Cooling-induced fractionation of mantle Li isotopes from the ultraslow-spreading Gakkel Ridge

Li isotopic compositions of magmatic rocks have gained considerable attention recently as probes of mantle-scale processes. However, the concentrations and isotopic composition of Li in mantle minerals from mid-ocean ridges remain relatively unconstrained. This is largely because of the general presence of seawater alteration in abyssal peridotites. Lithium elemental and isotopic compositions for mineral separates of coexisting olivine, clinopyroxene, orthopyroxene and bulk rocks of serpentine-free Gakkel Ridge peridotites were investigated. Bulk rocks have Li contents of 1.6 to 2.7 ppm and δ⁷Li values of 3 to 5‰, which fall within the range of reported normal pristine “MORB mantle” values. Lithium concentrations vary in the order cpx (2.1–4.7 ppm) > opx (0.9–1.7 ppm) ≥ olivine (0.4–0.9 ppm), the opposite found in “equilibrated” mantle peridotite xenoliths (Seitz and Woodland, 2000). The Li isotopic compositions indicate a systematic mineral variation with δ⁷Li_olivine (7.14‰–15.09‰) > δ⁷Li_opx (1.81‰–3.66‰) > δ⁷Li_cpx (?2.43‰ ? ?0.39‰). The δ⁷Li values of cpx are negatively correlated with their Li concentrations with the lightest value for the most enriched cpx grains. There is a first order negative linear correlation between Δ_{olivine–cpx} (δ⁷Li_olivine ? δ⁷Li_cpx) and ^ol/cpxD (Li_olivine/Li_cpx).Numerical simulations indicate that the observed systematic inter-mineral variations of Li concentrations and isotopic compositions could be explained by a cooling driven diffusive redistribution between minerals in a closed system if there is a temperature dependent partitioning of Li between olivine and clinopyroxene. The studied Gakkel Ridge abyssal peridotites may alternatively have cooled under a variable cooling rate with a rapid cooling before the Li system was closed, which is less likely given the tectonic setting. Our calculations confirm that Li systematics in minerals, especially in coexisting mineral phases could potentially be used as a mantle geospeedometer, even for slowly cooled mantle rocks.     

Enriched,HIMU-type peridotite and depleted recycled pyroxenite in the Canary plume: A mixed-up mantle

The Earth's mantle is chemically and isotopically heterogeneous, and a component of recycled oceanic crust is generally suspected in the convecting mantle [Hofmann and White, 1982. Mantle plumes from ancient oceanic crust. Earth Planet. Sci. Lett. 57, 421–436]. Indeed, the HIMU component (high µ = ²³⁸U/²⁰⁴Pb), one of four isotopically distinct end-members in the Earth's mantle, is generally attributed to relatively old (≥ 1–2 Ga) recycled oceanic crust in the form of eclogite/pyroxenite, e.g. [Zindler and Hart, 1986. Chemical geodynamics. Ann. Rev. Earth Planet. Sci. 14, 493–571]. Although the presence of the recycled component is generally supported by element and isotopic data, little is known about its physical state at mantle depths. Here we show that the concentrations of Ni, Mn and Ca in olivine from the Canarian shield stage lavas, which can be used to assess the physical nature of the source material (peridotite versus olivine-free pyroxenite) [Sobolev et al., 2007. The amount of recycled crust in sources of mantle-derived melts. Science 316, 412–417], correlate strongly with bulk rock Sr, Nd and Pb isotopic ratios. The most important result following from our data is that the enriched, HIMU-type (having higher ²⁰⁶Pb/²⁰⁴Pb than generally found in the other mantle end-members) signature of the Canarian hotspot magmas was not caused by a pyroxenite/eclogite constituent of the plume but appears to have been primarily hosted by peridotite. This implies that the old (older than ~ 1 Ga) ocean crust, which has more evolved radiogenic isotope compositions, was stirred into/reacted with the mantle so that there is not significant eclogite left, whereas younger recycled oceanic crust with depleted MORB isotopic signature (< 1 Ga) can be preserved as eclogite, which when melted can generate reaction pyroxenite.     

