Um sensível espectrômetro de massa de fonte sólida e sua aplicação à análise de K, Rb e Sr

Um espectrômetro de massa de fonte sólida de alta sensibilidade e construído de vidro Pyrex é descrito com detalhe. Um sistema de vácuo convencional, constituído de uma bomba mecânica e uma bomba de difusão de mercúrio de duplo estágio, possibilita obter-se, após cerca de 6 horas de contínuo bombeamento, pressão adequada para início de análise de materiais sólidos pela técnica de ionização térmica. Por esta técnica, quantidades tão pequenas quanto alguns micromicrogramas de potássio ou rubídio podem ser analisadas, enquanto que para estrôncio, quantidades tão pequenas quanto 0,1 μg podem ser dosadas. É apresentada também a precisão média obtida na análise desses elementos, bem como a precisão na medida das razões isotópicas. Finalmente, uma série de resultados obtidos em diferentes tipos de rochas empregando-se tal aparelho, é submetida a estudos estatísticos para melhor aquilatar o comportamento do mesmo.

Petrogenesis of syntectonic granites emplaced at the transition from thrusting to transcurrent tectonics in post-collisional setting: Whole-rock and Sr-Nd-Pb isotope geochemistry in the Neoproterozoic Quatro Ilhas and Mariscal Granites, Southern Brazil

The Neoproterozoic post-collisional period in southern Brazil (650-580 Ma) is characterized by substantial volumes of magma emplaced along the active shear zones that compose the Southern Brazilian Shear Belt. The early-phase syntectonic magmatism (630-610 Ma) is represented by the porphyritic, high-K, metaluminous to peraluminous Quatro Ilhas Granitoids and the younger heterogranular, slightly peraluminous Mariscal Granite. Quatro II has Granitoids include three main petrographic varieties (muscovite-biotite granodiorite mbg; biotite monzogranite - bmz: and leucogranite - lcg) that, although sharing some significant geochemical characteristics, are not strictly comagmatic, as shown by chemical and Sr-Nd-Pb isotope data. The most primitive muscovite-biotite granodiorite was produced by contamination of more mafic melts (possibly with some mantle component) with peraluminous crustal melts; the biotite monzogranite, although more felsic, has higher Ca, MgO,TiO2 and Ba, and lower K2O, FeOt, Sr and Rb contents, possibly reflecting some mixing with coeval mafic magmas of tholeiitic affinity; the leucogranite may be derived from pure crustal melts. The Mariscal Granite is formed by two main granite types which occur intimately associated in the same pluton, one with higher K (5-6.5 wt.% K2O) high Rb and lower CaO, Na2O, Ba and Zr as compared to the other (3-5 wt.% of K2O). The two Mariscal Granite varieties have compositional correspondence with fine-grained granites (fgg) that occur as tabular bodies which intruded the Quatro Ilhas Granoitoids before they were fully crystallized, and are inferred to correspond to the Mariscal Granite feeders, an interpretation that is reinforced by similar U-Pb zircon crystallization ages. The initial evolution of the post-collisional magmatism, marked by the emplacement of the Quatro Ilhas Granitoids varieties, activated sources that produced mantle and crustal magmas whose emplacement was controlled both by flat-lying and transcurrent structures. The transition from thrust to transcurrent-related tectonics coincides with the increase in the proportion of crustal-derived melts. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas and may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of orthogneiss protoliths. (C) 2012 Elsevier B.V. All rights reserved.

Chemical, and Sr and Li isotopic composition of pore fluids and sediments from ODP Leg 170 and Leg 205 sites

Pore fluid and sediment chemical and isotopic data were obtained for samples from Ocean Drilling Program (ODP) Leg 205 Sites 1253, 1254, and 1255 in the Costa Rica subduction zone. The chemical and isotopic data reported here were generated in our shore-based laboratories to complement shipboard inorganic geochemical data. Li isotopic analyses were carried out by L.-H. Chan at Louisiana State University (USA). The data reported herein include fluoride, bromide, rubidium, cesium, and barium concentrations; Li and Sr isotopic compositions in pore fluids; and Rb, Cs, and Ba concentrations in representative bulk sediments. The data also include new pore fluid fluoride and bromide concentrations from corresponding ODP Leg 170 Sites 1039, 1040, and 1043. O.M. Saether's Site 1039 and 1040 fluoride concentration data are shown for comparison. Basal sediment fluoride concentrations and Li and Sr isotope ratios at both Sites 1253 and 1039 show reversals that approach modern seawater values. Br/Cl ratios are, however, conservative throughout the sediment section at Sites 1039 and 1253. The observed sharp F and Br concentration maxima, Rb and K concentration minima, the most radiogenic 87Sr/86Sr ratios, and highest 7Li values along the décollement and fracture zone (Sites 1040, 1043, 1254, and 1255) strengthen the evidence obtained during Leg 170 that a deeply sourced fluid, originating from fluid-rock reactions at ~150°C and corresponding to between 10 and 15 km depth, is transporting solutes to the ocean.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Sr-Nd isotopic analyses of sand-sized sediment from the San Francisco Bay coastal system

