First stars XIV. Sulfur abundances in extremely metal-poor stars

Context. Precise S abundances are important in the study of the early chemical evolution of the Galaxy. In particular the site of the formation remains uncertain because, at low metallicity, the trend of this alpha-element versus [Fe/H] remains unclear. Moreover, although sulfur is not bound significantly in dust grains in the ISM, it seems to behave differently in DLAs and old metal-poor stars. Aims. We attempt a precise measurement of the S abundance in a sample of extremely metal-poor stars observed with the ESO VLT equipped with UVES, taking into account NLTE and 3D effects. Methods. The NLTE profiles of the lines of multiplet 1 of S I were computed with a version of the program MULTI, including opacity sources from ATLAS9 and based on a new model atom for S. These profiles were fitted to the observed spectra. Results. We find that sulfur in EMP stars behaves like the other alpha-elements, with [S/Fe] remaining approximately constant below [Fe/H] = -3. However, [S/Mg] seems to decrease slightly with increasing [Mg/H]. The overall abundance patterns of O, Na, Mg, Al, S, and K are most closely matched by the SN model yields by Heger & Woosley. The [S/Zn] ratio in EMP stars is solar, as also found in DLAs. We derive an upper limit to the sulfur abundance [S/Fe] < +0.5 for the ultra metal-poor star CS 22949-037. This, along with a previously reported measurement of zinc, argues against the conjecture that the light-element abundance pattern of this star (and by analogy, the hyper iron-poor stars HE 0107-5240 and HE 1327-2326) would be due to dust depletion.

Mn, Cu, and Zn abundances in barium stars and their correlations with neutron capture elements

Barium stars are optimal sites for studying the correlations between the neutron-capture elements and other species that may be depleted or enhanced, because they act as neutron seeds or poisons during the operation of the s-process. These data are necessary to help constrain the modeling of the neutron-capture paths and explain the s-process abundance curve of the solar system. Chemical abundances for a large number of barium stars with different degrees of s-process excesses, masses, metallicities, and evolutionary states are a crucial step towards this goal. We present abundances of Mn, Cu, Zn, and various light and heavy elements for a sample of barium and normal giant stars, and present correlations between abundances contributed to different degrees by the weak-s, mains, and r-processes of neutron capture, between Fe-peak elements and heavy elements. Data from the literature are also considered in order to better study the abundance pattern of peculiar stars. The stellar spectra were observed with FEROS/ESO. The stellar atmospheric parameters of the eight barium giant stars and six normal giants that we analyzed lie in the range 4300 < T(eff)/K < 5300, -0.7 < [Fe/H] <= 0.12 and 1.5 <= log g < 2.9. Carbon and nitrogen abundances were derived by spectral synthesis of the molecular bands of C(2), CH, and CN. For all other elements we used the atomic lines to perform the spectral synthesis. A very large scatter was found mainly for the Mn abundances when data from the literature were considered. We found that [Zn/Fe] correlates well with the heavy element excesses, its abundance clearly increasing as the heavy element excesses increase, a trend not shown by the [Cu/Fe] and [Mn/Fe] ratios. Also, the ratios involving Mn, Cu, and Zn and heavy elements usually show an increasing trend toward higher metallicities. Our results suggest that a larger fraction of the Zn synthesis than of Cu is owed to massive stars, and that the contribution of the main-s process to the synthesis of both elements is small. We also conclude that Mn is mostly synthesized by SN Ia, and that a non-negligible fraction of the synthesis of Mn, Cu, and Zn is owed to the weak s-process.

Major- and trace-element composition of REE-rich turkestanite from peralkaline granites of the Morro Redondo Complex, Graciosa Province, south Brazil

Turkestanite, a rare Th- and REE-bearing cyclosilicate in the ekanite-steacyite group was found in evolved peralkaline granites from the Morro Redondo Complex, south Brazil. It occurs with quartz, alkali feldspar and an unnamed Y-bearing silicate. Electron microprobe analysis indicates relatively homogeneous compositions with maximum ThO(2), Na(2)O and K(2)O contents of 22.4%, 2.93% and 3.15 wt.%, respectively, and significant REE(2)O(3) abundances (5.21 to 11.04 wt.%). The REE patterns show enrichment of LREE over HREE, a strong negative Eu anomaly and positive Ce anomaly, the latter in the most transformed crystals. Laser ablation inductively coupled plasma mass spectrometry trace element patterns display considerable depletions in Nb, Zr, Hf, Ti and Li relative to whole-rock sample compositions. Observed compositional variations suggest the influence of coupled substitution mechanisms involving steacyite, a Na-dominant analogue of turkestanite, iraqite, a REE-bearing end-member in the ekanite-steacyite group, ekanite and some theoretical end-members. Turkestanite crystals were interpreted as having precipitated during post-magmatic stages in the presence of residual HFSE-rich fluids carrying Ca, the circulation of which was enhanced by deformational events.