Isotopic fractionation of zinc in tektites

Tektites are terrestrial natural glasses produced during a hypervelocity impact of an extraterrestrial projectile onto the Earth's surface. The similarity between the chemical and isotopic compositions of tektites and terrestrial upper continental crust implies that the tektites formed by fusion of such target rock. Tektites are among the driest rocks on Earth. Although volatilization at high temperature may have caused this extreme dryness, the exact mechanism of the water loss and the behavior of other volatile species during tektite formation are still debated. Volatilization can fractionate isotopes, therefore, comparing the isotope composition of volatile elements in tektites with that of their source rocks may help to understand the physical conditions during tektite formation.For this study, we have measured the Zn isotopic composition of 20 tektites from four different strewn fields. Almost all samples are enriched in heavy isotopes of Zn compared to the upper continental crust. On average, the different groups of tektites are isotopically distinct (listed from the isotopically lightest to the heaviest): Muong-Nong type indochinites (δ^66/64Zn = 0.61 ± 0.30‰); North American bediasites (δ^66/64Zn = 1.61 ± 0.49‰); Ivory Coast tektites (δ^66/64Zn = 1.66 ± 0.18‰); the Australasian tektites (others than the Muong Nong-type indochinites) (δ^66/64Zn = 1.84 ± 0.42‰); and Central European moldavites (δ^66/64Zn = 2.04 ± 0.19‰). These results are contrasted with a narrow range of δ^66/64Zn = 0–0.7‰ for a diverse spectrum of upper continental crust materials.The elemental abundance of Zn is negatively correlated with δ^66/64Zn, which may reflect that isotopic fractionation occurred by evaporation during the heating event upon tektite formation. Simple Rayleigh distillation predicts isotopic fractionations much larger than what is actually observed, therefore, such a model cannot account for the observed Zn isotope fractionation in tektites. We have developed a more realistic model of evaporation of Zn from a molten sphere: during its hypervelocity trajectory, the molten surface of the tektite will be entrained by viscous coupling with air that will then induce a velocity field inside the molten sphere. This velocity field induces significant radial chemical mixing within the tektite that accelerates the evaporation process. Our model, albeit parameter dependent, shows that both the isotopic composition and the chemical abundances measured in tektites can be produced by evaporation in a diffusion-limited regime.     

Oxygen isotope constraints on the origin and differentiation of the Moon

We report new high-precision laser fluorination three-isotope oxygen data for lunar materials. Terrestrial silicates with a range of δ¹⁸O values (− 0.5 to 22.9‰) were analyzed to independently determine the slope of the terrestrial fractionation line (TFL; λ = 0.5259 ± 0.0008; 95% confidence level). This new TFL determination allows direct comparison of lunar oxygen isotope systematics with those of Earth. Values of Δ¹⁷O for Apollo 12, 15, and 17 basalts and Luna 24 soil samples average 0.01‰ and are indistinguishable from the TFL. The δ¹⁸O values of high- and low-Ti lunar basalts are distinct. Average whole-rock δ¹⁸O values for low-Ti lunar basalts from the Apollo 12 (5.72 ± 0.06‰) and Apollo 15 landing sites (5.65 ± 0.12‰) are identical within error and are markedly higher than Apollo 17 high-Ti basalts (5.46 ± 0.11‰). Evolved low-Ti LaPaz mare-basalt meteorite δ¹⁸O values (5.67 ± 0.05‰) are in close agreement with more primitive low-Ti Apollo 12 and 15 mare basalts. Modeling of lunar mare-basalt source composition indicates that the high- and low-Ti mare-basalt mantle reservoirs were in oxygen isotope equilibrium and that variations in δ¹⁸O do not result from fractional crystallization. Instead, these differences are consistent with mineralogically heterogeneous mantle sources for mare basalts, and with lunar magma ocean differentiation models that result in a thick feldspathic crust, an olivine–pyroxene-rich mantle, and late-stage ilmenite-rich zones that were convectively mixed into deeper portions of the lunar mantle. Higher average δ¹⁸O (WR) values of low-Ti basalts compared to terrestrial mid ocean ridge basalts (Δ=0.18‰) suggest a possible oxygen isotopic difference between the terrestrial and lunar mantles. However, calculations of the δ¹⁸O of lunar mantle olivine in this study are only 0.05‰ higher than terrestrial mantle olivine. These observations may have important implications for understanding the formation of the Earth–Moon system.     

