Stable isotope ratios in shells of marine organisms

Oxygen and carbon isotope analyses have been carried out on calcareous skeletons of important recent groups of organisms. Annual temperature ranges and distinct developmental stages can be reconstructed from single shells with the aid of the micro-sampling technique made possible by modern mass-spectrometers. This is in contrast to the results of earlier studies which used bulk sampIes. The skeletons analysed are from Bermuda, the Philippines, the Persian Gulf and the continental margin off Peru. In these environments, seasonal salinity ranges and thus annual variations in the isotopic composition of the water are small. In addition, environmental parameters are weIl documented in these areas. The recognition of seasonal isotopic variations is dependant on the type of calcification. Shells built up by carbonate deposition at the margin, such as molluscs, are suitable for isotopic studies. Analysis is more difficult where chambers are added at the margin of the shell but where older chambers are simultaneously covered by a thin veneer of carbonate e. g. in rotaliid foraminifera. Organisms such as calcareous algae or echinoderms that thicken existing calcareous parts as weIl as growing in length and breadth are the most difficult to analyse. All organisms analysed show temperature related oxygen-isotope fractionation. The most recent groups fractionate oxygen isotopes in accordance with established d18O temperature relationships (Tab. 18, Fig. 42). These groups are deep-sea foraminifera, planktonic foraminifera, serpulids, brachiopods, bryozoa, almost all molluscs, sea urchins, and fish (otoliths). A second group of organisms including the calcareous algae Padina, Acetabularia, and Penicillus, as weIl as barnacles, cause enrichment of the heavy isotope 18O. Finally, the calcareous algae Amphiroa, Cymopolia and Halimeda, the larger foraminifera, corals, starfish, and holothurians cause enrichment of the lighter isotope 16O. Organisms causing non-equilibrium fractionation also record seasonal temperature variations within their skeletons which are reflected in stable-oxygen-isotope patterns. With the exception of the green algae Halimeda and Penicillus, all organisms analysed show lower d13C values than calculated equilibrium values (Tab. 18, Fig. 42). Especially enriched with the lighter isotope 12C are animals such as hermatypic corals and larger foraminifera which exist in symbiosis with other organisms, but also ahermatypic corals, starfish, and holothurians. With increasing age of the organisms, seven different d13C trends were observed within the skeletons. 1) No d13C variations are observed in deep-sea foraminifera presumably due to relatively stable environmental conditions. 2) Lower d13C values occur in miliolid larger foraminifera and are possibly related to increased growth with increasing age of the foraminifera. 3) Higher values are found in planktonic foraminifera and rotaliid larger foraminifera and can be explained by a slowing down of growth with increasing age. 4) A sudden change to lower d13C values at a distinct shell size occurs in molluscs and is possibly caused by the first reproductive event. 5) A low-high-Iow cycle in calcareous algae is possibly caused by variations in the stage of calcification or growth. 6) A positive correlation between d18O and d13C values is found in some hermatypic corals, all ahermatypic corals, in the septa of Nautilus and in the otoliths of fish. In hermatypic corals from tropical areas, this correlation is the result of the inverse relationship between temperature and light caused by summer cloud cover; in other groups it is inferred to be due to metabolic processes. 7) A negative correlation between d18O and d13C values found in hermatypic corals from the subtropics is explained by the sympathetic relationship between temperature and light in these latitudes. These trends show that the carbon isotope fractionation is controlled by the biology of the respective carbonate producing organisms. Thus, the carbon isotope distribution can provide information on the symbiont-host relationship, on metabolic processes and calcification and growth stages during ontogenesis of calcareous marine organisms.

