogene planktonic foraminifera and may result from decreasing metabolic rates through ontogeny or endosymbiont digestion prior to gametogenesis. The ontogenetic delta13C increases of 1.04?, 0.76?, 0.83?, and 0.77? in R. fructicosa, P. palpebra, P. acervulinoides, and P. multicamerata, respectively, may indicate the presence of photosymbionts. However, our review and critique of the current literature discussing photosymbiont effects on stable isotope values in living and fossil planktonic foraminifera suggests that conclusions regarding the presence of photosymbionts in fossil taxa may be more equivocal than previously thought.

Nd and Sm content and isotopic composition of the carbonate-free clay fraction of sediment core HU90-013-013

Sm-Nd concentrations and Nd isotopes were investigated in the fine fraction of two Labrador Sea cores to reconstruct the deep circulation patterns through changes in sedimentary supply since the last glacial stage. Three sources are involved: the North American Shield, Palaeozoic rocks from northeastern Greenland, and mid-Atlantic volcanism. The variable input of these sources provides constraints on the relative sedimentary supply, in conjunction with inception of deep currents. During the last glacial stage a persistent but sluggish current occurred inside the Labrador Basin. An increasing discharge of volcanic material driven by the North East Atlantic Deep Water is documented since 14.3 kyr, signaling the setup of a modern-like deep circulation pattern throughout the Labrador, Irminger, and Iceland basins. During the last deglacial stage the isotopic record was punctually influenced by erosion processes related mainly to ice-sheet instabilities, especially 11.4, 10.2, and 9.2 kyr ago.

Biogeochemical, sedimentological and isotopic sediment record of Lake Dojran

A Late Glacial to Holocene sediment sequence (Co1260, 717 cm) from Lake Dojran, located at the boarder of the F.Y.R. of Macedonia and Greece, has been investigated to provide information on climate variability in the Balkan region. A robust age-model was established from 13 radiocarbon ages, and indicates that the base of the sequence was deposited at ca. 12 500 cal yr BP, when the lake-level was low. Variations in sedimentological (H2O, TOC, CaCO3, TS, TOC/TN, TOC/TS, grain-size, XRF, d18Ocarb, d13Ccarb, d13Corg) data were linked to hydro-acoustic data and indicate that warmer and more humid climate conditions characterised the remaining period of the Younger Dryas until the beginning of the Holocene. The Holocene exhibits significant environmental variations, including the 8.2 and 4.2 ka cooling events, the Medieval Warm Period and the Little Ice Age. Human induced erosion processes in the catchment of Lake Dojran intensified after 2800 cal yr BP.

Chemical and isotopic composition of carbonate veins from ODP Leg 209

Carbonate veins hosted in ultramafic basement drilled at two sites in the Mid Atlantic Ridge 15°N area record two different stages of fluid-basement interaction. A first generation of carbonate veins consists of calcite and dolomite that formed syn- to postkinematically in tremolite-chlorite schists and serpentine schists that represent gently dipping large-offset faults. These veins formed at temperatures between 90 and 170 °C (oxygen isotope thermometry) and from fluids that show intense exchange of Sr and Li with the basement (87Sr/86Sr = 0.70387 to 0.70641, d7Li L-SVEC = + 3.3 to + 8.6 per mil). Carbon isotopic compositions range to high d13C PDB values (+ 8.7 per mil), indicating that methanogenesis took place at depth. The Sr-Li-C isotopic composition suggests temperatures of fluid-rock interaction that are much higher (T > 350-400 °C) than the temperatures of vein mineral precipitation inferred from oxygen isotopes. A possible explanation for this discrepancy is that fluids cooled conductively during upflow within the presumed detachment fault. Aragonite veins were formed during the last 130 kyrs at low-temperatures within the uplifted serpentinized peridotites. Chemical and isotopic data suggest that the aragonites precipitated from cold seawater, which underwent overall little exchange with the basement. Oxygen isotope compositions indicate an increase in formation temperature of the veins by 8-12 °C within the uppermost ~ 80 m of the subseafloor. This increase corresponds to a high regional geothermal gradient of 100-150 °C/km, characteristic of young lithosphere undergoing rapid uplift.

Molecular and isotopic compositions of hydrocarbons at DSDP Site 76-533

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (d13C = -68 per mil; C1/C2 = 5000) was the dominant gas (>90%); (2) little fractionation in the C1/C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experiments; (3) the percent of C3, i-C4, and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) C1/C2 ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also contained trace amounts of saturated, acyclic, cyclic, and aromatic C5-C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (d13C of -68 per mil for methane and a C1/C2 ratio of about 6000). Regular trends in the d13C of methane (about -95 to -60 per mil) and C1/C2 ratios (about 25000 to 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

(Table 1) Li, B and Sr isotopic composition and concentration in ODP Leg 209 samples