Mantle-derived carbon in Hercynian granites. Stable isotopes signatures and C/He associations in the thermomineral waters,N-Portugal

Na–HCO₃–CO₂-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO₂-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO₂-rich waters. The δ²H and δ¹⁸O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO₂ (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO₂ inorganic origin for the gas. δ¹³C_CO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO₂. Such an assumption is supported by the ³He/⁴He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression).     

Subduction erosion of forearc mantle wedge implicated in the genesis of the South Sandwich Island (SSI) arc: Evidence from boron isotope systematics

The South Sandwich volcanic arc is sited on a young oceanic crust, erupts low-K tholeiitic rocks, is characterized by unexotic pelagic and volcanogenic sediments on the down-going slab, and simple tectonic setting, and is ideal for assessing element transport through subduction zones. As a means of quantifying processes attending transfer of subduction-related fluids from the slab to the mantle wedge, boron concentrations and isotopic compositions were determined for representative lavas from along the arc. The samples show variable fluid-mobile/fluid-immobile element ratios and high enrichments of B/Nb (2.7 to 55) and B/Zr (0.12 to 0.57), similar to those observed in western Pacific arcs. δ¹¹B values are among the highest so far reported for mantle-derived lavas; these are highest in the central part of the arc (+ 15 to + 18‰) and decrease toward the southern and northern ends (+ 12 to + 14‰). δ¹¹B is roughly positively correlated with B concentrations and with ⁸⁷Sr/⁸⁶Sr ratios, but poorly coupled with other fluid-mobile elements such as Rb, Ba, Sr and U. Peridotites dredged from the forearc trench also have high δ¹¹B (ca. + 10‰) and elevated B contents (38–140 ppm). Incoming pelagic sediments sampled at ODP Site 701 display a wide range in δ¹¹B (+ 5 to ? 13‰; average = ? 4.1‰), with negative values most common. The unusually high δ¹¹B values inferred for the South Sandwich mantle wedge cannot easily be attributed to direct incorporation of subducting slab materials or fluids derived directly therefrom. Rather, the heavy B isotopic signature of the magma sources is more plausibly explained by ingress of fluids derived from subduction erosion of altered frontal arc mantle wedge materials similar to those in the Marianas forearc. We propose that multi-stage recycling of high-δ¹¹B and high-B serpentinite (possibly embellished by arc crust and volcaniclastic sediments) can produce extremely ¹¹B-rich fluids at slab depths beneath the volcanic arc. Infiltration of such fluids into the mantle wedge likely accounts for the unusual magma sources inferred for this arc.     

Osmium isotope and highly siderophile element systematics of the lunar crust

Coupled ¹⁸⁷Os/¹⁸⁸Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 ± 0.3 pg g^? 1 Os, 1.5 ± 0.6 pg g^? 1 Ir, 6.8 ± 2.7 pg g^? 1 Ru, 16 ± 15 pg g^? 1 Pt, 33 ± 30 pg g^? 1 Pd and 0.29 ± 0.10 pg g^? 1 Re (～ 0.00002 × CI) and Re/Os ratios that were modestly elevated (¹⁸⁷Re/¹⁸⁸Os = 0.6 to 1.7) relative to CI chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (～ 0.00007 × CI) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle–crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments.If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust–mantle concentration ratios (D-values) must be ≤ 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re. Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust–mantle HSE partitioning for the Earth and Moon are somewhat surprising. Low HSE abundances in the lunar crust, coupled with estimates of HSE concentrations in the lunar mantle implies there may be a ‘missing component’ of late-accreted materials (as much as 95%) to the Moon if the Earth/Moon mass-flux estimates are correct and terrestrial mantle HSE abundances were established by late accretion.     

