Geochemistry of dikes and lavas from the north wall of the Hess Deep Rift

An investigation of ~1-m.y.-old dikes and lavas from the north wall of the Hess Deep Rift (2°15'N, 101°30'W) collected during Alvin expeditions provides a detailed view of the evolution of fast spreading oceanic crust. The study area encompasses 25 km of an east-west flow line, representing ~370,000 years of crustal accretion at the East Pacific Rise. Samples analyzed exhibit depleted incompatible trace element abundances and ratios [(La/Sm)N < 1]. Indices of fractionation (MgO), and incompatible element ratios (La/Sm, Nb/Ti) show no systematic trends along flow line. Rather, over short (<4 m) and long (~25 km) distances, significant variations are observed in major and trace element concentrations and ratios. Modeling of these variations attests to the juxtaposition of dikes of distinct parental magma compositions. These findings, combined with studies of segmentation of the subaxial magma chamber and lateral magma transport in dikes along rift-dominated systems, suggest a more realistic model of the magmatic system underlying the East Pacific Rise relative to the commonly assumed twodimensional model. In this model, melts from a heterogeneous mantle feed distinct portions of a segmented axial magma reservoir. Dikes emanating from these distinct reservoirs transport magma along axis, resulting in interleaved dikes and host lavas with different evolutionary histories. This model suggests the use of axial or flow line lava compositions to infer the evolution of axial magma chambers should be approached with caution because dikes may never erupt lava or may transport magma significant distances along axis and erupt lavas far from their axial magma chamber of origin.

INTCAL98

The focus of this paper is the conversion of radiocarbon ages to calibrated (cal) ages for the interval 24,00-0 cal BP (Before Present, 0 cal BP = AD 1950), based upon a sample set of dendrochronologically dated tree rings, uranium-thorium dated corals, and varve-counted marine sediment. The 14C age-cal age information, produced by many laboratories, is converted to 14C profiles and calibration curves, for the atmosphere as well as the oceans. We discuss offsets in measured 14C ages and the errors therein, regional 14C age diferences, tree-coral 14C age comparisons and the time dependence of marine reservoir ages, and evaluate decadal vs. single-year 14C results. Changes in oceanic deepwater circulation, especialy for the 16,00-1,00 cal BP interval, are reflected in the Delta14C values of INTCAL98.

Terrigenous proxy record from ODP Site 202-1237 and sediment core RRV9702a-69PC

ODP Site 1237 and sediment core RRV9702a-69PC were investigated for siliciclastic grain-size distributions and changes in geochemical composition to reconstruct southeast trade-wind variability during the past 5 Ma. Because both, working and archive halves of all ODP Site 1237 cores were completely depleted between 3.3 and 8.1 meters composite depths, (mcd), the corresponding sections of pre-site survey core RRV9702A-69PC were sampled and investigated to fill the gap.

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Composition of ferromanganese crusts from the Atlantic, Pacific and Indian Oceans

A collection of layered ferromanganese ores (27 samples) from the Atlantic and Pacific oceans was studied. Trace element and PGE contents were determined layer-by-layer (up to 10 microlayers) in 13 of these samples. The trace, rare earth, and platinum group element distributions, including their layer-to-layer variations, were compared in hydrogenic and hydrothermal crusts from different regions. It was found that the main PGE variations (by a factor of 10-50) are related to their layer-to-layer variations within a given ore field. The distributions of PGE and trace elements are strongly heterogeneous, which is related, first, to different contents of the elements in the layers of different age in ferromanganese crusts (FMC) and, second, to the observed regional heterogeneity and influence of hydrothermal fluids. Geochemical data indicate that CFC formation was mainly caused by the hydrochemical precipitation of material from seawater. This process was accompanied by diagenetic phenomena, water-rock interaction, and influence of volcanic and hydrothermal sources.