Geochemistry and isotopic composition of gabbros from ODP Hole 118-375B

Gabbros drilled from the shallow (720 m) east wall of the Atlantis II transform on the Southwest Indian Ridge (SWIR; 32°43.40', 57°16.00') provide the most complete record of the stratigraphy and composition of the oceanic lower crust recovered from the ocean basins to date. Lithologies recovered include gabbro, olivine gabbro, troctolite, trondhjemite, and unusual iron-titanium (FeTi) oxide-rich gabbro containing up to 30% FeTi oxides. The plutonic rock sequence represents a tholeiitic fractionation trend ranging from primitive magmas having Mg numbers of 67 to 69 that fractionated troctolites, to highly evolved liquids that crystallized two-pyroxene, FeTi oxide-rich gabbros and, ultimately, trondhjemite. Isotopic compositions of unaltered Leg 118 gabbros are distinct from Indian Ocean mid-ocean ridge basalts (MORB) in having higher 143Nd/144Nd (0.51301-0.51319) and lower 206Pb/204Pb values (17.35-17.67); 87Sr/86Sr values (0.7025-0.7030) overlap those of SWIR basalts, but are generally lower than MORBs from the Southeast Indian Ridge or the Rodrigues Triple Junction. More than one magma composition may have been introduced into the magma chamber during its crystallization history, as suggested by the higher 87Sr/86Sr, 206Pb/204Pb, and lower 143Nd/144Nd values of chromium-rich olivine gabbros from the bottom of Hole 735B. Whole-rock gabbro and plagioclase mineral separate 87Sr/86Sr values are uniformly low (0.7027-0.7030), irrespective of alteration and deformation. By contrast, 87Sr/86Sr values for clinopyroxene (0.7025-0.7039) in the upper half of Hole 735B are higher than coexisting plagioclase and reflect extensive replacement of clinopyroxene by amphibole. Hydrothermal veins and breccias have elevated 87Sr/86Sr values (0.7029-0.7035) and indicate enhanced local introduction of seawater strontium. Oxygen- and hydrogen-isotope results show that secondary amphiboles have uniform dD values of -49 to -54 per mil and felsic hydrothermal veins range from -46 to - 77 per mil. Oxygen-isotope data for secondary amphibole and visibly altered gabbros range to low values (+1.0-+5.5 per mil), and O-isotope disequilibrium between coexisting pyroxene and plagioclase pairs from throughout the stratigraphic column indicates that seawater interacted with much of the gabbro section, but at relatively low water/rock ratios. This is consistent with the persistence of low 87Sr/86Sr values, even in gabbros that were extensively deformed and altered.

Calcium isotope ratios of porewaters of ODP Leg 204 holes

The calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during Ocean Drilling Program (ODP) provides first insight into the different processes that control Ca geochemistry in clastic marine, organic-rich sedimentary environments. In 4 sites drilled during Leg 204 at Hydrate Ridge (Cascadia Margin, offshore Oregon/USA), sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section. These reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate, which is reflected in a pronounced decrease in calcium concentration. Although Ca isotope fractionation is observed during carbonate precipitation, Ca concentration in the pore fluids from ODP Leg 204 is decoupled from Ca isotopy, which seems to be mainly controlled by the release of light Ca isotopes that completely overprint the carbonate formation effect. Different processes, such as the release of organically bound Ca, ion exchange and ion pair formation may be responsible for the released light Ca. Deeper within the sedimentary section, additional processes such as ash alteration influence the Ca isotopic composition of the porewater. Two sites, drilled into the deeper core of the accretionary prism, reveal the nature of fluids which have reacted with the oceanic basement. These deep fluids are characterized by relatively high Ca concentrations and low d44/40Ca ratios.

Seawater carbonate chemistry and biological processes of foraminifera, Globigerinoides ruber and Globigerinella siphonifera during experiments, 2011

Specimens of two species of planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera, were grown under controlled laboratory conditions at a range of temperatures (18-31 °C), salinities (32-44 psu) and pH levels (7.9-8.4). The shells were examined for their calcium isotope compositions (d44/40Ca) and strontium to calcium ratios (Sr/Ca) using Thermal Ionization Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. Although the total variation in d44/40Ca (~0.3 per mill) in the studied species is on the same order as the external reproducibility, the data set reveals some apparent trends that are controlled by more than one environmental parameter. There is a well-defined inverse linear relationship between d44/40Ca and Sr/Ca in all experiments, suggesting similar controls on these proxies in foraminiferal calcite independent of species. Analogous to recent results from inorganically precipitated calcite, we suggest that Ca isotope fractionation and Sr partitioning in planktic foraminifera are mainly controlled by precipitation kinetics. This postulation provides us with a unique tool to calculate precipitation rates and draws support from the observation that Sr/Ca ratios are positively correlated with average growth rates. At 25 °C water temperature, precipitation rates in G. siphonifera and G. ruber are calculated to be on the order of 2000 and 3000 µmol/m**2/h, respectively. The lower d44/40Ca observed at 29 °C in both species is consistent with increased precipitation rates at high water temperatures. Salinity response of d44/40Ca (and Sr/Ca) in G. siphonifera implies that this species has the highest precipitation rates at the salinity of its natural habitat, whereas increasing salinities appear to trigger higher precipitation rates in G. ruber. Isotope effects that cannot be explained by precipitation rate in planktic foraminifera can be explained by a biological control, related to a vacuolar pathway for supply of ions during biomineralization and a pH regulation mechanism in these vacuoles. In case of an additional pathway via cross-membrane transport, supplying light Ca for calcification, the d44/40Ca of the reservoir is constrained as -0.2 per mill relative to seawater. Using a Rayleigh distillation model, we calculate that calcification occurs in a semi-open system, where less than half of the Ca supplied by vacuolization is utilized for calcite precipitation. Our findings are relevant for interpreting paleo-proxy data on d44/40Ca and Sr/Ca in foraminifera as well as understanding their biomineralization processes.