A lithium isotopic study of sub-greenschist to greenschist facies metamorphism in an accretionary prism,New Zealand

To investigate the behavior of Li during low-grade metamorphism and fluid flux in an accretionary prism we measured the Li concentrations ([Li]) and isotopic compositions (δ⁷Li) of sub-greenschist and greenschist-facies Otago Schist composites, as well as cross-cutting quartz veins, which are interpreted to have precipitated from slab-derived fluids. The average [Li] of sub-greenschist facies composites (41 ± 13 μg/g, 2σ) is statistically distinct (97% confidence level, student t test) to that of greenschist facies composites (34 ± 9 μg/g, 2σ), which have experienced mass addition of silica in the form of quartz veins having [Li] between 0.4–2.3 μg/g. A linear regression of the correlation between [Li] and calculated mass additions suggests that the depletion of [Li] in greenschist facies composites is due to both dilution from the addition of the quartz veins, as well as metamorphic dehydration. The [Li] of both groups of composites correlates with their CIA (Chemical Index of Alteration) values (50–58), which are low, consistent with the inferred graywacke protolith of the Otago Schist. The δ⁷Li of sub-greenschist and greenschist facies composites are remarkably constant, with an average δ⁷Li of 0.2 ± 1.7 (2σ) and ?0.5 ± 1.9 (2σ), respectively, and comparable to that of the average upper continental crust. Thus, metamorphism has had no discernable effect on δ⁷Li in these samples. The Li isotopic signature of the schists is similar to that seen in pelitic sedimentary rocks and likely reflects the δ⁷Li of the protoliths. The surprisingly light δ⁷Li of the quartz veins (?2.8 to ?1.4) likely records kinetic fractionation associated with Li ingress into the veins from surrounding wallrock.An isotopic equilibrium fluid flow model indicates that: 1) if the [Li] of slab-derived fluids is less than a few μg/g, the δ⁷Li of the overlying lithologies (i.e., the schists) is not significantly influenced by the fluid flux, regardless of the δ⁷Li of the fluids, 2) the slab-derived fluids will have heavy δ⁷Li of > + 10 after reacting with the prism sediments during their ascent, and 3) the [Li] of the slab-derived fluids is likely in the range of 0 < [Li] ≤ 41(μg/g). Thus, isotopically heavy slab-derived fluids that traverse sediments in accretionary prisms may leave little trace in the rocks and their surface compositional characteristics will reflect the net result of their interaction with the sediments of the prism.     

Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ⁹⁸Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ⁹⁸Mo = + 2.17‰ (± 0.12), which agrees well with a δ⁹⁸Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ⁹⁸Mo of + 1.02‰, consistent with recent findings of positive δ⁹⁸Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ⁹⁸Mo ～ ? 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ⁹⁸Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ⁹⁸Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ⁹⁸Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ⁹⁸Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H₂S levels, while δ⁹⁸Mo may be primarily affected by annual variations in Mn refluxing.     

Lithospheric contributions to high-MgO basanites from the Cumbre Vieja Volcano,La Palma,Canary Islands and evidence for temporal variation in plume influence