Isotope geochemistry of Ninetyeast Ridge basalts

The Ninetyeast Ridge lavas have Sr and Nd isotopic ratios intermediate between those of Indian Ocean MORBs and those of the very enriched Kerguelen hot spot. In an Nd-Sr isotope diagram, they also plot close to the fields of St. Paul Island lavas and of the early magmatism on Kerguelen Archipelago. The Ninetyeast Ridge lavas were generated by mixing among at least three components: a depleted, MORB-type component, such as the one erupted today on the Southeast Indian Ridge; a very enriched, high- Sr/ Sr, low-epsilon-Nd, OIB-type component (the Kerguelen hot spot); and an OIB-type component comparable to that sampled from the St. Paul (and Amsterdam) lavas. The Ninetyeast Ridge lavas show a typical Dupal anomaly signature and Pb, Sr, and Nd isotopic systematics indicate that the Kerguelen hot spot was involved in the ridge's formation as the Indian plate moved northward. The different sites cored during ODP Leg 121 show a trend in their isotopic compositions, from less radiogenic Pb/ Pb ratios and intermediate 87Sr/86Sr and 143Nd/**Nd ratios in the oldest lavas (Site 758) toward more radiogenic 206Pb/204Pb, higher epsilon-Nd, and lower 87Sr/86Sr values in the youngest lavas (Site 756). The lavas from Site 757 have 206Pb/204Pb ratios intermediate between those of the lavas from Sites 756 and 758 and higher 87Sr/86Sr and lower epsilon-Nd values. The relative proportions of the hot spot(s) and MORB component have evolved with time, reflecting differences of tectonic setting: the relative proportion of the Kerguelen hot spot component appears lower in the younger Site 756 lavas than in the older lavas from Sites 757 and 758. Site 756 coincides with the beginning of rifting at the Southeast Indian Ridge, about 43 Ma ago. The formation of the early Kerguelen Archipelago lavas may have drained most of the plume-derived material toward the Antarctic plate. Alternatively, the proximity of the spreading-ridge axis may account for the isotopic similarity of the Site 756 lavas to young lavas erupted on the Southeast Indian Ridge, from 33? to 37?S. The older lavas of Ninetyeast Ridge may have formed when the hot spot and ridge axis did not exactly coincide. The involvement of the third component, a St. Paul hot spot, in the genesis of the Ninetyeast Ridge lavas, especially for the Site 756 lavas, is clearly indicated by Sr, Pb, and Nd isotope systematics and also by trace element ratios. These data, together with those from the Kerguelen Plateau, indicate that the Kerguelen hot spot has been active more or less continuously in the South Indian Ocean for at least 115 Ma. This could indicate that the plume, and by inference the Dupal anomaly, is deep seated in origin.

Isotopic geochemistry of granitoids in the Jinshajiang suture zone, SW China

The Jinshajiang suture zone, located in the eastern part of the Tethyan tectonic domain, is noticeable for a large-scale distribution of Late Jurassic to Triassic granitoids. These granitoids were genetically related to the evolution of the Paleo-Tethys Ocean. The Beiwu, Linong and Lunong granitoids occur in the middle zone of the Jinshajiang Suture Zone, and possess similar geochemical features, indicating they share a common magma source. SIMS zircon U-Pb dating reveals the Beiwu, Linong and Lunong granitic intrusions were emplaced at 233.9±1.4 Ma (2 sigma), 233.1 ±1.4 Ma (2 sigma) and 231.0±1.6 Ma (2 sigma), respectively. All of these granitoids are enriched in abundances of Si (SiO2 =65.2-73.5 wt.%), and large-ion-lithophile-elements (LILEs), but depleted in high-field-strength-elements contents (HFSEs, e.g., Nb, Ta, Ti). In addition, they have low P2O5 contents (0.06-0.11 wt.%), A/CNK values ([molecular Al2O3/(CaO+Na2O+K2O)], mostly<1.1) and 10000Ga/Al ratios (1.7-2.2), consistent with the characteristics of I-type granites. In terms of isotopic compositions, these granitoids have high initial 87Sr/86Sr ratios (0.7078-0.7148), Pb isotopic compositions [(206Pb/204Pb)t=18.213-18.598, (207Pb/204Pb)t=15.637-15.730 and (208Pb/204Pb)t=38.323-38.791], zircon d18O values (7. per mil-9.3 per mil) and negative eNd(t) values (-5.1 to -6.7), suggesting they were predominantly derived from the continental crust. Their Nb/Ta ratios (average value=8.6) are consistent with those of the lower continental crust (LCC). However, variable ?Hf(t) values (-8.6 to +2.8) and the occurrences of mafic microgranular enclaves (MMEs) suggest that mantle-derived melts and lower crustal magmas were involved in the generation of these granitoids. Moreover, the high Pb isotopic ratios and elevated zircon d18O values of these rocks indicate a significant contribution of the upper crustal composition. We propose a model in which the Beiwu, Linong and Lunong granitoids were generated under a late collisional or post-collisional setting. It is possible that this collision was completed before Late Triassic. Decompression induced mantle-derived magmas underplated and provided the heat for the anatexis of the crust. Hybrid melts including mantle-derived and the lower crustal magmas were then generated. The hybrid melts thereafter ascended to a shallow depth and resulted in some degree of sedimentary rocks assimilation. Such three-component mixing magmas source and subsequent fractional crystallization could be responsible for the formation of the Beiwu, Linong and Lunong granitoids.

