Helium and carbon isotopes in fluorites: implications for mantle carbon contribution in an ancient subduction zone

The concentrations of helium and carbon in fluorite associated with Cretaceous to Neogene (90–13 Ma) granitic magmatism in the Japanese arc have been measured. Concentrations of Li, U, Th and Gd were measured to correct for secondary generated ³He. The CO₂/³He of fluorites are almost uniform (1.5×10¹⁰–4×10¹⁰) and in fair agreement with the range of present island arc volcanic gases. The calculated mantle C contribution in the Mesozoic subduction zone appear to have been identical to the present one (7–19%) indicating that the C flux from the mantle in supra-subduction zone environments has remained fairly constant during the past 70 million years.     

Geodynamic implications of deep mantle upwelling in the source of Tertiary volcanics from the Veneto region (South-Eastern Alps)

Major and trace element and Sr–Nd–Hf–Pb isotopic data for the most primitive Tertiary lavas from the Veneto region (South-Eastern Alps, Italy) show the typical features of HIMU hotspot volcanism, variably diluted by a depleted asthenospheric mantle component (⁸⁷Sr/⁸⁶Sr_i=0.70306–0.70378; _Ndi=+3.9 to +6.8; _Hfi=+6.4 to +8.1, ²⁰⁶Pb/²⁰⁴Pb_i=18.786–19.574). P-wave seismic tomography of the mantle below the Veneto region shows the presence of low-velocity anomalies at depth, which is consistent with possible upwellings of plume material. Between the depths of 100–250 km the velocity anomalies are approximately 2–2.5% slower than average, implying a temperature excess of about 220–280 K, in agreement with estimates for other mantle plumes in the world. In this context, the Veneto volcanics may represent the shallow expression of a mantle upflow. The presence of a HIMU-DM component in a collision environment has significant geodynamic implications. Slab detachment and ensuing rise of deep mantle material into the lithospheric gap is proposed to be a viable mechanism of hotspot magmatism in a subduction zone setting.     

The relationship between calc-alkaline volcanism and within-plate continental rift volcanism: evidence from Scottish Palaeozoic lavas

Lower Carboniferous lavas from the Midland Valley and adjacent regions of Scotland are mildly alkaline and intraplate in nature. The sequence is dominated by basalt and hawaiite, although mugearite, benmoreite, trachyte and rhyolite are also present. Basic volcanic rocks display the LIL element and LREE enrichment typical of intraplate alkali basalt terrains. Low initial⁸⁷Sr/⁸⁶Sr (0.7029–0.7046), high ε_Nd (−0.4 to +5.6) and moderately radiogenic²⁰⁶Pb/²⁰⁴Pb (17.77–18.89) ratios are also comparable with alkali basalts from other continental rifts and oceanic islands.When the Carboniferous lavas are compared with subduction-related lavas of Old Red Sandstone age, erupted in and around the Midland Valley ca. 50 Ma earlier (at 410 Ma) remarkable similarities are apparent. Significant overlap occurs in Nd and Pb isotopic compositions. Sr isotopic compositions are, however, more radiogenic in the older subduction-related lavas. This, combined with high K and Rb concentrations in ORS lavas may be explained by the incorporation of a sediment component derived from the subducted slab, which by Lower Carboniferous times had been lost from the mantle source region by convection. A pronounced negative Nb anomaly in the ORS subduction-related lavas may be explained by the retention of a Nb-bearing phase in the mantle during hydrous melting of the mantle wedge above the subduction zone.Allowing for the effects of the added component from the subducted slab, there appears to be no necessity to invoke separate mantle source regions for the two suites of lavas: both may have been derived from chemically similar portions of mantle. If volcanic arc lavas are derived from the mantle wedge, the implication is that such a source lies at relatively shallow depth within the upper mantle: the same may therefore apply to the Carboniferous continental rift basalts. This evidence, combined with the fact that there is no evident hot-spot trail across the Midland Valley despite a long period of within-plate volcanism and rapid plate movements during the Carboniferous, suggests that the alkali basalt magmatism is not the product of a deep-seated mantle plume. Rather, the volcanism appears to owe more to passive rifting and to diapiric upwelling from a source region within the uppermost mantle.     

