Sr/Ca and Cd/Ca ratios of benthic foraminifera in surface deep-sea sediments

Measurements of Sr/Ca of benthic foraminifera show a linear decrease with water depth which is superimposed upon significant variability identified by analyses of individual foraminifera. New data for Cd/Ca support previous work in defining a contrast between waters shallower and deeper than ~2500 m. Measured element partition coefficients in foraminiferal calcium carbonate relative to sea water (D) have been described by means of a one-box model in which elements are extracted by Rayleigh distillation from a biomineralization reservoir that serves for calcification with a constant fractionation factor (alpha), such that D = (1 - f**alpha)/(l - f), where f is the proportion of Ca remaining after precipitation. A modification to the model recognises differences in element speciation. The model is consistent with differences between D[Sr], D[Ba], and D[Cd] in benthic but not planktonic foraminifera. Depth variations in D for Sr and Ba are consistent with the model, as are differences in depth variation of D[Cd] in calcitic and aragonitic benthic foraminifera. The shallower depth variations may reflect increasing calcification rates with increasing water depth to an optimum of about 2500 m. Observations of unusually lower DCd for some deep waters, not accompanied by similar [Sr], or D[Ba] may be because of dissolution or a calcification response to a lower carbonate saturation state.

(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.

U-Pb geochronology and Nd isotope contributions to the interpretation of a peculiar ring massif: the Santa Eulália plutonic complex (SW Iberia, Portugal)

The Santa Eulalia plutonic complex (SEPC) is a late-Variscan granitic body placed in the Ossa-Morena Zone. The host rocks of the complex belong to metamorphic formations from Proterozoic to Lower Paleozoic. The SEPC is a ring massif (ca. 400 km2 area) composed by two main granitic facies with different colours and textures. From the rim to the core, there is (i) a peripheral pink medium- to coarse-grained granite (G0 group) involving large elongated masses of mafic and intermediate rocks, from gabbros to granodiorites (M group), and (ii) a central gray medium-grained granite (G1 group). The mafic to intermediate rocks (M group) are metaluminous and show wide compositions: 3.34–13.51 wt% MgO; 0.70–7.20 ppm Th; 0.84–1.06 (Eu/Eu*)N (Eu* calculated between Sm and Tb); 0.23–0.97 (Nb/Nb*)N (Nb* calculated between Th and La). Although involving the M-type bodies and forming the outer ring, the G0 granites are the most differentiated magmatic rocks of the SEPC, with a transitional character between metaluminous and peraluminous: 0.00–0.62 wt% MgO; 15.00–56.00 ppm Th; and 0.19–0.42 (Eu/Eu*)N ; 0.08–0.19 (Nb/Nb*)N [1][2]. The G1 group is composed by monzonitic granites with a dominant peraluminous character and represents the most homogeneous compositional group of the SEPC: 0.65–1.02 wt% MgO; 13.00–16.95 ppm Th; 0.57–0.70 (Eu/Eu*)N ; 0.14–0.16 (Nb/Nb*)N . According to the SiO2 vs. (Na2O+K2O–CaO) relationships, the M and G1 groups predominantly fall in the calc-alkaline field, while the G0 group is essencially alkali-calcic; on the basis of the SiO2 vs. FeOt/(FeOt+MgO) correlation, SEPC should be considered as a magnesian plutonic association [3]. New geochronological data (U-Pb on zircons) slightly correct the age of the SEPC, previously obtained by other methods (290 Ma, [4]). They provide ages of 306  2 Ma for the M group, 305  6 Ma for the G1 group, and 301  4 Ma for the G0 group, which confirm the late-Variscan character of the SEPC, indicating however a faintly older emplacement, during the Upper Carboniferous. Recent whole-rock isotopic data show that the Rb-Sr system suffered significant post-magmatic disturbance, but reveal a consistent set of Sm-Nd results valuable in the approach to the magmatic sources of this massif: M group (2.9 < Ndi < +1.8); G1 group (5.8 < Ndi < 4.6); G0 group (2.2 < Ndi < 0.8). These geochemical data suggest a petrogenetic model for the SEPC explained by a magmatic event developed in two stages. Initially, magmas derived from long-term depleted mantle sources (Ndi < +1.8 in M group) were extracted to the crust promoting its partial melting and extensive mixing and/or AFC magmatic evolution, thereby generating the G1 granites (Ndi < 4.6). Subsequently, a later extraction of similar primary magmas in the same place or nearby, could have caused partial melting of some intermediate facies (e.g. diorites) of the M group, followed by magmatic differentiation processes, mainly fractional crystallization, able to produce residual liquids compositionally close to the G0 granites (Ndi < 0.8). The kinetic energy associated with the structurally controlled (cauldron subsidence type?) motion of the G0 liquids to the periphery, would have been strong enough to drag up M group blocks as those occurring inside the G0 granitic ring.