Re-Os isotope and highly siderophile element systematics of the Parana continental flood basalts (Brazil)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Re-Os isotope and highly siderophile element systematics of the Parana continental flood basalts (Brazil)

Basalts of the Parana continental flood basalt (PCFB) province erupted through dominantly Proterozoic continental crust during the Cretaceous. In order to examine the mantle source(s) of this major flood basalt province, we studied Os, Sr, Nd, and Pb isotope systematics, and highly siderophile element (HSE) abundances in tholeiitic basalts that were carefully chosen to show the minimal effects of crustal contamination. These basalts define a precise Re-Os isochron with an age of 131.6 +/- 2.3 Ma and an initial Os-187/Os-188 of 0.1295 +/- 0.0018 (gamma Os-187 = +2.7 +/- 1.4). This initial Os isotopic composition is considerably more radiogenic than estimates of the contemporary Depleted Mantle (DM). The fact that the Re-Os data define a well constrained isochron with an age similar to Ar-40/Ar-39 age determinations, despite generally low Os concentrations, is consistent with closed-system behavior for the HSE. Neodymium, Sr, and Pb isotopic data suggest that the mantle source of the basalts had been variably hybridized by melts derived from enriched mantle components. To account for the combined Os, Nd, Sr, and Pb isotopic characteristics of these rocks, we propose that the primary melts formed from metasomatized asthenospheric mantle (represented by arc-mantle peridotite) that underwent mixing with two enriched components, EM-I and EM-II. The different enriched components are reflected in minor isotopic differences between basalts from southern and northern portions of the province. The Tristan da Cunha hotspot has been previously suggested to be the cause of the Parana continental flood basalt magmatism. However, present-day Tristan da Cunha lavas have much higher Os-187/Os-188 isotopic compositions than the source of the PCFB. These data, together with other isotopic and elemental data, preclude making a definitive linkage between the Tristan plume and the PCFB. (C) 2012 Elsevier B.V. All rights reserved.

OXYGEN ABUNDANCES IN LOW- AND HIGH-alpha FIELD HALO STARS AND THE DISCOVERY OF TWO FIELD STARS BORN IN GLOBULAR CLUSTERS

Oxygen abundances of 67 dwarf stars in the metallicity range -1.6 < [Fe/H] < -0.4 are derived from a non-LTE analysis of the 777 nm O I triplet lines. These stars have precise atmospheric parameters measured by Nissen and Schuster, who find that they separate into three groups based on their kinematics and alpha-element (Mg, Si, Ca, Ti) abundances: thick disk, high-alpha halo, and low-alpha halo. We find the oxygen abundance trends of thick-disk and high-alpha halo stars very similar. The low-alpha stars show a larger star-to-star scatter in [O/Fe] at a given [Fe/H] and have systematically lower oxygen abundances compared to the other two groups. Thus, we find the behavior of oxygen abundances in these groups of stars similar to that of the a elements. We use previously published oxygen abundance data of disk and very metal-poor halo stars to present an overall view (-2.3 < [Fe/H] < +0.3) of oxygen abundance trends of stars in the solar neighborhood. Two field halo dwarf stars stand out in their O and Na abundances. Both G53-41 and G150-40 have very low oxygen and very high sodium abundances, which are key signatures of the abundance anomalies observed in globular cluster (GC) stars. Therefore, they are likely field halo stars born in GCs. If true, we estimate that at least 3% +/- 2% of the local field metal-poor star population was born in GCs.

Partial melting within the lower crust – Constraints from bulk rock geochemical data and trace element mineral analyses of granulites and migmatites from Central Finland