O, S, Sr, and Pb isotope variations in volcanic rocks from the Northern Mariana Islands: implications for crustal recycling in intra-oceanic arcs

Quaternary lavas from the Northern Mariana Islands have respective O- and S-isotope ranges ofδ¹⁸O = +5.7 to +6.6 (‰ SMOW) andδ³⁴S = +2.0to+20.7 (‰ CDT). Chemically evolved andesites and dacites with meanδ¹⁸O = +6.3 ± 0.2 are slightly enriched in¹⁸O with respect to unfractionated basalts of<53%SiO₂ with meanδ¹⁸O = +6.0 ± 0.1. This¹⁸O enrichment can be explained in terms of differentiation of parental mafic magmas havingδ¹⁸O values between +5.7 to +6.2‰ through closed-system crystal fractionation because the lavas from all nine islands of the arc define a coherentδ¹⁸OSiO₂ trend. The S-isotope composition of oxidized magmas is not modified extensively through the degassing of SO₂; therefore, the meanδ³⁴S value of ca. +11‰ for the Mariana lavas is considered to be representative of their source region.The enrichment of¹⁸O and³⁴S in Mariana Arc parental magmas relative to ocean floor basalts withδ¹⁸O ca. + 5.7‰ andδ³⁴S = ca.0.3‰ is attributed to the recycling of¹⁸O- and³⁴S-rich crustal components (sediment withδ¹⁸O = ca. + 25‰ and seawater sulfate withδ³⁴S = ca. +20‰ into the upper mantle source region for these arc magmas. This interpretation is consistent with enrichments of radiogenic Sr and Pb in the same lavas relative to ocean-floor basalts erupted either side of the arc, which are presumed to share a common upper mantle source. This enrichment is considered to reflect the mixing of two components, one having a typical upper mantle composition and the other having a more radiogenic character similar to that of western Pacific pelagic sediments.     

Variation in noble gas isotopic composition of gas samples from the Aegean arc, Greece

In contrast to most other arcs with oceanic plate subduction, the Aegean arc is characterized by continent–continent subduction. Noble gas abundances and isotopic compositions of 45 gas samples have been determined from 6 volcanoes along the arc, 2 islands in the back-arc region and 7 sites in the surrounding areas. The ³He/⁴He ratios of the samples ranged from 0.027R_A to 6.2R_A (R_A denotes the atmospheric ³He/⁴He ratio of 1.4×10⁻⁶), demonstrating that even the maximum ³He/⁴He ratio in the region is significantly lower than the maximum ratios of most oceanic subduction systems, which are equal to the MORB value of 8±1 R_A. Regional variations in the ³He/⁴He ratio were observed both along and across the arc. The maximum ³He/⁴He ratio was obtained from Nisyros volcano located in the eastern end of the arc, and the ratio decreased westward possibly reflecting the difference in potential degree of crustal assimilation or the present magmatic activity in each volcano. Across the volcanic arc, the ³He/⁴He ratio decreased with an increasing distance from the arc front, reaching a low ratio of 0.063R_A in Macedonia, which suggested a major contribution of radiogenic helium derived from the continental crust. At Nisyros, a temporal increase in ³He/⁴He ratio due to ascending subsurface magma was observed after the seismic crisis of 1995–1998 and mantle neon was possibly detected. The maximum ³He/⁴He ratio (6.2R_A) in the Aegean region, which is significantly lower than the MORB value, is not probably due to crustal assimilation at shallow depth or addition of slab-derived helium to MORB-like mantle wedge, but inherent characteristics of the subcontinental lithospheric mantle (SCLM) beneath the Aegean arc.     

Homogenization and lowering of O/O in mid-crustal rocks during extension-related magmatism in eastern Nevada

The oxygen isotope systematics of Tertiary volcanic rocks of east-central Nevada and of plutonic and metamorphic rocks of the Ruby Mountains-East Humboldt Range core complex provide complementary evidence for major¹⁸O-depletion and ¹⁸O/¹⁶O homogenization of mid-crustal rocks during metamorphism and magmatism. The δ¹⁸O value of crustal source material for silicic volcanic rocks decreased from between +9 and +11‰ to between +7 and +8‰ over 5 Ma. Mid-crustal metasedimentary and granitic rocks in the East Humboldt Range have δ¹⁸O values very similar to the volcanic rocks and values are lower and more homogeneous at deeper structural levels. Exchange with deep-seated mantle-derived igneous rocks, or fluids derived therefrom, is the most plausible¹⁸O-depletion mechanism. Intrusion of these mafic magmas promoted crustal melting and fluid migration. Homogenization of ¹⁸O/¹⁶O resulted from migration of high-temperature fluids and melts at mid-crustal levels, and was less effective at higher structural levels where the crust was dominated by less permeable carbonate rocks.     

