Experiment: The effect of temperature, salinity and growth rate on the stable hydrogen isotopic composition of long chain alkenones produced by Emiliania huxleyi and Gephyrocapsa oceanica

Two haptophyte algae, Emiliania huxleyi and Gephyrocapsa oceanica, were cultured at different temperatures and salinities to investigate the impact of these factors on the hydrogen isotopic composition of long chain alkenones synthesized by these algae. Results showed that alkenones synthesized by G. oceanica were on average depleted in D by 30 compared to those of E. huxleyi when grown under similar temperature and salinity conditions. The fractionation factor, alpha alkenones-H2O, ranged from 0.760 to 0.815 for E. huxleyi and from 0.741 to 0.788 for G. oceanica. There was no significant correlation of alpha alkenones-H2O with temperature but a positive linear correlation was observed between alpha alkenones-H2O and salinity with ~3 change in fractionation per salinity unit and a negative correlation between alpha alkenones-H2O and growth rate. This suggests that both salinity and growth rate can have a substantial impact on the stable hydrogen isotopic composition of long chain alkenones in natural environments.

Mineralogy, isotopic composition of oxygen, hydrogen and carbon, and oxygen isotopic temperature of deep-sea silica and coexisting carbonates (Table 1)

Water extracted from opal-CT ("porcellanite", "cristobalite"), granular microcrystalline quartz (chert), and pure fibrous quartz (chalcedony) in cherts from the JOIDES Deep Sea Drilling Project is 56? to 87? depleted in deuterium relative to the water in which the silica formed. This large fractionation is similar in magnitude and sign to that observed for hydroxyl in clay minerals and suggests that water extracted from these forms of silica has been derived from hydroxyl groups within the silica. Delta18O-values for opal-CT at sites 61, 64, 70B and 149 vary from 34.3? to 37.2? and show no direct correlation with depth of burial. Granular microcrystaUine quartz in these cores is 0.5 ? depleted in 18O relative to coexisting opal-CT at sediment depths of 100 m and the depletion increases to 2? for sediments buried below 384 m. These relationships suggest that opal-CT forms before significant burial while granular microcrystalline quartz forms during deeper burial at warmer temperatures. The temperature at which opal-CT forms is thus probably approximately equal to the temperature of the overlying bottom water. Isotopic temperatures deduced for opal-CT formation are preliminary and very approximate, but yield Eocene deep-water temperatures of 5-13°C, and 6°C for the upper Cretaceous sample. Pure euhedral quartz crystals lining a cavity in opal-CT at 388 m in core 8-70B-4-CC have a ~delta18O value of +29.8? and probably formed near maximum burial. The isotopic temperature is approximately 32 ° C.

Benthic foraminifera asemblages and isotopic composition of surface sediment samples off Morocco

The influence of different primary productivity regimes on live (Rose Bengal stained) and dead benthic foraminiferal distribution, as well as on the stable carbon isotopic composition of foraminiferal tests, was investigated in sediment surface samples (0-1 cm) from the upwelling region off Morocco between Cape Ghir (31°N) and Cape Yubi (27°N). A combination of factor analysis, detrended correspondence analysis (DCA) and canonical correspondence analysis (CCA) was applied to the benthic foraminiferal data sets. Five major assemblages for both the live and dead fauna were revealed by factor analysis. In the cape regions organic matter fluxes are enhanced by high chlorophyll-a concentrations in the overlying surface waters. Here, benthic foraminiferal faunas are characterized by identical live and dead assemblages, high standing stocks, and low species delta13C values, indicating constant year-round high productivity. Bulimina marginata dominates the unique fauna at the shallowest station off Cape Ghir indicating highest chlorophyll-a concentrations. Off both capes, the succession of the Bulimina aculeata/Uvigerina mediterranea assemblage, the Sphaeroidina bulloides/Gavelinopsis translucens assemblage, and the Hoeglundina elegans assemblage from the shelf to the deep sea reflects the decrease in chlorophyll-a concentrations, hence the export flux. In contrast, the area between the capes is characterized by differently composed live and dead assemblages, low standing stocks, and less depleted delta13C values, thus reflecting low primary productivity. High foraminiferal numbers of Epistominella exigua, Eponides pusillus, and Globocassidulina subglobosa in the dead fauna indicate a seasonally varying primary productivity signal. Significantly lower mean delta13C values were recorded in Bulimina mexicana, Cibicidoides kullenbergi, H. elegans, U. mediterranea and Uvigerina peregrina. Cibicidoides wuellerstorfi is a faithful recorder of bottom water delta13C in the Canary Islands regions. The mean delta13C signal of this species is not significantly influenced by constant high organic matter fluxes. The species-specific offset between live and dead specimens is the same.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