Oxygen and hydrogen isotopes measured in the Northeast Atlantic

Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 d18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, dD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5 per mil for d18O and 0 to 2 per mil for dD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high d18O (0.5-1.1 per mil) and dD (3-6 per mil) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (d18O: -0.1 to 0.5 per mil; dD: -1 to 4 per mil) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed d18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0.46 described previously by Pierre et al. (1994, J. Mar. Syst. 5 (2), 159-170.) for the tropical to subtropical Northeast Atlantic. This slope decreases to 0.46 for the subtropical North Atlantic Central Water (NACW) and the MOW and to 0.32 for the surface waters of the upper 50 m. The dD-salinity mixing lines have estimated slopes of 3.01 for the complete data, 1.26 for the MOW, 3.47 for the NACW, and 2.63 for the surface waters. The slopes of the d18O-dD relationship are significantly lower than the one for the Global Meteoric Water Line with 5.6 for the complete data set, 2.30 for the MOW, 4.79 for the NACW, and 3.99 for the surface waters. The lower slopes in all the relationships clearly reflect the impact of the evaporation surplus in the subtropics.

Oxygen isotope composition of clinoptilolites

Oxygen isotope ratios were obtained from authigenic clinoptilolites from Barbados Accretionary Complex, Yamato Basin, and Exmouth Plateau sediments (ODP Sites 672, 797, and 762) in order to investigate the isotopic fractionation between clinoptilolite and pore water at early diagenetic stages and low temperatures. Dehydrated clinoptilolites display isotopic ratios for the zeolite framework (delta 18Of) that extend from +18.7? to +32.8? (vs. SMOW). In combination with associated pore water isotope data, the oxygen isotopic fractionation between clinoptilolite and pore fluids could be assessed in the temperature range from 25ºC to 40ºC. The resulting fractionation factors of 1.032 at 25ºC and 1.027 at 40ºC are in good agreement with the theoretically determined oxygen isotope fractionation between clinoptilolite and water. Calculations of isotopic temperatures illustrate that clinoptilolite formation occurred at relatively low temperatures of 17ºC to 29ºC in Barbados Ridge sediments and at 33ºC to 62ºC in the Yamato Basin. These data support a low-temperature origin of clinoptilolite and contradict the assumption that elevated temperatures are the main controlling factor for authigenic clinoptilolite formation. Increasing clinoptilolite delta18Of values with depth indicate that clinoptilolites which are now in the deeper parts of the zeolite-bearing intervals had either formed at lower temperatures (17-20ºC) or under closed system conditions.

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.

Composition of native Cu, Cu isotope and mineral analysis from different samples of ODP and DSDP

Ocean drilling has revealed that, although a minor mineral phase, native Cu ubiquitously occurs in the oceanic crust. Cu isotope systematics for native Cu from a set of occurrences from volcanic basement and sediment cover of the oceanic crust drilled at several sites in the Pacific, Atlantic and Indian oceans constrains the sources of Cu and processes that produced Cu**0. We propose that both hydrothermally-released Cu and seawater were the sources of Cu at these sites. Phase stability diagrams suggest that Cu**0 precipitation is favored only under strictly anoxic, but not sulfidic conditions at circum-neutral pH even at low temperature. In the basaltic basement, dissolution of primary igneous and potentially hydrothermal Cu-sulfides leads to Cu**0 precipitation along veins. The restricted Cu-isotope variations (delta 65Cu = 0.02-0.19 per mil) similar to host volcanic rocks suggest that Cu**0 precipitation occurred under conditions where Cu+-species were dominant, precluding Cu redox fractionation. In contrast, the Cu-isotope variations observed in the Cu**0 from sedimentary layers yield larger Cu-isotope fractionation (delta 65Cu = 0.41-0.95 per mil) suggesting that Cu**0 precipitation involved redox processes during the diagenesis, with potentially seawater as the primary Cu source. We interpret that native Cu precipitation in the basaltic basement is a result of low temperature (20°-65 °C) hydrothermal processes under anoxic, but not H2S-rich conditions. Consistent with positive delta 65Cu signatures, the sediment cover receives major Cu contribution from hydrogenous (i.e., seawater) sources, although hydrothermal contribution from plume fallout cannot be entirely discarded. In this case, disseminated hydrogenous and/or hydrothermal Cu might be diagenetically remobilized and reprecipitated as Cu**0 in reducing microenvironment.

(Table 2) Silicon isotope data for sponge spicules from ODP Hole 113-689B

The silicon isotope composition (d30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The d30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2 per mil to -3.7 per mil (n = 6), corresponding to the production of opal that has a d30Si value 3.8 per mil +/- 0.8 per mil more negative than seawater silicic acid and a fractionation factor (a) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The d30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1 per mil to -3.0 per mil, overlapping the range observed for sponges growing in modern seawater.