Isotope characteristics of submarine lavas from the Philippine Sea: implications for the origin of arc and basin magmas of the Philippine tectonic plate

Igneous rocks from the Philippine tectonic plate recovered on Deep Sea Drilling Project Legs 31, 58 and 59 have been analyzed for Sr, Nd and Pb isotope ratios. Samples include rocks from the West Philippine Basin, Daito Basin and Benham Rise (40–60 m.y.), the Palau-Kyushu Ridge (29–44 m.y.) and the Parece Vela and Shikoku basins (17–30 m.y.). Samples from the West Philippine, Parece Vela and Shikoku basins are MORB (mid-ocean ridge basalt)-like with ⁸⁷Sr/⁸⁶Sr= 0.7026−0.7032, ¹⁴³Nd/¹⁴⁴Nd= 0.51300−0.51315, and ²⁰⁶Pb/²⁰⁴Pb= 17.8−18.1. Samples from the Daito Basin and Benham Rise are OIB (oceanic island basalt)-like with ⁸⁷Sr/⁸⁶Sr= 0.7038−0.7040, ¹⁴³Nd/¹⁴⁴Nd= 0.51285−0.51291 and ²⁰⁶Pb/²⁰⁴Pb= 18.8−19.2. All of these rocks have elevated ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb compared to the Northern Hemisphere Regression Line (NHRL) and have δ²⁰⁷Pb values of 0 to +6 and δ²⁰⁸Pb values of +32 to +65. Lavas from the Palau-Kyushu Ridge, a remnant island arc, have ⁸⁷Sr/⁸⁶Sr= 7032−0.7035, ¹⁴³Nd/¹⁴⁴Nd= 0.51308−0.51310 and ²⁰⁶Pb/²⁰⁴Pb= 18.4−18.5. Unlike the basin magmas erupted before and after them, these lavas plot along the NHRL and have Pb-isotope ratios similar to modern Pacific plate MORB's. This characteristic is shared by other Palau-Kyushu Arc volcanic rocks that have been sampled from submerged and subaerial portions of the Mariana fore-arc.At least four geochemically distinct magma sources are required for these Philippine plate magmas. The basin magmas tap Source 1, a MORB-mantle source that was contaminated by EMI (enriched mantle component 1 [31]) and Source 2, an OIB-like mantle source with some characteristics of EMII (enriched mantle component 2 [31]). The arc lavas are derived from Source 3, a MORB-source or residue mantle including Sr and Pb from the subducted oceanic crust, and Source 4, MORB-source or residue mantle including a component with characteristics of HIMU (mantle component with high U/Pb [31]). These same sources can account for many of the isotopic characteristics of recent Philippine plate arc and basin lavas. The enriched components in these sources which are associated with the DUPAL anomaly were probably introduced into the asthenosphere from the deep mantle when the Philippine plate was located in the Southern Hemisphere 60 m.y.b.p.     

Geochemical approach to magmatic evolution of Mt. Erciyes stratovolcano Central Anatolia, Turkey

