Geochemistry of samples from Valtournenche, Western Italian Alps

Slices of polycyclic metasediments (marbles and meta-cherts) are tectonically amalgamated with the polydeformed basement of the Dent Blanche tectonic system along a major Alpine shear zone in the Western Alps (Becca di Salé area, Valtournenche Valley). A combination of techniques (structural analysis at various scales, metamorphic petrology, geochronology and trace element geochemistry) was applied to determine the age and composition of accessory phases (titanite, allanite and zircon) and their relation to major minerals. The results are used to reconstruct the polyphase structural and metamorphic history, comprising both pre-Alpine and Alpine cycles. The pre-Alpine evolution is associated with low-pressure high-temperature metamorphism related to Permo-Triassic lithospheric thinning. In meta-cherts, microtextural relations indicate coeval growth of allanite and garnet during this stage, at ~ 300 Ma. Textures of zircon also indicate crystallization at HT conditions; ages scatter from 263-294 Ma, with a major cluster of data at ~ 276 Ma. In impure marble, U-Pb analyses of titanite domains (with variable Al and F contents) yield apparent 206Pb/238U dates range from Permian to Jurassic. Chemical and isotopic data suggest that titanite formed at Permian times and was then affected by (extension-related?) fluid circulation during the Triassic and Jurassic, which redistributed major elements (Al and F) and partially opened the U-Pb system. The Alpine cycle lead to early blueschist facies assemblages, which were partly overprinted under greenschist facies conditions. The strong Alpine compressional overprint disrupted the pre-Alpine structural imprint and/or reactivated earlier structures. The pre-Alpine metamorphic record, preserved in these slices of metasediments, reflects the onset of the Permo-Triassic lithospheric extension to Jurassic rifting.

Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.

Geochemistry of boninite and harzburgite of ODP Leg 125 basement samples

Holes drilled into the volcanic and ultrabasic basement of the Izu-Ogasawara and Mariana forearc terranes during Leg 125 provide data on some of the earliest lithosphere created after the start of Eocene subduction in the Western Pacific. The volcanic basement contains three boninite series and one tholeiite series. (1) Eocene low-Ca boninite and low-Ca bronzite andesite pillow lavas and dikes dominate the lowermost part of the deep crustal section through the outer-arc high at Site 786. (2) Eocene intermediate-Ca boninite and its fractionation products (bronzite andesite, andesite, dacite, and rhyolite) make up the main part of the boninitic edifice at Site 786. (3) Early Oligocene intermediate-Ca to high-Ca boninite sills or dikes intrude the edifice and perhaps feed an uppermost breccia unit at Site 786. (4) Eocene or Early Oligocene tholeiitic andesite, dacite, and rhyolite form the uppermost part of the outer-arc high at Site 782. All four groups can be explained by remelting above a subduction zone of oceanic mantle lithosphere that has been depleted by its previous episode of partial melting at an ocean ridge. We estimate that the average boninite source had lost 10-15 wt% of melt at the ridge before undergoing further melting (5-10%) shortly after subduction started. The composition of the harzburgite (<2% clinopyroxene, Fo content of about 92%) indicates that it underwent a total of about 25% melting with respect to a fertile MORB mantle. The low concentration of Nb in the boninite indicates that the oceanic lithosphere prior to subduction was not enriched by any asthenospheric (OIB) component. The subduction component is characterized by (1) high Zr and Hf contents relative to Sm, Ti, Y, and middle-heavy REE, (2) light REE-enrichment, (3) low contents of Nb and Ta relative to Th, Rb, or La, (4) high contents of Na and Al, and (5) Pb isotopes on the Northern Hemisphere Reference Line. This component is unlike any subduction component from active arc volcanoes in the Izu-Mariana region or elsewhere. Modeling suggests that these characteristics fit a trondhjemitic melt from slab fusion in amphibolite facies. The resulting metasomatized mantle may have contained about 0.15 wt% water. The overall melting regime is constrained by experimental data to shallow depths and high temperatures (1250? C and 1.5 kb for an average boninite) of boninite segregation. We thus envisage that boninites were generated by decompression melting of a diapir of metasomatized residual MORB mantle leaving the harzburgites as the uppermost, most depleted residue from this second stage of melting. Thermal constraints require that both subducted lithosphere and overlying oceanic lithosphere of the mantle wedge be very young at the time of boninite genesis. This conclusion is consistent with models in which an active transform fault offsetting two ridge axes is placed under compression or transpression following the Eocene plate reorganization in the Pacific. Comparison between Leg 125 boninites and boninites and related rocks elsewhere in the Western Pacific highlights large regional differences in petrogenesis in terms of mantle mineralogy, degree of partial melting, composition of subduction components, and the nature of pre-subduction lithosphere. It is likely that, on a regional scale, the initiation of subduction involved subducted crust and lithospheric mantle wedge of a range of ages and compositions, as might be expected in this type of tectonic setting.