New geochemical and isotopic data are presented from the oldest part of the Cumbre Vieja volcano, La Palma (Canary Islands), located near the assumed emergence of the Canary mantle plume. The volcanics comprise a suite dominated by basanite flows with subordinate amounts of phono-tephrite, tephri-phonolite and phonolite flows and intrusives. Two compositionally different basanite groups have been identified, both with HIMU (high-μ)-type incompatible trace element characteristics: Primitive high-MgO basanites (10.7–12.1% MgO), found only at the base of a stratigraphic profile near Fuencaliente on the south coast, and intermediate-MgO basanites (6.0–7.3% MgO), exposed in the upper part of the profile and widespread on the east coast of La Palma. The high-MgO basanites are interpreted as near-primary mantle melts (primary composition 14–15% MgO) derived by progressive melting (2.9% to 4.5%) of a common lithospheric mantle source. Model calculations indicate that it is not possible to generate the intermediate-MgO basanites from the high-MgO group by crystal fractionation of observed phenocrysts. Relative to intermediate-MgO basanites, the high-MgO flows have lower concentrations of LIL and HFS elements, except for Ti, which is markedly enriched in the primitive rocks (3.7–4.7% TiO₂ vs 3.4–3.9% TiO₂). Fuencaliente volcanics display limited temporal isotopic variations suggested to be a result of mixing of melts originating from the rising plume and the metazomatized lithospheric mantle. ⁸⁷Sr / ⁸⁶Sr and ¹⁴³Nd / ¹⁴⁴Nd ratios range 0.70305–0.70311 and 0.51285–0.51291, respectively, while the corresponding ranges in Pb-isotope ratios are ²⁰⁶Pb / ²⁰⁴Pb = 19.46–19.64, ²⁰⁷Pb / ²⁰⁴Pb = 15.55–15.61, and ²⁰⁸Pb / ²⁰⁴Pb = 39.16–39.53. The overall variation of the Cumbre Vieja isotopic data can be accounted for by mixtures of three mantle components in the proportions 72–79% plume source (LVC = low velocity component), 9–16% depleted mantle (DM) and up to 12% enriched mantle (EMI). Negative Δ7 / 4 Pb (− 0.6 to − 5.4) in the Cumbre Vieja volcanics suggest derivation from a young HIMU mantle source. The relative abundance of plume source material increase in younger rocks in the Fuencaliente section, suggesting waning plume–lithosphere interaction during the emplacement of this part of the Cumbre Vieja volcano. The high-MgO volcanics define regular and systematic geochemical trends, interpreted as partial melting trends, when plotted against abundances of highly incompatible elements (P, Ce). Evaluation of minor and trace element variation in consecutive melts suggests control by residual amphibole, phlogopite, garnet and a Ti-bearing phase, possibly ilmenite. The melting mode changed gradually, allowing increasing input from residual phlogopite during partial melting. The residual mineralogy constrains the source region of the high-MgO basanites to the lowermost oceanic lithospheric mantle, presumably around 100 km depths.     

Sr and Nd isotope composition of the metamorphic,sedimentary and ultramafic xenoliths of Lanzarote (Canary Islands): Implications for magma sources

The lavas produced by the Timanfaya eruption of 1730–1736 (Lanzarote, Canary Islands) contain a great many sedimentary and metamorphic (metasedimentary), and mafic and ultramafic plutonic xenoliths. Among the metamorphosed carbonate rocks (calc-silicate rocks [CSRs]) are monomineral rocks with forsterite or wollastonite, as well as rocks containing olivine ± orthopyroxene ± clinopyroxene ± plagioclase; their mineralogical compositions are identical to those of the mafic (gabbros) and ultramafic (dunite, wherlite and lherzolite) xenoliths. The ⁸⁷Sr/⁸⁶Sr (around 0.703) and ¹⁴³Nd/¹⁴⁴Nd (around 0.512) isotope ratios of the ultramafic and metasedimentary xenoliths are similar, while the ¹⁴⁷Sm/¹⁴⁴Nd ratios show crustal values (0.13–0.16) in the ultramafic xenoliths and mantle values (0.18–0.25) in some CSRs. The apparent isotopic anomaly of the metamorphic xenoliths can be explained in terms of the heat source (basaltic intrusion) inducing strong isotopic exchange (⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd) between metasedimentary and basaltic rocks. Petrofabric analysis also showed a possible relationship between the ultramafic and metamorphic xenoliths.     

Thermal history and origin of the Tanzanian Craton from Pb isotope thermochronology of feldspars from lower crustal xenoliths

Common and radiogenic Pb isotopic compositions of plagioclase and anti-perthitic feldspars from granulite-facies lower crustal xenoliths from the Labait Volcano on the eastern margin of the Tanzanian Craton have been measured via laser ablation MC-ICP-MS. Common Pb in plagioclase and a single stage Pb evolution model indicate that the lower crust of the Tanzanian Craton was extracted from mantle having a ²³⁸U/²⁰⁴Pb of 8.1 ± 0.3 and a ²³²Th/²³⁸U of 4.3 ± 0.1 at 2.71 ± 0.09 Ga (all uncertainties are 2σ). Since 2.4 Ga, some orthoclase domains within anti-perthites have evolved with a maximum ²³⁸U/²⁰⁴Pb of 6 and ²³²Th/²³⁸U of 4.3. The spread in Pb isotopic composition in the anti-perthitic feldspars yields single crystal Pb–Pb isochrons of ～ 2.4 Ga, within uncertainty of U–Pb zircon ages from the same sample suite. The Pb isotopic heterogeneities imply that these granulites resided at temperatures < 600 °C in the lower crust of the Tanzanian Craton from ca. 2.4 Ga to the present. In concert with the chemistry of surface samples, mantle xenoliths, and lower crustal xenoliths, our data imply that the cratonic lithosphere in Tanzania formed ca. ～ 2.7 Ga, in a convergent margin setting, and has remained undisturbed since 2.7 Ga.     