Erciyes stratovolcano, culminating at 3917 m, is located in the Cappadocian region of central Anatolia. During its evolution, this Quaternary volcano produced pyroclastic deposits and lava flows. The great majority of these products are calc-alkaline in character and they constitute Kocdag and Erciyes sequences by repeated activities. Alkaline activity is mainly observed in the first stages of Kocdag and approximately first-middle stages of Erciyes sequences. Generally, Kocdag and Erciyes stages terminate by pyroclastic activities. The composition of lavas ranges from basalt to rhyolite (48.4–70.5 wt.% SiO₂). Calc-alkaline rocks are represented mostly by andesites and dacites. Some compositional differences between alkaline basaltic, basaltic and andesitic rocks were found; while the composition of dacites remain unchanged. All these volcanics are generally enriched in LIL and HFS elements relative to the orogenic values except Rb, Ba, Nb depleted alkaline basalt. ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd isotopic composition of the volcanics range between 0.703344–0.703964, 0.512920–0.512780 for alkaline basalts and change between 0.704322–0.705088, 0.512731–0.512630 for alkaline basaltic rocks whereas calc-alkaline rocks have relatively high Sr and Nd isotopic ratios (0.703434–0.705468, 0.512942–0.512600). Low Rb, Ba, Nb content with high Zr/Nb, low Ba/Nb, La/Yb ratio and low Sr isotopic composition suggest an depleted source component, while high Ba, Rb, Nb content with high La/Yb, Ba/Nb, low Zr/Nb and low ⁸⁷Sr/⁸⁶Sr ratios indicate an OIB-like mantle source for the generation of Erciyes alkaline magma. These elemental and ratio variations also indicate that the different mantle sources have undergone different degree of partial melting episodes. The depletion in Ba, Rb, Nb content may be explained by the removal of these elements from the source by slab-derived fluids which were released from pre-collisional subduction, modified the asthenospheric mantle. The chemically different mantle sources interacted with crustal materials to produce calc-alkaline magma. The Ba/Nb increase of calc-alkaline samples indicates the increasing input of crustal components to Erciyes volcanics. Sr and Nd isotopic compositions and elevated LIL and HFS element content imply that calc-alkaline magma may be derived from mixing of an OIB-like mantle melts with a subduction-modified asthenospheric mantle and involvement of crustal materials in intraplate environments.     

Nitrogen isotope geochemistry of basaltic glasses: implications for mantle degassing and structure?

The nitrogen isotope geochemistry of 15 basaltic glasses has been investigated using stepped heating and high sensitivity static vacuum mass spectrometry. At low temperature (< 600°C) the glasses release small amounts of nitrogen with δ¹⁵N_AIR, averaging −0.3‰, suggesting surficial adsorption of atmospheric nitrogen. At high temperature, usually with a maximum at 1000°C, indigenous nitrogen with a concentration ranging from 0.2 to 2.1 ppm is released. The δ¹⁵N values of this high temperature release show a wide range from −4.5‰ to +15.5‰. There is no correlation between N ppm and δ¹⁵N, and the samples apparently form 3 groups with distinctive δ¹⁵N. Six MORB glasses from the Mid-Atlantic Ridge, East Pacific Rise and Juan de Fuca Ridge define a group with δ¹⁵N = +7.5 ± 1.3‰. In contrast two Indian Ocean MORB glasses (Carlsberg Ridge and Gulf of Aden) gave negative δ¹⁵N averaging −3.2‰. Glasses from Loihi Seamount have high δ¹⁵N averaging +14.0 ± 1.0‰. Comparison of the δ¹⁵N data with the mantle models derived from helium and argon isotope studies suggests that the wide range in δ¹⁵N may reflect in part heterogeneities in the mantle related to its degassing history. It is possible, however, that magmatic degassing processes have also affected nitrogen isotopic compositions, and the data cannot yet be unambiguously interpreted in terms of source variations.     

Using postglacial sea level, crustal velocities and gravity-rate-of-change to constrain the influence of thermal effects on mantle lateral heterogeneities

Lateral heterogeneities in the mantle can be caused by thermal, chemical and non-isotropic pre-stress effects. Here, we investigate the possibility of using observations of the glacial isostatic adjustment (GIA) process to constrain the thermal contribution to lateral variations in mantle viscosity. In particular, global historic relative sea level, GPS in Laurentide and Fennoscandia, altimetry together with tide-gauge data in the Great Lakes area, and GRACE data in Laurentide are used. The lateral viscosity perturbations are inferred from the seismic tomography model S20A by inserting the scaling factor β to determine the contribution of thermal effects versus compositional heterogeneity and non-isotropic pre-stress effects on lateral heterogeneity in mantle viscosity. When β = 1, lateral velocity variations are caused by thermal effects alone. With β < 1, the contribution of thermal effect decreases, so that for β = 0, there is no lateral viscosity variation and the Earth is laterally homogeneous. These lateral viscosity variations are superposed on four different reference models which differ significantly in the lower mantle viscosity. The Coupled Laplace Finite Element method is used to predict the GIA response on a spherical, self-gravitating, compressible, viscoelastic Earth with self-gravitating oceans, induced by the ICE-4G deglaciation model.Results show that the effect of β on uplift rates and gravity rate-of-change is not simple and involves the trade-off between the contribution of lateral viscosity variations in the transition zone and in the lower mantle. Models with small viscosity contrast in the lower mantle cannot explain the observed uplift rates in Laurentide and Fennoscandia. However, the RF3S20 model with a reference viscosity profile simplified from Peltier's VM2 with the value of β around 0.2–0.4 is found to explain most of the global RSL data, the uplift rates in Laurentide and Fennoscandia and the BIFROST horizontal velocity data. In addition, the changes in GIA signals caused by changes in the value of β are large enough to be detected by the data, although uncertainty in other parameters in the GIA models still exists. This may encourage us to further utilize GIA observations to constrain the thermal effect on mantle lateral heterogeneity as geodetic and satellite gravity measurements are improved.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