Molecular hydrogen (H2) mixing ratio and stable isotopic composition (dD) at the Cabauw tall tower in the Netherlands (2008-2012)

Measurements of the stable isotopic composition (dD(H2) or dD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (X(H2)) measurements for understanding the atmospheric H2 cycle. dD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by X(H2) values that reach up to 1 ppm and low dD values. An isotopic source signature analysis yields an apparent source signature below -400 per mil, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (-340 per mil), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in (H2) at lower sampling levels (20 and 60m) with respect to higher sampling levels (120 and 200m). There was a significant shift to lower median dD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising features come to light when a non-background location is studied, revealing remaining gaps in our understanding.

Geochemistry, and Nd- and Pb-isotopic composition of basalts from the upper oceanic crust of the Costa Rica Rift

The DSDP/ODP Hole 504B, drilled in the 5.9 Ma southern flank of the Costa Rica Rift, represents the deepest section through modern ocean floor basaltic basement. The hole penetrates a 570 m thick volcanic zone, a 210 m thick transition zone of volcanic rocks and dykes, and 1056 m of dykes. A representative selection of these basalt types has been investigated with respect to Nd and Pb isotopes. The epsilonNd of the basalts varies from 7.62 to 11.16. This range in the Nd-isotope composition represents about 67% of the total range reported for Pacific MORB. The Pb-isotope composition also shows significant variation, with 206Pb/204Pb varying from 17.90 to 18.82. The isotopic data show that a small volume of enriched mantle existed in the source. The large ranges in isotopic composition in a single drill hole demonstrate the importance of small-scale mantle heterogeneities in the petrogenesis of MORB. Fractional melting and extraction of small magma batches by channelled flow, and small, short-lived crustal magma reservoirs, with limited potential for mixing of the mantle derived magmas, are favored by these isotopic data.

(Table 1) K, Rb and Sr concentrations and Sr isotopic composition of sediments and igneous rocks from DSDP Hole 30-286

To evaluate the possible contribution of ocean floor sediments during the genesis of the volcanism of Vanuatu (New Hebrides) active margin, we have determined the balance of Sr isotopes and K, Rb and Sr contents for the stratigraphic column of site 286 (leg 30, DSDP). This site is located on the oceanic plate that will be subducted. Analyses have been performed on sedimentary and igneous rocks, before and after acid leaching. The Sr isotopic data do not support the occurrence of some continental component in arc magmas of this active margin which is really intraoceanic. It is demonstrated that the d'Entrecasteaux fracture zone results from the intense fracturing of typical oceanic crust. The analyses of the volcanogenic components of the sediments show a change in the source of volcanoclastic detritus from the Loyalty islands in the Eocene to the volcanic arc of Vanuatu (New Hebrides) during Pliocene and Quaternary times. The determined balance of Sr isotopes and of K, Rb, Sr contents, may be used for calculation of multicomponent melting mixing models for the origin of Vanuatu arc magmas, but we emphasize that in these models the Sr isotopes cannot be considered as an appropriated tracer of sediment contribution.

Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ∼3.7 Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9Be/10Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patterns and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9Be/10Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ56/54Fe) in subsamples of 1-3 mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0 ± 0.4 mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ56/54Fe values, when averaged over sample increments representing 0.25 to 0.75 Ma, were homogeneous within uncertainty along the nodule radius, at -0.12 ± 0.07 ‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ56/54Fe value of -0.12 ‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.

Formation of seep carbonates along the makran convergent margin, northern Arabian sea and a molecular and isotopic approach to constrain the carbon isotopic composition of parent methane