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects.

Biostratigraphy and Sr isotopic composition of sediments from DSDP Legs 12, 14, 15, 17, 20-22, and 30

We present the data used to construct the Cenozoic and Cretaceous portion of the Phanerozoic curve of seawater 87Sr/86Sr that had been given in summary form by W.H. Burke co-workers. All Cenozoic samples (128) and 22 Cretaceous samples are foram-nannofossil oozes and limestones from DSDP cores distributed among 13 sites in the Atlantic, Pacific and Indian Oceans, and the Caribbean Sea. Non-DSDP Cretaceous samples (126) include limestone, anhydrite and phosphate samples from North America, Europe and Asia. Determination of the 87Sr/86Sr value of seawater at particular times in the past is based on comparison of ratios derived from coeval marine samples from widely separated geographic areas. These samples are characterized by a wide variety of diagenetic and burial histories. The large size and cosmopolitan nature of the data set decreases the likelihood that, among coeval data, systematic error has been introduced by a similar pattern of diagenetic alteration of the ratios. There is good clustering of data points throughout the Cenozoic and Cretaceous curve. The consistency of data is illustrated by Cenozoic and Cretaceous data plots that include a separate symbol for each DSDP site and non-DSDP sample location. More than 98% of the data points are enclosed by upper and lower lines that define a narrow band. For any given time, the correct seawater ratio probably lies within this band. A line drawn within the band represents our estimate of the actual seawater ratio as a function of time. The general configuration of the Cenozoic and Cretaceous curve appears to be strongly influenced by the history of plate interactions and sea-floor spreading. Specific rises and falls in the 87Sr/86Sr of seawater, however, may be caused by a variety of factors such as variation in lithologic composition of the crust exposed to weathering, configuration and topographic relief of continents, volcanic activity, rate of sea-floor spreading, extent of continental inundation by epeiric seas, and variations in both climate and paleooceanographic conditions. Many or all of these factors are probably related to global tectonic processes, yet their combined effect on the temporal variation of seawater 87Sr/86Sr can complicate a direct platetectonic interpretation for portions of the seawater curve.

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Trace element abundances and Sr and Nd isotope compositions in bulk sediments from DSDP Legs 6 and 20

Rare earth element and Nd isotopic data for ten representative samples of Lower Cretaceous to Miocene pelagic sediments from the western Pacific indicate a wide range of compositions for sediments being subducted beneath the Mariana and Volcano arcs. All samples are enriched in light rare earth elements and show negative Eu and Ce anomalies. The values of e-Nd range from +0.6 to -7.3. These data are used to calculate the Bulk Western Pacific Sediment (BWPS), which is characterized by low Sr/Nd (10), Ba/La (13), and e-Nd (-5.2) and high 87Sr/86Sr (0.7078) compared to that of Mariana and Volcano arc lavas. This composite sediment is used to refine a mixing model for the origin of Mariana and Volcano arc melts. Some lavas from the northern Mariana Arc have Ba/La higher than that of BWPS, which indicates that a third component is required. The high Ba/La in the mantle source for these lavas is interpreted to result from multiple episodes of fluid fractionation. The mixing model indicates that a minor amount of sediment and a low proportion of metasomatic fluid fluxes the mantle source at a late stage when the subarc mantle is already highly metasomatized. This model also suggests that the mantle source for arc melts is affected more by metasomatic fluids than by melting or bulk mixing of sediments.