Sr, Nd, O and H isotopic ratios in Ascension Island lavas and plutonic inclusions; cogenetic origin

Eighteen basic rocks from Ascension Island (South Atlantic) give a mean⁸⁷Sr/⁸⁶Sr ratio of 0.70311 ± 17 for both volcanics and plutonic inclusions. The late-stage differentiated rocks (rhyolites and granitic inclusions) have much higher⁸⁷Sr/⁸⁶Sr ratios, up to 0.712. All these rocks display the same range of Nd isotopic compositions (ε_Ndvalues from6.9to11.1with a mean on12samples of8.4 ± 0.6) implying a cogenetic relation between the two sequences. The D/H systematics lead to the same conclusion.In the NdSr diagram, the data plot close to the mantle array and show a positive correlation. This suggests a mixing between a depleted MORB-type mantle, i.e. the upper mantle, and a hot-spot with less depleted geochemical characteristics, i.e. the OIB mantle source.The total range of δ¹⁸O values lies between 4.8‰ for plagioclase cumulates and 6.7‰ for the most evolved rocks (peralkaline granites and comendites). The basic rocks have values around 5.3‰, typical of mantle-derived material. These oxygen data indicate that the high⁸⁷Sr/⁸⁶Sr ratios in the most evolved rocks (both volcanic and plutonic terms) result from the combination of two different processes: incorporation of slight amounts (< 1%) of high-temperature altered oceanic crust by the magma in the late stages of the differentiation process and then in-situ Rb decay since the time of formation of these rocks. Both processes were very effective because of the high Rb and low Sr contents of these evolved rocks.Oxygen isotope systematics in the Ascension Island granites and rhyolites indicate that a fractional crystallization process alone does not produce δ¹⁸O values higher than 6.7‰, i.e. that the ultimate δ¹⁸O enrichment, relative to the initial basic magma, is not greater than 1.5‰.     

Mantle-derived volatiles in continental crust: the Massif Central of France

CO₂-rich gases and groundwaters from springs and boreholes originating within the basement of the Massif Central have variable³He/⁴He ratios with correspondingR/R_a values ranging from 0.8 to 5.5 and 0.3 to 2.8 respectively, indicating the presence of a significant component of mantle helium. Molar concentrations of rare gases in the CO₂-rich gases are approximately 5 orders of magnitude greater than in the waters and suggest that a near-surface Henry's Law fractionation has occurred between exsolving CO₂ and water.δ¹³C values of the CO₂-rich gases are in the range −4.2 to −6.1‰, i.e. in that range normally attributed to mantle carbon, but which could also represent an average crustal composition and therefore do not discriminate between mantle and crustal sources.C/³He ratios show 4 orders of magnitude variation from 1.4 × 10¹² to 5 × 10⁸ and, compared to a mantleC/³He ratio of 10⁹, indicate that either a complex fractionation has occurred between mantle helium and mantle CO₂ or more likely that mantle rare gases have been diluted by large quantities of CO₂ with an average crustal carbon isotope composition. The regional distribution of³He and C does not show any obvious relationship to age or proximity of volcanic centres or major faults, suggesting that mantle-derived C and He components decoupled from their silicate melt sources at some depth.The results from this area of active fluid circulation suggest that C-isotope data derived from metamorphic terrains should be interpreted with great caution, but that input of some mantle-derived carbon is expected to accompany crustal extension.     