Development of new analytical procedures of isotope geochemistry by mass spectrometry. Application to the study of high-pressure metamorphic rocks from the Iberian Massif

319 p.

The 1998-2001 submarine lava balloon eruption at the Serreta Ridge (Azores archipelago): constraints from volcanic facies architecture, isotope geochemistry and magnetic data

The most recent submarine eruption observed offshore the Azores archipelago occurred between 1998-2001 along the submarine Serreta ridge (SSR), ~4-5 nautical miles WNW of Terceira Island. This submarine eruption delivered abundant basaltic lava balloons floating at the sea surface and significantly changed the bathymetry around the eruption area. Our work combines bathymetry, volcanic facies cartography, petrography, rock magnetism and geochemistry in order to (1) track the possible vent source at seabed, (2) better constrain the Azores magma source(s) sampled through the Serreta submarine volcanic event, and (3) interpret the data within the small-scale mantle source heterogeneity framework that has been demonstrated for the Azores archipelago. Lava balloons sampled at sea surface display a radiogenic signature, which is also correlated with relatively primitive (low) 4He/3He isotopic ratios. Conversely, SSR lavas are characterized by significantly lower radiogenic 87Sr/86Sr, 206Pb/204Pb and 208Pb/204Pb ratios than the lava balloons and the onshore lavas from the Terceira Island. SSR lavas are primitive, but incompatible trace-enriched. Apparent decoupling between the enriched incompatible trace element abundances and depleted radiogenic isotope ratios is best explained by binary mixing of a depleted MORB source and a HIMU­type component into magma batches that evolved by similar shallower processes in their travel to the surface. The collected data suggest that the freshest samples collected in the SSR may correspond to volcanic products of an unnoticed and more recent eruption than the 1998-2001 episode.

In search of a hidden long-term isolated sub-chondritic 142Nd/144Nd reservoir in the deep mantle : implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic 142Nd/144Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in 186Os/188Os and 187Os/188Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic 143Nd/144Nd and high 207Pb/206Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic 142Nd/144Nd. High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable 142Nd/144Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle. We then evaluate mass balance in the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε143Nd estimates of the reservoirs in the μ142Nd = 0 Earth, where μ142Nd is ((measured 142Nd/144Nd/terrestrial standard 142Nd/144Nd)−1 * 10−6) and the μ142Nd = 0 Earth is the proportion of the silicate Earth with 142Nd/144Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd unless the μ142Nd = 0 Earth has a ε143Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age 142Nd–143Nd isochron for the Earth intersects μ142Nd = 0 at ε143Nd of +8 ± 2 providing a minimum ε143Nd for the μ142Nd = 0 Earth. The high ε143Nd of the μ142Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε143Nd. If the EER formed early after solar system formation (0–70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ142Nd = 0 Earth must have a bulk ε143Nd more radiogenic than DMM and additional high ε143Nd material is required to balance the Nd isotope systematics of the Earth.