Authigenic carbonate deposits have been sampled with the remotely operated vehicle ‘MARUM-QUEST 4000 m’ from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The δ18Ocarbonate values range from 1.3 to 4.2‰ V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low δ13Ccarbonate values (as low − 54.6‰ V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by δ13Cmethane values ranging from − 70.3 to − 66.7‰ V-PDB, and also by back-calculations considering δ13Cmethane values of carbonate and incorporated lipid biomarkers. These calculations (Δδ13Cmethane–carbonate, Δδ13CANME–methane, Δδ13CMOX–methane) prove to be useful to assess the carbon stable isotope composition of seeping methane if this has not been determined in the first place; such an approach represents a useful tool to reconstruct fluid composition of ancient seeps. AOM is also revealed by lipid biomarkers of anaerobic methane oxidizing archaea such as crocetane, pentamethylicosane (PMI), and sn2-hydroxyarchaeol strongly depleted in 13C (δ13C values as low as − 127‰ V-PDB). Biomarkers of sulphate-reducing bacteria are also abundant, showing slightly less negative δ13C values, but still significantly 13C-depleted (average values as low as − 101‰). Other bacterial biomarkers, such as bacteriohopanepolyols (BHPs), hopanols, and hopanoic acids are detected in most carbonates, but are particularly common in seep carbonates from the non-OMZ sites. The BHP patterns of these carbonates and their low δ13C values resemble patterns of aerobic methanotrophic bacteria. In the shallower OMZ sites, BHPs revealed much lower contents and varying compositions, most likely reflecting other sources than aerobic methanotrophic bacteria. 230Th/U carbonate ages indicate that AOM-induced carbonate precipitation at the deeper non-OMZ seeps occurred mainly during the late Pleistocene-Holocene transition, i.e. between 19 and 15 ka before present, when the global sea level was lower than today.

(Table 1) Isotopic and trace-element composition of ODP Leg 127/128 basalts

The western Pacific includes many volcanic island arc and backarc complexes, yet multi-isotopic studies of them are rare. Basement rocks of the Sea of Japan backarc basin were encountered at Sites 794,795, and 797, and consisted of basaltic sills and lava flows. These rocks exhibit a broad range in isotopic composition, broader than that seen in any other western Pacific arc or backarc system: 87Sr/86Sr = 0.70369 to 0.70499, 143Nd/144Nd = 0.51267 to 0.51317, 206Pb/204Pb = 17.64 to 18.36. The samples form highly correlated arrays between very depleted mid-ocean ridge basalt (MORB) and the Pacific pelagic sediment fields on Pb-Pb plots. Similarly, on plots of Sr-Pb and Nd-Pb, the Sea of Japan samples lie on mixing curves between depleted mantle and enriched mantle ("EM II"), which is interpreted to be of average crustal or pelagic sediment composition. The source of these backarc rocks appears to be a MORB-like mantle source, contaminated by pelagic sediments. Unlike the Mariana and Izu arc/backarc systems, Japanese arc and backarc rocks are indistinguishable from each other in a Sr-Nd isotope plot, and have similar trends in Pb-Pb plots. Thus, sediment contamination of the mantle wedge appears to control the isotopic compositions of both the arc and backarc magmas. Two-component mixing calculations suggest that the percentage of sediments in the magma source varies from 0.5% to 2.5%.

Isotopic and trace element composition of basalts from DSDP Leg 82 Holes

Sr and Nd isotopic composition of 23 basalts from Sites 556-559 and 561-564. are reported. The 87Sr/86Sr ratios in fresh glasses and leached whole rocks range from 0.7025 to 0.7034 and are negatively correlated with the initial 143Nd/ 144Nd compositions, which range from 0.51315 to 0.51289. The Sr and Nd isotopic compositions (in glasses or leached samples) lie within the fields of mid-ocean ridge basalts (MORB) and ocean island basalts (OIB) from the Azores on the Nd-Sr mantle array/fan plot. In general, there is a correlation between the trace element characteristics and the 143Nd/144Nd composition (i.e., samples with Hf/Ta>7 and (Ce/Sm)N<1 [normal-MORB] have initial 143Nd/144Nd>0.51307, whereas samples with Hf/Ta<7 and (Ce/Sm)N>1 (enriched-MORB) have initial 143Nd/144Nd compositions <0.51300). A significant deviation from this general rule is found in Hole 558, where the N-MORB can have, within experimental limits, identical isotopic compositions to those found in associated E-MORB. The plume-depleted asthenosphere mixing hypothesis of Schilling (1975), White and Schilling (1978) and Schilling et al. (1977) provides a framework within which the present data can be evaluated. Given the distribution and possible origins of the chemical and isotopic heterogeneity observed in Leg 82 basalts, and some other basalts in the area, it would appear that the Schilling et al. model is not entirely satisfactory. In particular, it can be shown that trace element data may incorrectly estimate the plume component and more localized mantle heterogeneity (both chemical and isotopic) may be important.