Helium isotopic variability within single diamonds from the Orapa kimberlite pipe

The distribution and isotopic composition of helium has been measured in a suite of well-characterized one-carat diamonds from the Orapa kimberlite, Botswana. Crushing of the diamonds in vacuo indicates that most of the helium is contained by the matrix (generally greater than 90%), rather than by the inclusions. Step-heating experiments, performed on inclusion-free fragments remaining after crushing, indicate that the³He/⁴He ratio is variablewithin individual diamonds. The fragments, as small as 10 mg, were heated in two timed steps, both at 2000°C. In every case, lower³He/⁴He ratios are observed in the first graphitization step (0.05–3 × atmospheric), while the last heating step releases helium with systematically higher³He/⁴He ratio (30–80 × atmospheric). We suggest that this internal isotopic variability is the result of stepwise graphitization: the first heating step initiates graphitization, which nucleates around defects, and the second heating step graphitizes the relatively defect-free regions of the diamond. The³He/⁴He ratio measured, using the partial graphitization technique, differs by up to a factor of 100 within a single specimen. The inclusion-free fragments release small quantities of helium below 2000°C, which suggests that helium release is obtained only by graphitization. The³He contents of the monocrystalline diamonds are relatively constant (at 3 × 10⁻¹³ cm³ STP/gram) and indicate that most of the isotopic variability is due to radiogenic⁴He. The variations in⁴He content are either related to zoning of Th and U in the diamonds (i.e., in-situ decay), to zoning of inherited⁴He, or to implantation of α-particles from a Th and U rich environment (i.e., kimberlite). Because the Orapa diamonds were mined from roughly 40 m depth in the kimberlite, spallation reactions from cosmic ray interactions are not a significant source of³He. However, calculations based on the age of the kimberlite (90 m.y.) and reasonable Th and U abundances suggest that most of the³He in the Orapa diamonds could be produced by⁶Li(n, α)T in the diamond. Although this may not be true of all diamonds, nuclear reactions in the crust and mantle (including spallation reactions at the surface) can explain many of the high³He/⁴He ratios previously reported for diamonds.     

Lithium isotope systematics of lavas from the Cook–Austral Islands: Constraints on the origin of HIMU mantle

Radiogenic isotope variations in lavas from the Cook–Austral volcanic chain have delineated three distinct mantle sources: a HIMU component, a depleted component (DM), and an enriched component (EM). To better constrain the mantle sources for South Pacific hot spot volcanism, we determined lithium isotopic compositions of lavas from Raivavae, Rapa, Mangaia and Tubuai of the volcanic chain. The study includes whole rock and mineral analyses. In general, δ⁷Li of most olivines resemble bulk rock composition whereas clinopyroxenes are variably lighter. This implies that clinopyroxene is more susceptible to diffusion-induced fractionation, in agreement with previous studies. Olivine δ⁷Li values span a narrower range than whole rock values, and do not extend to the very heavy compositions previously reported in HIMU bulk lavas. This discrepancy likely reflects alteration of bulk lavas, and suggests that Li-isotope analyses of bulk lavas should be interpreted with caution. Olivines from HIMU lavas have heavy δ⁷Li values (up to 6.2‰), and extend beyond the range reported for fresh MORB. Correlations between Li-isotopes and radiogenic isotopes suggest that the heavy δ⁷Li values in HIMU olivines are a source characteristic and not the result of post-magmatic alteration. Although the Li-isotope composition of recycled, dehydrated oceanic crust is currently under debate, our results suggest that HIMU lavas derive from a source containing recycled dehydrated oceanic crust, and that the “heavy” Li-isotope signature of altered oceanic crust is partially preserved during passage through the subduction factory.     