This PhD thesis concerns geochemical constraints on recycling and partial melting of Archean continental crust. A natural example of such processes was found in the Iisalmi area of Central Finland. The rocks from this area are Middle to Late Archean in age and experienced metamorphism and partial melting between 2.7-2.63 Ga. The work is based on extensive field work. It is furthermore founded on bulk rock geochemical data as well as in-situ analyses of minerals. All geochemical data were obtained at the Institute of Geosciences, University of Mainz using X-ray fluorescence, solution ICP-MS and laser ablation-ICP-MS for bulk rock geochemical analyses. Mineral analyses were accomplished by electron microprobe and laser ablation ICP-MS. Fluid inclusions were studied by microscope on a heating-freezing-stage at the Geoscience Center, University Göttingen. Part I focuses on the development of a new analytical method for bulk rock trace element determination by laser ablation-ICP-MS using homogeneous glasses fused from rock powder on an Iridium strip heater. This method is applicable for mafic rock samples whose melts have low viscosities and homogenize quickly at temperatures of ~1200°C. Highly viscous melts of felsic samples prevent melting and homogenization at comparable temperatures. Fusion of felsic samples can be enabled by addition of MgO to the rock powder and adjustment of melting temperature and melting duration to the rock composition. Advantages of the fusion method are low detection limits compared to XRF analyses and avoidance of wet-chemical processing and use of strong acids as in solution ICP-MS as well as smaller sample volumes compared to the other methods. Part II of the thesis uses bulk rock geochemical data and results from fluid inclusion studies for discrimination of melting processes observed in different rock types. Fluid inclusion studies demonstrate a major change in fluid composition from CO2-dominated fluids in granulites to aqueous fluids in TTG gneisses and amphibolites. Partial melts were generated in the dry, CO2-rich environment by dehydration melting reactions of amphibole which in addition to tonalitic melts produced the anhydrous mineral assemblages of granulites (grt + cpx + pl ± amph or opx + cpx + pl + amph). Trace element modeling showed that mafic granulites are residues of 10-30 % melt extraction from amphibolitic precursor rocks. The maximum degree of melting in intermediate granulites was ~10 % as inferred from modal abundances of amphibole, clinopyroxene and orthopyroxene. Carbonic inclusions are absent in upper-amphibolite facies migmatites whereas aqueous inclusion with up to 20 wt% NaCl are abundant. This suggests that melting within TTG gneisses and amphibolites took place in the presence of an aqueous fluid phase that enabled melting at the wet solidus at temperatures of 700-750°C. The strong disruption of pre-metamorphic structures in some outcrops suggests that the maximum amount of melt in TTG gneisses was ~25 vol%. The presence of leucosomes in all rock types is taken as the principle evidence for melt formation. However, mineralogical appearance as well as major and trace element composition of many leucosomes imply that leucosomes seldom represent frozen in-situ melts. They are better considered as remnants of the melt channel network, e.g. ways on which melts escaped from the system. Part III of the thesis describes how analyses of minerals from a specific rock type (granulite) can be used to determine partition coefficients between different minerals and between minerals and melt suitable for lower crustal conditions. The trace element analyses by laser ablation-ICP-MS show coherent distribution among the principal mineral phases independent of rock composition. REE contents in amphibole are about 3 times higher than REE contents in clinopyroxene from the same sample. This consistency has to be taken into consideration in models of lower crustal melting where amphibole is replaced by clinopyroxene in the course of melting. A lack of equilibrium is observed between matrix clinopyroxene / amphibole and garnet porphyroblasts which suggests a late stage growth of garnet and slow diffusion and equilibration of the REE during metamorphism. The data provide a first set of distribution coefficients of the transition metals (Sc, V, Cr, Ni) in the lower crust. In addition, analyses of ilmenite and apatite demonstrate the strong influence of accessory phases on trace element distribution. Apatite contains high amounts of REE and Sr while ilmenite incorporates about 20-30 times higher amounts of Nb and Ta than amphibole. Furthermore, trace element mineral analyses provide evidence for magmatic processes such as melt depletion, melt segregation, accumulation and fractionation as well as metasomatism having operated in this high-grade anatectic area.

Noble metal abundances in ODP Leg 115 basalts (Table 1)

A comparison of 50 basalts recovered at Sites 706, 707, 713, and 715 along the Reunion hotspot trace during Ocean Drilling Program Leg 115 in the Indian Ocean shows that seafloor alteration had little effect on noble metal concentrations (Au, Pd, Pt, Rh, Ru, and Ir), determined by inductively coupled plasma-mass spectrometry (ICP-MS), which generally tend to decrease with magma evolution. Their compatible-element behavior may be related to the precipitation of Ir-Os-based alloys, chromite, sulfides, and/or olivine and clinopyroxene in some combination. The simplest explanation indicates silicate control of concentrations during differentiation. Basalts from the different sites show varying degrees of alkalinity. Noble metal abundances tend to increase with decreasing basalt alkalinity (i.e., with increasing percentages of mantle melting), indicating that the metals behave as compatible elements during mantle melting. The retention of low-melting-point Au, Pd, and Rh in mantle sulfides, which mostly dissolve before significant proportions of Ir-Os-based alloys melt, explains increasing Pd/Ir ratios with decreasing alkalinity (increasing melting percentages) in oceanic basalts. High noble metal concentrations in Indian Ocean basalts (weighted averages of Au, Pd, Rh, Pt, Ru, and Ir in Leg 115 basalts are 3.2, 8.1, 0.31, 7.3, 0.22, and 0.11 ppb, respectively), compared with basalts from some other ocean basins, may reflect fundamental primary variations in upper- mantle noble metal abundances