Use of 3D visualisation to enhance groundwater stable isotope data and its interpretation, Lockyer Valley, southeast Queensland

The use of stable isotope ratios δ18O and δ2H are well established in assessment of groundwater systems and their hydrology. The conventional approach is based on x/y plots and relation to various MWL’s, and plots of either ratio against parameters such as Clor EC. An extension of interpretation is the use of 2D maps and contour plots, and 2D hydrogeological vertical sections. An enhancement of presentation and interpretation is the production of “isoscapes”, usually as 2.5D surface projections. We have applied groundwater isotopic data to a 3D visualisation, using the alluvial aquifer system of the Lockyer Valley. The 3D framework is produced in GVS (Groundwater Visualisation System). This format enables enhanced presentation by displaying the spatial relationships and allowing interpolation between “data points” i.e. borehole screened zones where groundwater enters. The relative variations in the δ18O and δ2H values are similar in these ambient temperature systems. However, δ2H better reflects hydrological processes, whereas δ18O also reflects aquifer/groundwater exchange reactions. The 3D model has the advantage that it displays borehole relations to spatial features, enabling isotopic ratios and their values to be associated with, for example, bedrock groundwater mixing, interaction between aquifers, relation to stream recharge, and to near-surface and return irrigation water evaporation. Some specific features are also shown, such as zones of leakage of deeper groundwater (in this case with a GAB signature). Variations in source of recharging water at a catchment scale can be displayed. Interpolation between bores is not always possible depending on numbers and spacing, and by elongate configuration of the alluvium. In these cases, the visualisation uses discs around the screens that can be manually expanded to test extent or intersections. Separate displays are used for each of δ18O and δ2H and colour coding for isotope values.

A vibrational spectroscopic study of the mineral hinsdalite (Pb,Sr)Al3(PO4)(SO4)(OH)6

The objective of this research is to determine the molecular structure of the mineral hinsdalite using vibrational spectroscopy. The mineral hinsdalite (Pb,Sr)Al3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites. The mineral is interesting because it contains two oxyanions, phosphate and sulphate, which is unusual. The formation of hinsdalite offers a mechanism for the removal of phosphate from the environment. The mineral has been characterised by Raman spectroscopy and infrared spectroscopy. The spectra are then related to the molecular structure of the mineral. Bands at various wavenumbers are assigned to the different vibrational modes of hinsdalite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. The Raman spectrum is characterised by an intense sharp band at 982 cm-1 with a component band at 997 cm-1 assigned to the ν1 (PO4)3- symmetric stretching modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated. Hinsdalite is characterised by disordered phosphate/sulphate tetrahedra and non-equivalent phosphate units are observed in the vibrational spectrum of hinsdalite.

Volcanology and petrology of submarine volcanoes of the New Hebrides island arc

The New Hebrides Island Arc, an intra-oceanic island chain in the southwest Pacific, is formed by subduction of the Indo-Australian Plate beneath the Pacific Plate. The southern end of the New Hebrides Island Arc is an ideal location to study the magmatic and tectonic interaction of an emerging island arc as this part of the island chain is less than 3 million years old. A tectonically complex island arc, it exhibits a change in relative subduction rate from ~12cm/yr to 6 cm/yr before transitioning to a left-lateral strike slip zone at its southern end. Two submarine volcanic fields, Gemini-Oscostar and Volsmar, occur at this transition from normal arc subduction to sinistral strike slip movement. Multi-beam bathymetry and dredge samples collected during the 2004 CoTroVE cruise onboard the RV Southern Surveyor help define the relationship between magmatism and tectonics, and the source for these two submarine volcanic fields. Gemini-Oscostar volcanic field (GOVF), dominated by northwest-oriented normal faults, has mature polygenetic stratovolcanoes with evidence for explosive subaqueous eruptions and homogeneous monogenetic scoria cones. Volsmar volcanic field (VVF), located 30 km south of GOVF, exhibits a conjugate set of northwest and eastwest-oriented normal faults, with two polygenetic stratovolcanoes and numerous monogenetic scoria cones. A deep water caldera provides evidence for explosive eruptions at 1500m below sea level in the VVF. Both volcanic fields are dominated by low-K island arc tholeiites and basaltic andesites with calcalkalic andesite and dacite being found only in the GOVF. Geochemical signatures of both volcanic fields continue the along-arc trend of decreasing K2O with both volcanic fields being similar to the New Hebrides central chain lavas. Lavas from both fields display a slight depletion in high field strength elements and heavy rare earth elements, and slight enrichments in large-ion lithophile elements and light rare earth elements with respect to N-MORB mantle. Sr and Nd isotope data correlate with heavy rare earth and high field strength element data to show that both fields are derived from depleted mantle. Pb isotopes define Pacific MORB mantle sources and are consistent with isotopic variation along the New Hebrides Island Arc. Pb isotopes show no evidence for sediment contamination; the subduction component enrichment is therefore a slab-derived enrichment. There is a subtle spatial variation in source chemistry which sees a northerly trend of decreasing enrichment of slab-derived fluids.