Description and geochemical composition of manganese nodules retrieved from Lake Ontario, Canada

A large deposit of ferromanganese oxide coated sands and scattered manganese nodules occurs in the northern portion of Lake Ontario. The Mn and Fe contents of the concretions are similar to those in concretions from other environments, while their Ni, Cu, and Co contents are lower than in deep-sea nodules, but higher than in most previously described lacustrine concretions. Pb and Zn are high in the coatings and exceed the concentrations found in many previously analyzed Mn deposits. Within the deposit, Mn, Ni, Co, and Zn contents are correlated, and they vary inversely with Fe. Mn, Fe, Ni, Cu, and Pb are present in the interstitial waters of the sediments underlying the deposit in higher concentrations than in the overlying lake waters, thus providing a potential source of metals for concretion formation.The origin and compositional variations in the deposit possibly can be explained in terms of the fractionation and precipitation of Fe and Mn as a result of redox variations in the lake sediments. Eh increases from south to north across the deposit in such a way that iron may be selectively oxidized and precipitated in the south and manganese, in the north. The upward diffusion of Mn, Fe, and associated elements from the underlying sediments probably provides the principal source of the metals in the south of the deposit, while metal-enriched bottom waters are probably the principal source in the north.

Lithologic and geochemical composition of samples from the Circum Superior Belt, North America

The ca. 1880 Ma Circum-Superior Large Igneous Province (LIP) consists of a number of discontinuous segments known to cover a significant portion of the margin of the Superior Province craton in North America. New geochemical and isotopic data from western segments of this LIP support a common origin for the these segments and suggest that magmatism in the Lake Superior region may have been fed through the ~ 600 km long Pickle Crow dyke from a source north of the Fox River Belt in northeastern Manitoba. The Fox River Belt, Pickle Crow dyke and sections of the Hemlock Formation in the Lake Superior region possess trace element signatures which are similar to those of more recent oceanic plateaux. The Hemlock Formation displays a heterogeneous geochemical signature. This chemical heterogeneity can in part be explained by lithospheric contamination and possibly by source heterogeneity. The tectonomagmatic setting in which these igneous rocks were formed could have involved a mantle plume. Evidence supporting a plume origin includes high MgO volcanic rocks, high calculated degrees of partial melting and geochemical signatures similar to those of oceanic plateaux.

Chemical composition of basalts from coarse debris of the Kara Sea bottom sediments

Study of basaltic debris from the Kara Sea bottom has shown its similarity to traps of the Eastern Siberia in mineralogy, structures and chemical composition. In comparison with oceanic tholeiites, the source of traps and Kara Sea basin basaltic melts was enriched in REE and some other incompatible elements. K-Ar dating of two samples of supposed autochtonous location from the eastern part of the Kara Sea basin has shown 209 and 218 Ma - younger than traps (247-248 Ma). Origin of Siberian traps used to connect with action of the mantle plume (Iceland plume, according to geodinamic reconstruction). Our new age data may be interpreted as an evidence of the Siberian plate moving over the head of plume.

Geochemistry of ferromanganese deposits from the Wombat Plateau

Ferromanganese crusts, nodules, and ferromanganese-rich sediments were recovered on the Wombat Plateau, northwest Australian continental margin, by dredging during Bureau of Mineral Resources cruise 56 of Rig Seismic and by drilling during ODP Leg 122 of JOWES Resolution. We report here the chemistry and mineralogy of the ferromanganese crusts, nodules, and associated ferromanganese-rich sediments. The ferromanganese deposits from the ODP sites are up to 40 cm thick and probably formed in Late Cretaceous to Eocene times. Those from outcrops usually formed in several phases, and their age is unconstrained except that the substrates are Mesozoic. The samples were recovered from present-day water depths of 2000-4600 m, on the Wombat Plateau adjacent to the Argo Abyssal Plain. Both the nodules and crusts are primarily vernadite (delta-MnO2) and are chemically and mineralogically similar, and not dissimilar from ferromanganese deposits found elsewhere on Australian and other marginal plateaus. They are markedly different from most deep-sea deposits. The only crystalline iron phase identified within the ferromanganese deposits is goethite. Concentrations of metals of potential economic interest are generally low compared to those from vernadite-rich seamount crusts and nodules and from abyssal nodules from areas of high resource potential in the Pacific Ocean. Maximum metal values reach 0.55% Co, 0.58% Ni, and 0.20% Cu in deposits containing 4.8% to 30.9% Fe and 4.4% to 21.1% Mn.