(Table 2) Trace element composition of seleceted clast and matrix materials from ODP Site 125-786

Shipboard examination of volcanic and sedimentary strata at Site 786 suggested that at least four types of breccias are present: flow-top breccias, associated with cooling and breakup on the upper surface of lava flows; autobreccias, formed by in-situ alteration at the base of flows; fault-gouge breccias; and true sedimentary breccias derived from weathering and erosion of underlying flows. It is virtually impossible to assess the origin of breccia matrix by textural and mineralogical analyses alone. However, it is fundamental for our understanding of breccia provenance to determine the source component of the matrix material. Whether the matrix is uniquely clastderived can be determined by geochemical fingerprinting. Trace elements that are immobile during weathering and alteration do not change their relative abundances. A contribution to the matrix from any source with an immobile trace element signature different from that of the clasts would appear as a perturbation of the trace element signature of the matrix. Trace element analysis of bulk samples from clasts and matrix material in individual breccia units was undertaken in a fashion similar to that used by Brimhall and Dietrich (1987, doi:10.1016/0016-7037(87)90070-6) in analyzing soil provenance: (1) to help distinguish between sedimentary and volcanic breccias, (2) to determine the degree of mixing and depth of erosion in sedimentary breccias, and (3) to analyze the local provenance of the individual breccia components (matrix and clasts). The following elements were analyzed by X-ray fluorescence (XRF): Rb, Sr, Ba, U, Zr, Cu, Zn, Ti, Cr, and V. Of these elements, Zr and Ti probably exhibit truly immobile behavior (Humphris and Thompson, 1978, doi:10.1016/0016-7037(78)90222-3 ). The remaining elements are useful as a reference for the extent of compositional change during the formation of matrix material (Brimhall and Dietrich, 1987, doi:10.1016/0016-7037(87)90070-6).

Major and rare earth element composition of ODP Site 191-1179 sediments, northwest Pacific

Depth profiles of major element and rare earth element (REE) abundances in sediment samples (mainly siliceous ooze and clay) recovered from Holes 1179B and 1179C at Site 1179, Ocean Drilling Program Leg 191 (41.4°N, 159.6°E) were determined. The oxidation states of Mn and Ce were determined by X-ray absorption near-edge structure. Some geochemical indicators were tested, including the MnO/TiO2 ratios, a bivariate diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), and other discrimination diagrams. The oxidation state of Mn is reduced Mn(II) in the depth profile below 0.60 meters below seafloor (mbsf), which is consistent with relatively low and high abundances of Mn in the sediments and pore waters, respectively. It is possible that the diagenetic effect on the oxidation state and abundance of Mn makes it difficult for the MnO/TiO2 ratio to reflect the depositional environment. The normalized ratio of La and Ce does not change very much with depth, suggesting that the diagenetic effect does not affect the REE signature in the sediments. On the diagram of La/Ce vs. Al2O3/(Al2O3+Fe2O3), the sediments studied here plot at the boundary of the pelagic and continental margin fields. This suggests that continental material has contributed to the sediment to some degree, even though Site 1179 is in a pelagic region of the northwestern Pacific Ocean, >1600 km from Japan.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Rare earth element data for sediments from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. Sum REE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlates slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and La_n/Yb_n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Chemical element concentrations in sediments from DSDP Holes 60-458 and 60-459

The development of laser ablation-inductively coupled plasma-mass spectrometry has revolutionized the analysis of tephras by providing (1) an efficient and precise method for determining abundances of a wide variety of trace elements at low concentrations in individual glass shards and (2) assessment of geochemical heterogeneities within individual ash horizons. This development is important for petrogenetic studies of intraoceanic arc systems, where tephras provide the most complete temporal record of magmatism. Results from the Izu-Bonin and Mariana arc systems indicate that despite close geographical proximity and similar tectonic evolution, they contrast strongly in terms of geochemical evolution since 35 Ma. Whereas the Mariana tephras have exceptional compositional diversity, ranging from low-K (Oligocene), to high-K (Miocene), and subsequently medium-K compositions (Pliocene-Quaternary), the Izu-Bonin arc has been dominated by low-K compositions throughout. The Mariana increases in K are paralleled by increases in abundances of incompatible trace elements and by increased values of diagnostic ratios (e.g., Nb/yb and Th/yb) regarded as monitors of potential mantle-source fertility. The relative uniformity of Nb/yb and Nb/Zr ratios in Izu-Bonin tephras indicates that cyclic processes of backarc basin development and mantle depletion do not necessarily induce large-scale temporal geochemical variations in the associated arc. Temporal variability within the Mariana arc, and its divergence from the Izu-Bonin arc ca. 13 Ma, can be traced to a major injection of subducted sediment in the Mariana system at this time.