Geochemistry and radionuclide content of sediment and water samples obtained from the Ob and Irtysh river, Russia

This paper reports the results of the investigations of 2006-2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River. In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration. Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 µm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300-500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 µm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.

Major-oxides and trace-elements at DSDP Hole 78-543A

Four chemically distinct basalts were cored in 44 m of basement penetration at Deep Sea Drilling Project Site 543, in Upper Cretaceous crust just seaward of the deformation front of the Barbados Ridge and north of the Tiburon Rise. All four types are moderately fractionated abyssal tholeiites. The four types have different magnetic inclinations, all of reversed polarity, suggesting eruption at different times which recorded secular variation of the earth's magnetic field. Extensive replacement of Plagioclase by K-feldspar has occurred at the top of the basalts, giving analyses with K2O contents up to 5 %. The earliest stages of alteration were dominantly oxidative, resulting in fractures lined with celadonite and dioctahedral smectite, and pervasive replacement of olivine and most intersertal glass with iron hydroxides and green clay minerals. Latef, non-oxidative alteration resulted in formation of olive-green clays and pyrite veins in a portion of the rocks. Basalts affected by this alteration actually lost K2O (to abundances lower than in adjacent fresh basalt glasses), and gained MgO (to abundances higher than in the glasses). Finally, fractures and interpillow voids were lined with calcite, sealing in much fresh glass. Oxygen-isotope measurements on the calcite indicate that this occurred at 12 to 25C. Either altering fluids were warm or the basalts had become buried with a considerable thickness of sediments, such that temperatures increased until a conductive thermal gradient was established, when the veining occurred.

Chemical and isotopic compositions of rocks, ores, and hydrothermal minerals from the Rainbow and Logachev-2 hydrothermal fields

The aim of this paper is to analyze and compare mineralogy and geochemistry of copper-zinc sulfide ores from the Logachev-2 and Rainbow hydrothermal fields of the Mid-Atlantic Ridge (MAR) confined to serpentinite protrusions. It was found that Zn(Fe) and Cu, Fe(Zn) sulfides had been deposited in black smokers pipes almost simultaneously from intermittently flowing, nonequilibrium H2S-low solutions of different temperatures. Pb isotope composition confirmed that the deep oceanic crust had been a source of lead. The ores from the Rainbow field are 20-fold higher in Co than ores restricted to basalts and show a high ratio of Co/Ni=46. The ores from the Rainbow field are enriched in 34S isotope (aver. d34S=10 per mil) because of constant flow of cold sea water into the subsurface zone of the hydrothermal system. Ores from the Logachev-2 field are 8 times higher in gold compared to other MAR regions. Sulfide ores from the Rainbow and Logachev-2 fields have no analogues among MAR ore occurrences in terms of enrichment in valuable components (Zn, Cd, Co, and Au).

Microthermometry and Raman analysis of fluid inclusions in different generations of quartz veins of the Athabasca Basin

The Athabasca Basin (Canada) contains the highest grade unconformity-type uranium deposits in the world. Underlying the Athabasca Group sedimentary rocks of the Dufferin Lake zone are variably graphitic pelitic schists (VGPS), altered to chlorite and hematite (Red/Green Zone: RGZ), and locally bleached near the unconformity during paleoweathering and/or later fluid interaction, leading to a loss of graphite near the unconformity. Fluid inclusions were examined in different generations of quartz veins, using microthermometry and Raman analysis, to characterize and compare the different fluids that interacted with the RGZ and the VGPS. In the VGPS, CH4-, N2- and CO2-rich fluids circulated. CH4- and N2-rich fluids could be the result of the breakdown of graphite to CH4/CO2, whereas N2-rich fluid is interpreted to be the result of breakdown of feldspars/micas to NH4+/N2. In the RGZ, highly saline fluids interpreted to be basinally derived have been recorded. The circulation of the two types of fluids (carbonic and brines) occurred at two different distinct events: 1) during the retrograde metamorphism of the basement rocks before the deposition of the Athabasca Basin for the carbonic fluids, and 2) after the deposition of the Athabasca Basin for the brines. Thus, in addition to possibly be related to graphite depletion in the RGZ, the brines can be linked to uranium mineralization.

Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.