The origins and concentrations of water,carbon, nitrogen and noble gases on Earth

The isotopic compositions of terrestrial hydrogen and nitrogen are clearly different from those of the nebular gas from which the solar system formed, and also differ from most of cometary values. Terrestrial N and H isotopic compositions are in the range of values characterizing primitive meteorites, which suggests that water, nitrogen, and other volatile elements on Earth originated from a cosmochemical reservoir that also sourced the parent bodies of primitive meteorites. Remnants of the proto-solar nebula (PSN) are still present in the mantle, presumably signing the sequestration of PSN gas at an early stage of planetary growth. The contribution of cometary volatiles appears limited to a few percents at most of the total volatile inventory of the Earth. The isotope signatures of H, N, Ne and Ar can be explained by mixing between two end-members of solar and chondritic compositions, respectively, and do not require isotopic fractionation during hydrodynamic escape of an early atmosphere.The terrestrial inventory of ⁴⁰Ar (produced by the decay of ⁴⁰K throughout the Earth's history) suggests that a significant fraction of radiogenic argon may be still trapped in the silicate Earth. By normalizing other volatile element abundances to this isotope, it is proposed that the Earth is not as volatile-poor as previously thought. Our planet may indeed contain up to ~ 3000 ppm water (preferred range: 1000–3000 ppm), and up to ~ 500 ppm C, both largely sequestrated in the solid Earth. This volatile content is equivalent to an ~ 2 (± 1) % contribution of carbonaceous chondrite (CI-CM) material to a dry proto-Earth, which is higher than the contribution of chondritic material advocated to account for the platinum group element budget of the mantle. Such a (relatively) high contribution of volatile-rich matter is consistent with the accretion of a few wet planetesimals during Earth accretion, as proposed by recent dynamical models.The abundance pattern of major volatile elements and of noble gases is also chondritic, with two notable exceptions. Nitrogen is depleted by one order of magnitude relative to water, carbon and most noble gases, which is consistent with either N retention in a mantle phase during magma generation, or trapping of N in the core. Xenon is also depleted by one order of magnitude, and enriched in heavy isotopes relative to chondritic or solar Xe (the so-called “xenon paradox”). This depletion and isotope fractionation might have taken place due to preferential ionization of xenon by UV light from the early Sun, either before Earth's formation on parent material, or during irradiation of the ancient atmosphere. The second possibility is consistent with a recent report of chondritic-like Xe in Archean sedimentary rocks that suggests that this process was still ongoing during the Archean eon (Pujol et al., 2011). If the depletion of Xe in the atmosphere was a long-term process that took place after the Earth-building events, then the amounts of atmospheric ¹²⁹Xe and ^131–136Xe, produced by the short-lived radioactivities of ¹²⁹I (T_1/2 = 16 Ma) and ²⁴⁴Pu (T_1/2 = 82 Ma), respectively, need to be corrected for subsequent loss. Doing so, the I–Pu–Xe age of the Earth becomes ≤ 50 Ma after start of solar system formation, instead of ~ 120 Ma as computed with the present-day atmospheric Xe inventory.     

Geoneutrinos and the energy budget of the Earth

The total energy loss of the Earth is well constrained by heat flux measurements on land, the plate cooling model for the oceans, and the buoyancy flux of hotspots. It amounts to 46 ± 2 TW. The main sources that balance the total energy loss are the radioactivity of the Earth's crust and mantle, the secular cooling of the Earth's mantle, and the energy loss from the core. Only the crustal radioactivity is well constrained. The uncertainty on each of the other components is larger than the uncertainty of the total heat loss. The mantle energy budget cannot be balanced by adding the best estimates of mantle radioactivity, secular cooling of the mantle, and heat flux from the core. Neutrino observatories in deep underground mines can detect antineutrinos emitted by the radioactivity of U and Th. Provided that the crustal contribution to the geoneutrino flux can be very precisely calculated, it will be possible to put robust constraints on mantle radioactivity and its contribution to the Earth's energy budget. Equally strong constraints could be obtained from a deep ocean observatory without the need of crustal correction. In the future, it may become possible to obtain directional information on the geoneutrino flux and to resolve radial variations in concentration of heat producing elements in the mantle.     