The fate of B, Cl and Li in the subducted oceanic mantle and in the antigorite breakdown fluids

We present an inventory of B, Cl and Li concentrations in (a) key minerals from a set of ultramafic samples featuring the main evolutionary stages encountered by the subducted oceanic mantle, and in (b) fluid inclusions produced during high-pressure breakdown of antigorite serpentinite. Samples correspond to (i) nonsubducted serpentinites (Northern Apennine and Alpine ophiolites), (ii) high-pressure olivine-bearing antigorite serpentinites (Western Alps and Betic Cordillera), (iii) high-pressure olivine-orthopyroxene rocks recording the subduction breakdown of antigorite serpentinites (Betic Cordillera). Two main dehydration episodes are recorded by the sample suite: partial serpentinite dewatering during formation of metamorphic olivine, followed by full breakdown of antigorite serpentine to olivine+orthopyroxene+fluid. Ion probe and laser ablation ICP-MS (LA ICP-MS) analyses of Cl, B and Li in the rock-forming minerals indicate that the hydrous mantle is an important carrier of light elements. The estimated bulk-rock B and Cl concentrations progressively decrease from oceanic serpentinites (46.7 ppm B and 729 ppm Cl) to antigorite serpentinites (20 ppm B and 221 ppm Cl) to olivine-orthopyroxene rocks (9.4 ppm B and 45 ppm Cl). This suggests release of oceanic Cl and B in subduction fluids, apparently without inputs from external sources. Lithium is less abundant in oceanic serpentinites (1.3 ppm) and the initial concentrations are still preserved in high-pressure antigorite serpentinites. Higher Li contents in olivine, Ti-clinohumite of the olivine-orthopyroxene rocks (4.9 ppm bulk rock Li), as well as in the coexisting fluid inclusions, suggest that their budget may not be uniquely related to recycling of oceanic Li, but may require input from external sources.Laser ablation ICP-MS analyses of fluid inclusions in the olivine-orthopyroxene rocks enabled an estimate of the Li and B concentrations in the antigorite breakdown fluid. The inclusion compositions were quantified using a range of salinity values (0.4-2 wt.% NaCl_equiv) as internal standards, yielding maximum average ^fluid/rockD_B∼5 and ^fluid/rockD_Li∼3.5. We also performed model calculations to estimate the B and Cl loss during the two dehydration episodes of serpentinite subduction. The first event is characterized by high fluid/rock partition coefficients for Cl (∼100) and B (∼60) and by formation of a fluid with salinity of 4-8 wt.% NaCl_equiv. The antigorite breakdown produces less saline fluids (0.4-2 wt.% NaCl_equiv) and is characterized by lower partition coefficients for Cl (25-60) and B (12-30). Our calculations indicate that the salinity of the subduction fluids decreases with increasing depths. ^fluid/rockD_B/^fluid/rockD_Cl<1 (∼0.5) indicates that Cl preferentially partitions into the evolved fluids relative to B and that the B/Cl of fluids progressively increases with increasing depths and temperatures.Despite light element release in fluids, appreciable B, Cl and Li are still retained in chlorite, olivine and Ti-clinohumite beyond the antigorite stability field. This permits a bulk storage of about 10 ppm B, 45 ppm Cl and 5 ppm Li, i.e., concentrations much higher than in mantle reservoirs. Chlorite is the Cl repository and its stability controls the Cl and H₂O budget beyond the antigorite stability; B and Li are bound in olivine and clinohumite. The subducted oceanic mantle thus retains light elements beyond the depths of arc magma sources, potentially introducing anomalies in the upper mantle.     

Age of the Archean Talga-Talga Subgroup, Pilbara Block, Western Australia, and early evolution of the mantle: new SmNd isotopic evidence

Archean komatiites, high-Mg basalts and tholeiites from the North Star Basalt and the Mount Ada Basalt formations of the Talga-Talga Subgroup, Warrawoona Group, Pilbara Block, Western Australia, define a linear correlation on the normal¹⁴³Nd/¹⁴⁴Nd vs.¹⁴⁷Sm/¹⁴⁴Nd isochron plot. The data give an age of 3712 ± 98 Ma and initialε_Nd(T) of +1.64 ± 0.40. The 3712 ± 98 Ma date is consistent with the regional stratigraphic sequence and available age data and the SmNd linear array may be interpreted as an isochron giving the eruption age of the Talga-Talga Subgroup. An alternative interpretation is that the isochron represents a mixing line giving a pre-volcanism age for the Subgroup. Consideration of geochemical and isotopic data indicates that the true eruptive age of the Talga-Talga Subgroup is possibly closer to about 3500 Ma. Regardless of the age interpretation, the new Nd isotopic data support an existence of ancient LREE-depleted reservoirs in the early Archean mantle, and further suggest that source regions for the Pilbara volcanic rocks were isotopically heterogeneous, withε_Nd(T) values ranging from at least 0 to +4.0.     