Biological responses of human bone marrow mesenchymal stem cells to Sr-M-Si (M = Zn, Mg) silicate bioceramics

Strontium (Sr), Zinc (Zn), magnesium (Mg), and silicon (Si) are reported to be essential trace elements for the growth and mineralization of bone. We speculated that the combination of these bioactive elements in bioceramics may be effective to regulate the osteogenic property of boneforming cells. In this study, two Sr-containing silicate bioceramics, Sr2ZnSi2O7 (SZS) and Sr2MgSi2O7 (SMS), were prepared. The biological response of human bone marrow mesenchymal stem cells (BMSCs) to the two bioceramics (in the forms of powders and dense ceramic bulks) was systematically studied. In powder form, the effect of powder extracts on the viability and alkaline phosphatase (ALP) activity of BMSCs was investigated. In ceramic disc form, both direct and indirect coculture of BMSCs with ceramic discs were used to investigate their biological response, including attachment, proliferation, ALP activity, and bone-related genes expression. Beta-tricalcium phosphate (b-TCP) and akermanite (Ca2MgSi2O7, CMS) were used as control materials. The results showed that the Sr, Zn, and Si (or Sr, Mg, and Si)-containing ionic products from SZS and SMS powders enhanced ALP activity of BMSCs, compared to those from b-TCP. Both SZS and SMS ceramic discs supported the growth of BMSCs, and most importantly, significantly enhanced the ALP activity and bone-related genes expression of BMSCs as compared to b-TCP. The results suggest that the specific combination of bioactive ions (Sr, Zn, Si, e.g.) in bioceramics is a viable way to improve the biological performance of biomaterials, and the form of materials and surface properties were nonnegligible factors to influence cell response.

Partial melt processing and electrical properties of Bi-Sr-Ca-Cu-o superconducting thick films on (100) MgO substrates

Superconducting thick films of Bi2Sr2CaCu2Oy (Bi-2212) on single-crystalline (100) MgO substrates have been prepared using a doctor-blade technique and a partial-melt process. It is found that the phase composition and the amount of Ag addition to the paste affect the structure and superconducting properties of the partially melted thick films. The optimum heat treatment schedule for obtaining high Jc has been determined for each paste. The heat treatment ensures attainment of high purity for the crystalline Bi-2212 phase and high orientation of Bi-2212 crystals, in which the c-axis is perpendicular to the substrate. The highest Tc, obtained by resistivity measurement, is 92.2 K. The best value for Jct (transport) of these thick films, measured at 77 K in self-field, is 8 × 10 3 Acm -2.

Reaction products between Bi-Sr-Ca-Cu-oxide thick films and alumina substrates

The structure and composition of reaction products between Bi-Sr-Ca-Cu-oxide (BSCCO) thick films and alumina substrates have been characterized using a combination of electron diffraction, scanning electron microscopy and energy dispersive X-ray spectrometry (EDX). Sr and Ca are found to be the most reactive cations with alumina. Sr4Al6O12SO4 is formed between the alumina substrates and BSCCO thick films prepared from paste with composition close to Bi-2212 (and Bi-2212 + 10 wt.% Ag). For paste with composition close to Bi(Pb)-2223 + 20 wt.% Ag, a new phase with f.c.c. structure, lattice parameter about a = 24.5 A and approximate composition Al3Sr2CaBi2CuOx has been identified in the interface region. Understanding and control of these reactions is essential for growth of high quality BSCCO thick films on alumina. (C) 1997 Elsevier Science S.A.