Himalayan metamorphic CO2 fluxes: Quantitative constraints from hydrothermal springs

Hot springs in the Marsyandi Valley, Nepal, vent CO₂ sourced from metamorphic fluids that mix with shallow groundwaters before degassing near the Earth's surface. The δ¹³C of spring waters ranges up to + 13‰, while that of the coexisting free gas phase is close to ? 4‰. Empirical and thermodynamic modelling of this isotopic fractionation suggests > 97 ± 1% CO₂ degassing. The calculated minimum total CO₂ degassing in the Marsyandi catchment is 5.4 × 10⁹ mol/yr from a Cl-based estimate of the spring water discharge to the Marsyandi River and the fraction of CO₂ degassed. Extrapolated to the whole of the Himalayas, this implies a probable minimum metamorphic CO₂ flux of 0.9 × 10¹² mol/yr, or ～ 13% of solid Earth CO₂ degassing. The calculated flux is a factor of three greater than the estimated CO₂ drawdown by silicate weathering in the Himalayas. Himalayan metamorphic degassing contributes a significant fraction of the global solid Earth CO₂ flux and implies that metamorphism may cause changes in long-term climate that oppose those resulting from the orogenic forcing of chemical weatherability.     

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.     

Primitive neon and helium isotopic compositions of high-MgO basalts from the Kerguelen Archipelago,Indian Ocean

The geochemical characteristics of mildly alkalic basalts (24–25 Ma) erupted in the southeastern Kerguelen Archipelago are considered to represent the best estimate for the composition of the enriched Kerguelen plume end-member. A recent study of picrites and high-MgO basalts from this part of the archipelago highlighted the Pb and Hf isotopic variations and suggested the presence of mantle heterogeneities within the Kerguelen plume itself. We present new helium and neon isotopic compositions for olivines from these picrites and high-MgO basalts (6–17 wt.% MgO) both to constrain the enriched composition of the Kerguelen plume and to determine the origin of isotopic heterogeneities involved in the genesis of Kerguelen plume-related basalts. The olivine phenocrysts have extremely variable ⁴He / ³He compositions between MORB and primitive values observed in OIB (∼90,000 to 40,000; i.e., R / R_a ∼8 to 18) and they show primitive neon isotopic ratios (average ²¹Ne / ²¹Ne_ext ∼0.044). The neon isotopic systematics and the ⁴He / ³He ratios that are lower than MORB values for the Kerguelen basalts clearly suggest that the Kerguelen hotspot belongs to the family of primitive hotspots, such as Iceland and Hawaii. The rare gas signature for the Kerguelen samples, intermediate between MORB and solar, is apparently inconsistent with mixing of a primitive component with a MORB-like source, but may result from sampling a heterogeneous part of the mantle with solar ³He / ²²Ne and with a higher (U, Th) / ³He ratio compared to typically high R / R_a hotspot basalts such as those from Iceland and Hawaii.     

Coupled silicon–oxygen isotope fractionation traces Archaean silicification

Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa.The δ³⁰Si and δ¹⁸O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (?0.64‰ < δ³⁰Si < ?0.01‰ and + 8.6‰ < δ¹⁸O < + 11.9‰) to silicified basalts (δ³⁰Si and δ¹⁸O values as high as + 0.81‰ and + 15.6‰, respectively). Cherts generally have positive isotope ratios (+ 0.21‰ < δ³⁰Si < + 1.05‰ and + 10.9 < δ¹⁸O < + 17.1), except two cherts, which have negative δ³⁰Si values, but high δ¹⁸O (up to + 19.5‰).The pronounced positive correlations between δ³⁰Si, δ¹⁸O and SiO₂ imply that the isotope variation is driven by the silicification process which coevally introduced both ¹⁸O and ³⁰Si into the basalts. The oxygen isotope variation in the basalts from about 8.6‰ to 15.6‰ is likely to represent temperature-dependent isotope fractionation during alteration. Our proposed model for the observed silicon isotope variation relies on a temperature-controlled basalt dissolution vs. silica deposition process.     