Spinel harzburgites from ODP Leg 209 (Sites 1272A, 1274A) drilled at the Mid-Atlantic ridge between 14°N and 16°N are highly serpentinized (50-100%), but still preserve relics of primary phases (olivine >= orthopyroxene >> clinopyroxene). We determined whole-rock B and Li isotope compositions in order to constrain the effect of serpentinization on d11B and d7Li. Our data indicate that during serpentinization Li is leached from the rock, while B is added. The samples from ODP Leg 209 show the heaviest d11B (+29.6 to +40.52 per mil) and lightest d7Li (-28.46 to +7.17 per mil) found so far in oceanic mantle. High 87Sr/86Sr ratios (0.708536 to 0.709130) indicate moderate water/rock ratios (3 to 273, on the average 39), in line with the high degree of serpentinization observed. Applying the known fractionation factors for 11B/10B and 7Li/6Li between seawater and silicates, serpentinized peridotite in equilibrium with seawater at conditions corresponding to those of the studied drill holes (pH: 8.2; temperature: 200 °C) should have d11B of +21.52 per mil and d7Li of +9.7 per mil. As the data from ODP Leg 209 are clearly not in line with this, we modelled a process of seawater-rock interaction where d11B and d7Li of seawater evolve during penetration into the oceanic plate. Assuming chemical equilibrium between fluid and a rock with d11B and d7Li of ODP Leg 209 samples, we obtain d11B and d7Li values of +50 to +60 per mil, -2 to +12 per mil, respectively, for the coexisting fluid. In the oceanic domain, no hydrothermal fluids with such high d11B have yet been found, but are predicted by theoretical calculations. Combining the calculated water/rock ratios with the d7Li and d11B evolution in the fluid, shows that modification of d7Li during serpentinization requires higher water/rock ratios than modification of d11B. Extremely heavy d11B in serpentinized oceanic mantle can potentially be transported into subduction zones, as the B budget of the oceanic plate is dominated by serpentinites. Extremely light d7Li is unlikely to survive as the Li budget is dominated by the oceanic crust, even at small fractions.

(Table 1) Gas molecules, isotopic composition and delta Deuterium in DSDP Holes 95-603D and 95-613

Methane is the major hydrocarbon gas measured in Vacutainer samples from Holes 603D and 613 ( C1/sumCn > 0.999). In Hole 613 the concentration of this dry hydrocarbon gas is highest (7.4 x 10 **5 ppm max.) in the upper 60 to 120 m, then decreases erratically to low trace levels by 261 m sub-bottom (lower Pliocene). No gas accumulations were observed in older sediments. Methane from both holes is strongly depleted in both 13C (d13C, - 75 to -85 per mil) and deuterium (D/H, - 175 to -262 per mil), indicating the biogenic origin of the methane. The C and H isotopic compositions support methanogenesis via the CO2-reduction pathway; this is also corroborated by the dissolved-sulfate and alkalinity minima at these depths. The relationship between D/H of the methane and coexisting interstitial water from Site 613 further show the methanogenesis to be primarily by CO2 reduction.

Depth, age, strontium isotopic ratios and trace elemental ratios of samples from thirteen DSDP and ODP holes

Large variations exist between published mid-Cretaceous (late Barremian to early Turonian stages) seawater Sr-isotope stratigraphies; this has resulted in disparate interpretations of crustal production rates. We report on a detailed investigation of seawater Sr-isotope stratigraphy based on foraminifers and, where available, on inoceramid bivalves from 12 mid-Cretaceous Deep Sea Drilling Project and Ocean Drilling Program sections. The effects of diagenesis are assessed using scanning electron microscope observations and trace-elemental analyses, but are best distinguished by comparing the 87Sr/86Sr values of similar-age samples from different sites. Strontium-isotope analyses compiled from 9 of 12 sites that have detailed age control define one band of common values. This band is used as a composite curve, which presumably represents seawater 87Sr/86Sr values. The composite curve shows a "trough" of markedly lower 87Sr/86Sr values in the Aptian and early Albian stages, higher but constant values for the middle Albian-Cenomanian stages, followed by a decrease in 87Sr/86Sr values in the early Turonian. Variations between published mid-Cretaceous Sr-isotope records result from diagenetic alteration, analytical problems, and the diverse biostratigraphic approaches and assumptions used to estimate sample ages. When preexisting age data are made consistent, the composite record shows close similarities with data sets derived from measurements of macrofossils in land sections of Europe and North America. The interval of decreased 87Sr/86Sr values in the Aptian-Albian stages overlaps with the pulse of mid-plate volcanic activity that produced the Ontong Java, Manihiki, and Kerguelen Plateaus. The exact age and the shape of the trough, however, are consistent with increased spreading rates at oceanic ridges, given the existing data on the timing of mid-plate volcanic activity.

(Table S1) Trace element and isotopic compositions of anhydrites sampled in the Manus Basin, Papua New Guinea

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate d34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate d34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.

(Table 1) Strontium isotopic ratios of interstitial waters from ODP Leg 125 holes

The strontium isotopic data presented here are from interstitial waters squeezed from unconsolidated serpentine, an unusual type of substrate that was recovered from Mariana and Bonin forearc seamounts and has not been previously drilled by the Deep Sea Drilling Project or Ocean Drilling Program. The texture and composition of some of these serpentine deposits from Conical Seamount, located on the Mariana forearc, indicate emplacement as low- or high-viscosity, cold gravitational flows, which are therefore neither sediment nor igneous rock. The strontium isotopic ratios of the interstitial waters from the unconsolidated serpentine range from 0.70912 to 0.70525 and trend toward a relatively less radiogenic composition with increasing sub-bottom depth. These strontium isotopic ratios are derived from at least two strontium sources: seawater and igneous. The strontium isotopic gradients from the interstitial waters from the Leg 125 sites are probably the result of diffusive transport of strontium from an igneous source deep within the lithosphere that may be contaminated with subducted or underplated sediment.