Geochemistry of Pliocene-Pleistocene volcanic rocks from the Izu Arc

The igneous geochemistry of lavas and breccias from the basement of Sites 790 and 791, and pumice clasts from the Pliocene-Pleistocene sedimentary section of Sites 788, 790, 791, and 793 were studied. Arc volcanism became silicic about 1.5 m.y. before the inception of rifting in the Sumisu Rift at 2 Ma, but eruption of these silicic magmas reflects changes in stress regime, especially during the last 130,000 yr, rather than crustal anatexis. Arc magmas have had a larger proportion of slab-derived components since the inception of rifting than before, but are otherwise similar. Rift basalts and rhyolites are derived from a different source than are arc andesites to rhyolites. The rift source has less slab-derived material and is an E-MORB-like source, in contrast to an N-MORB-type source overprinted with more slab-derived material beneath the arc. Rift magma types, in the form of rare pumice and lithic clasts, preceded the rift, and the earliest magmas that erupted in the rift already differed from those of the arc. The earliest large rift eruption produced an exotic explosion breccia ("mousse") despite eruption at >1800 mbsl. Although this rock type is attributed primarily to high magmatic water content, the clasts are more MORB-like in trace element and isotopic composition than are modern Mariana Trough basalts. After rifting began, arc volcanism continued to be predominantly silicic, with individual pumice deposits containing clasts that vary in composition by about 5 wt% SiO2, or about as much as in historical eruptions of submarine Izu Arc volcanoes. The overall variations in magma composition with time during the inception of arc rifting are broadly similar in the Sumisu Rift and Lau Basin, though newly tapped OIB-type mantle seems to be present earlier during basin formation in the Sumisu than Lau case.

Isotopic composition and major and trace element concentrations of mafic rocks obtained from western Dronning Maud Land

On the basis of new bulk major and trace element (including REE) as well as Sm-Nd and Rb-Sr isotope data, used in conjunction with available geochronological data, a post-tectonic mafic igneous province and four groups of pre- to syntectonic amphibolite are distinguished in the polymetamorphic Maud Belt of western Dronning Maud Land, East Antarctica. Protoliths of the Group 1 amphibolites are interpreted as volcanic arc mafic intrusions with Archaean to Palaeoproterozoic Nd model ages and depletion in Nb and Ta. Isotopic and lithogeochemical characteristics of this earliest group of amphibolite indicate that the Maud Belt was once an active continental volcanic arc. The most likely position of this arc, for which a late Mesoproterozoic age (c. 1140 Ma) is indicated by available U-Pb single-zircon age data, was on the southeastern margin of the Kaapvaal-Grunehogna Craton. The protoliths of Group 2 amphibolites are attributed to the 1110 Ma Borgmassivet-Umkondo thermal event on the basis of comparable Nd model ages and trace element distributions. Group 3 amphibolite protoliths are characterized by mid-ocean ridge basalt-type REE patterns and low Th/Yb ratios, and they are related to Neoproterozoic extension. Group 4 amphibolite protoliths are distinguished by high Dy/Yb ratios and are attributed to a phase of syntectonic Pan-African magmatism as indicated by Rb-Sr isotope data.

Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

Geochemistry of Lesser Antilles lavas

We present new U-series disequilibrium and radiogenic isotope data for 7 mafic lavas from the Lesser Antilles arc. These are combined with published data in an internally consistent model that quantitatively estimates the amount of sediment and fluid added to the source of the Lesser Antilles arc system. Some lavas form an array consistent with bulk sediment addition (0.2-2%) whereas others appear to require addition of 0.4-2% sediment melt, particularly in the south of the arc. Evidence for both bulk sediment and sediment melt addition can be found within both the northern and central sections of the arc suggesting a thermal structure whereby the upper portions of the subducted sediment pile lie close to their solidus beneath much of the arc. Addition of up to 5% fluid derived from altered oceanic crust to these sediment enriched mantle wedge source regions can simulate the majority of the lavas on a plot of 207Pb/204Pb versus Ce/Pb. By taking into account the range in calculated wedge compositions and allowing for some mobility of Th in the fluid, the same model can also account for much of the observed range of U-Th-Ra disequilibria, especially if the eclogitic residue contains trace amounts of rutile. The implication of this more complex model is that the time scales for fluid addition and differentiation could be significantly shorter than those estimated in some previous studies.