The transition from calc-alkaline to potassic orogenic magmatism in the Aeolian Islands,Southern Italy

The Aeolian volcanic arc displays a wide range of magmatic products. Mafic lavas range from hypersthene normative calc-alkaline basalts to silica-undersaturated potassic absarokites, although the former are spatially and temporally dominant, consistent with the subduction-zone tectonic setting. In addition, intermediate and acidic members of the various fractionation series may be recognised. Large variations in trace element and isotope ratios accompany the rapid calc-alkaline to potassic transition, and it is argued that these may be largely explained in terms of subduction-zone mantle enrichment involving components derived from both basaltic ocean crust and subducted sediments. In addition, it seems that the mantle wedge itself was substantially heterogeneous prior to the onset of subduction zone processes. Not only are these subduction components similar to those proposed in a number of island arcs, but they also resemble those recognised in the ultra-potassic lavas of the Roman province, supporting recent subduction-related petrogenetic models of the Roman magmatism. Although subducted sediment plays an important role in the generation of some potassic magmatism, it is not uniquely responsible for K₂O-rich lavas, which are also produced without a large sediment contribution.     

Isotope geochemistry and origin of calc-alkaline lavas from a caledonian continental margin volcanic arc

Analyses for major and trace elements, including REE, and Sr, Nd and Pb isotopes are reported from a suite of Siluro-Devonian lavas from Fife, Scotland. The rocks form part of a major calc-alkaline igneous province developed on the Scottish continental margin above a WNW-dipping subduction zone. Within the small area (ca. 15 km²) considered, rock types range from primitive basalts and andesites (high Mg, Ni and Cr) to lavas more typical of modern calc-alkaline suites with less than 30 ppm Ni and Cr. There is a marked silica gap between these rocks (< 62%) and the rare rhyolites (> 74%), yet the latter can be generated by fractional crystallization from the more mafic lavas. In contrast, variation in incompatible element concentrations and ratios in the mafic lavas can not be generated by fractional crystallization processes. Increasing SiO₂ is accompanied by increasing Rb, K, Pb, U and Ba relative to Sr and high field strength elements, increasing LREE enrichment and increasing _Sr calculated at 410 Ma, and by decreasing HREE, Eu/Eu*, Sm/Nd and _Nd (410). _Nd and _Sr are roughly anticorrelated and have more radiogenic compositions than the mantle array, in common with data reported elsewhere from this part of the arc. The correlation extrapolates up to cross the mantle array within the composition field of the contemporary MORB source, and extrapolates down towards the probable compositional range of Lower Palaeozoic greywackes, which may form the uppermost 8 km of the crust, or may be supplied to the source by subduction. One sample, however, lies within the mantle array, and closely resembles lavas from northwestern parts of the arc, where a mantle source with mild time-integrated Rb/Sr and LREE enrichment has been inferred. The lavas have relatively high initial ²⁰⁷Pb/²⁰⁴Pb for their ²⁰⁶Pb/²⁰⁴Pb, a feature which has been interpreted elsewhere as the result of incorporation of a sediment component into arc magmas. The systematic changes with increasing SiO₂ in isotopic and chemical parameters can be explained by mixing of a greywacke-derived component with depleted mantle. The various possible mixing mechanisms are discussed, and it is considered most likely that mixing occurred in the mantle source through greywacke subduction. The bulk of the Rb, K, Ba and Pb in the lavas is probably recycled from the crust, whereas less than some 40% of the Sr and Nd is recycled. The calc-alkaline chemical trends are solely a function of mixing with the sediment component.     

Helium isotopes in some historical lavas from Mount Vesuvius

³He/⁴He ratios in lavas erupted during the last 360 years at Mt. Vesuvius are between 2.2 and 2.7 R_A (R_A = atmospheric ratio of 1.39 × 10⁻⁶), and are among the lowest values measured in young volcanic rocks. They are also identical to values measured in summit crater fumaroles sampled during 1987–1991. This agreement indicates that the ³He/⁴He ratio in the crater fumaroles faithfully tracks the magmatic value. The relatively low and uniform ³He/⁴He ratio in the lavas reflects either a mantle source enriched in (U + Th)/³He, or a mixture of magmatic and crustal components.