(Table T1) Nd and Sr isotopic compositions, and Nd and Sm concentrations of glasses from ODP Leg 187 sites

The principal objective of Leg 187 was to locate the Indian/Pacific mantle boundary by sampling and analyzing 8- to 28-Ma seafloor basalts to the north of the Australian Antarctic Discordance (AAD). In this paper we present Sr and Nd isotopic data from basaltic glasses recovered from the 13 sites drilled during Leg 187. Our data show that the boundary region is characterized by a gradual east-west increase in 87Sr/86Sr, with a corresponding decrease in 143Nd/144Nd across a 150-km-wide zone located east and west of the 127°E Fracture Zone. The Sr-Nd isotopic composition of glasses therefore confirms the general conclusions derived by the Leg 187 shipboard scientific party in that the mantle boundary follows a west-pointing, V-shaped depth anomaly that stretches across the ocean floor from the Australian to the Antarctic continental margins. We document that two systematic trends of covariation between 87Sr/86Sr and 143Nd/144Nd can be distinguished, suggesting that the basalts sampled during Leg 187 formed through the interaction of three contrasting source components: (1) a component that lies within the broad spectrum of Indian-type mantle compositions, (2) a boundary component, and (3) a Pacific-type mantle component. The variations in elemental and isotopic compositions indicate that the boundary component represents a distinct mantle region that is associated with the boundary between the Pacific and the Indian mid-ocean-ridge basalt (MORB) sources rather than a dispersed mantle heterogeneity that was preferentially extracted in the boundary region. However, the origin of the boundary component remains an open question. The three components are not randomly intermixed. The Indian and the Pacific mantle sources both interacted with the boundary component, but they seem not to have interacted directly with each other. Large local variability in isotopic compositions of lavas from the mantle boundary region demonstrates that magma extraction processes were unable to homogenize the isotopic contrasts present in the mantle source in this region. Systematic variations in rare earth element (REE) concentrations across the depth anomaly cannot be explained solely by variations in source composition. The observed variations may be explained by an eastward increase and westward decrease in the degree of melting toward the mantle boundary region, compatible with a cooling of the Pacific mantle and a heating of the Indian mantle toward the mantle boundary.

Nd and Sr isotopic compositions and isotope dilution trace element concentrations from 7 sediment cores along the southeast Greenland margin

The Nd and Sr isotopic compositions of Quaternary glacial and glacimarine siliciclastic sediments deposited along the margin of southeast Greenland were determined to assess the roles of the Greenland, Iceland, and more distal ice sheets in delivering detritus to this portion of the northern North Atlantic. The isotopic compositions of detritus generated by portions of the southern Greenland Ice Sheet were defined through measurements of till and trough mouth fan sediments. Massive diamicts from the Scoresby Sund trough mouth fan show a restricted range of e-Nd (-11.8 to -16.6) and 87Sr/86Sr (0.7192-0.7246) consistent with their derivation from mixtures of sediments derived from Paleoproterozoic and/or Caledonian basement and Tertiary Greenland basalts. Further south at Kangerlussuaq, till isotopic compositions covary with the underlying basement type, with low e-Nd values in the inner fiord (-18.1) reflecting the erosion of the local Precambrian gneisses, but with higher e-Nd values (-2.3 to 2.5) found where the trough crosses East Greenland Tertiary basalts. Fine-grained (< 63 µm) sediments deposited along the southeast Greenland margin also show regular spatial isotopic variations. Ambient sediments and ice-rafted detritus in the southern Irminger Basin trend towards low e-Nd values (to ~ -28) and 87Sr/86Sr ratios (~ 0.711 to ~ 0.715) and are likely derived from proximal Archean gneisses of SE Greenland. Further north in the northern Irminger and Blosseville Basins, sediments trend toward much higher e-Nd (> -4) and low 87Sr/86Sr (< 0.709) reflecting a component derived from the local Iceland volcanic rocks and/or the East Greenland Tertiary basalts. In all three regions, the locally-derived detritus is intermixed with sediment with an intermediate e-Nd value (~ -10) and 87Sr/86Sr (~ 0.718) that was likely delivered by icebergs emanating from the Eurasian Ice Sheets and not from eastern Greenland. Deposition of glacial sediments from both proximal and distal (Eurasian) sources occurred adjacent to SE Greenland throughout the past 50 Ka, with periodic increases in IRD deposition at various times including those of Heinrich events 1, 2 and 4. These results suggest that at least the southern portions of the Greenland Ice Sheet experienced periodic instabilities during the Last Glacial period.