Os isotope heterogeneity of the upper mantle: Evidence from the Mayarí–Baracoa ophiolite belt in eastern Cuba

In an attempt to quantify the extent of geochemical heterogeneity within a restricted and well dated portion of the upper mantle, 27 chromite separates from the 90 My old chromite deposits in the Mayarí–Baracoa ophiolite belt in eastern Cuba have been investigated for platinum group element (PGE) concentrations and Re–Os isotopic systematics. The samples are characterized by systematically subchondritic initial ¹⁸⁷Os/¹⁸⁸Os ratios and substantial heterogeneity. The initial ¹⁸⁷Os/¹⁸⁸Os ratios vary with chromite chemistry and with geographical distribution, reflecting differences in the Os isotopic evolution for the different upper mantle sections represented by the ophiolite. Accordingly, the Os isotope data might be divided into three groups. In the Moa–Baracoa district, where the chromite bodies are located in the mantle–crust transition zone, the calculated initial γOs values average − 0.97 ± 0.69 (n = 13). In the Sagua de Tanamo district, where chromite chemistry is highly variable and their location in relation the mantle sequence is less clear, the initial γOs values are intermediate, with an average of − 1.77 ± 0.80 (n = 7). In the Mayarí district, where the chromite bodies are located in the lower part of the mantle sequence, initial γOs values average − 2.66 ± 0.29 (n = 7). These subchondritic (i.e. negative) initial γOs values are most simply explained by Re depletion during ancient partial melting and/or melt percolation events.The Os isotope heterogeneity documented here indicates a high degree of geochemical complexity on small to intermediate length scales in the upper mantle. Our results, in combination with data on chromites from the literature, show that an “average present-day Os isotopic composition” for the hypothetical depleted MORB mantle (DMM) reservoir cannot be precisely established beyond the statement that it is “broadly chondritic”. Indeed, the upper mantle cannot be considered a sufficiently homogeneous geochemical “reservoir” to serve meaningfully as a baseline against which geochemical “anomalies” are evaluated. On the other hand, our findings are consistent with the “Statistical Upper Mantle Assemblage” or “SUMA”-concept, according to which a high level of geochemical heterogeneity is maintained in the upper mantle at all relevant length scales, as a result of the plate-tectonic cycle and intra-mantle processes such as melt-migration and metasomatism.     

New constraints on the HIMU mantle from neon and helium isotopic compositions of basalts from the Cook–Austral Islands

High ⁴He/³He ratios of 100 000 to 160 000 found at HIMU ocean islands (“high μ,” where μ is the U/Pb ratio) are usually attributed to the presence of recycled oceanic crust in the HIMU mantle source. However, significantly higher ⁴He/³He ratios are expected in recycled crust after residence in the mantle for periods greater than 1 Ga. In order to better understand the helium isotopic signatures in HIMU basalts, we have measured helium and neon isotopic compositions in a suite of geochemically well-characterized basalts from the Cook–Austral Islands. We observe ⁴He/³He ratios ranging from 56 000 to 141 000, suggesting the involvement of mantle reservoirs both more and less radiogenic than the mantle source for mid-ocean ridge basalts (MORBs). In addition, we find that the neon isotopic compositions of HIMU lavas extend from the MORB range to compositions less nucleogenic than MORBs. The Cook-Austral HIMU He–Ne isotopic compositions, along with Sr, Nd, Pb, and Os isotopic compositions, indicate that in addition to recycled crust, a relatively undegassed mantle end-member (e.g., FOZO) is involved in the genesis of these basalts. The association of relatively undegassed mantle material with recycled crust provides an explanation for the close geographical association between HIMU lavas and EM (enriched mantle)-type lavas from this island chain: EM-type signatures represent a higher mixing proportion of relatively undegassed mantle material. Mixing between recycled material and relatively undegassed mantle material may be a natural result of entrainment processes and convective stirring in deep mantle.