Terrestrial Igneous Rocks Research Articles

Volatile systematics in terrestrial igneous apatite: from microanalysis to decoding magmatic processes

Apatite has been recognized as a robust tool for the study of magmatic volatiles in terrestrial and extraterrestrial systems due to its ability to incorporate various volatile components and its common occurrence in igneous rocks. Most previous studies have utilized apatite to study individual magmatic systems or regions. However, volatile systematics in terrestrial magmatic apatite formed under different geological environments has been poorly understood. In this study, we filtered a large compilation of data for apatite in terrestrial igneous rocks (n > 20,000), categorized the data according to tectonic settings, rock types, and bulk-rock compositions, and conducted statistical analyses of the F–Cl–OH–S–CO2 contents (~ 11,000 data for halogen and less for other volatiles). We find that apatite from volcanic arcs preserves a high Cl signature in comparison to other tectonic settings and the median Cl contents differ between arcs. Apatite in various types and compositions of igneous rocks shows overlapping F–Cl–OH compositions and features in some rock groups. Specifically, apatite in kimberlite is characterized as Cl-poor, whereas apatite in plutonic rocks can contain higher F and lower Cl contents than the volcanic counterparts. Calculation using existing partitioning models indicates that apatite with a high OH (or F) content does not necessarily indicate a H2O-rich (or H2O-poor) liquid because it could be a result of high (or low) magma temperature. Our work may provide a new perspective on the use of apatite to investigate volatile behavior in magma genesis and evolution across tectonic settings, volatile recycling at subduction zones, and the volcanic-plutonic connection.

Determination of Rare Earth Element Isotopic Compositions Using Sample-Standard Bracketing and Double-Spike Approaches.

Rare earth elements (REEs) have been found to have numerous uses to trace geological and cosmochemical processes through analyses of elemental patterns, radioactive decay, nucleosynthetic anomalies, and cosmogenic effects. Stable isotopic fractionation is one aspect of REE geochemistry that has been seldom studied, with most publications focusing on the development of analytical methodologies for individual REEs, and most applications concerning terrestrial igneous rocks. In this study, we present a method to systematically analyze stable isotopic fractionations of 8 REEs, including Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb, using sample-standard bracketing (SSB) and double-spike (DS) approaches. All REEs are separated and purified using a fluoropolymer pneumatic liquid chromatography (FPLC) system. We introduce procedures for identifying and correcting some isobaric interferences in double-spike data reduction. Several geostandards, including igneous rocks and sediments, are analyzed using SSB and DS methods. The results indicate that REE isotopic fractionation in igneous processes is limited, except for Eu. Other REEs can still be isotopically fractionated by low-temperature processes and kinetic effects at a high temperature.

Highest terrestrial 3He/4He credibly from the core.

The observation that many lavas associated with mantle plumes have higher 3He/4He ratios than the upper convecting mantle underpins geophysical, geodynamic and geochemical models of Earth's deep interior. High 3He/4He ratios are thought to derive from the solar nebula or from solar-wind-irradiated material that became incorporated into Earth during early planetary accretion. Traditionally, this high-3He/4He component has been considered intrinsic to the mantle, having avoided outgassing caused by giant impacts and billions of years of mantle convection1-4. Here we report the highest magmatic 3He/4He ratio(67.2 ± 1.8 times the atmospheric ratio) yet measured in terrestrial igneous rocks, in olivines from Baffin Island lavas. We argue that the extremely high-3He/4He helium in these lavas might derive from Earth's core5-9. The viability of the core hypothesis relaxes the long-standing constraint-based on noble gases in lavas associated with mantle plumes globally-that volatile elements from the solar nebula have survived in the mantle since the early stages of accretion.

Iron Isotope Systematics of the Skaergaard Intrusion and Implications for its Liquid Line of Descent

Abstract The Skaergaard intrusion is one of the most thoroughly studied layered mafic intrusions on Earth and an exceptional example of (near) closed-system magmatic differentiation. We report new Fe isotope data for whole rocks, and magnetite and ilmenite separates through the layered series (LS) and upper border series (UBS) of the intrusion. δ56Fe values for gabbroic rocks range from 0.033‰ to 0.151‰ with an abrupt step increase at the base of Lower Zone c (LZc) within LS with the appearance of cumulus magnetite and subsequent decline accompanying FeTi oxide fractionation. The lowest δ56Fe values are found near the Upper Zone b (UZb) to c (UZc) boundary followed by a sharp rise across UZc approaching the Sandwich Horizon. Magnetite–ilmenite separates straddle bulk rock compositions with fractionation factors (Δ56Femt-ilm) of 0.081‰ to 0.239‰, consistent with subsolidus equilibration. Granophyric rocks occurring as pods, sheets and wispy layers from the upper zone and UBS equivalents and having unradiogenic Sr similar to gabbroic rocks of Skaergaard, are isotopically heavier than their host ferrodiorites (Δ56Fegranophyre-ferrodiorite ≥ 0.1‰) reaching a maximum δ56Fe of 0.217‰ in UBS. A fused xenolith from UBS has δ56Fe = 0.372‰. This range in δ56Fe spans much of that reported for terrestrial igneous rocks, and like the global dataset, shows a pronounced increase in δ56Fe with inferred silica content of modeled Skaergaard liquids. Forward modeling of closed system fractional solidification was undertaken to account for Fe isotope systematics, first by testing published liquid lines of descent (LLD), and then by exploring improvements and considering the impacts of liquid immiscibility, crustal contamination, fluid exsolution and diffusional processes. Our modeling relies on published Fe+2 and Fe+3 force constants for magmatic minerals and silicate glasses, and the most reliable estimates of the average bulk composition and mass proportions of the well-defined subzones of the intrusion. We show that the increase in δ56Fe across the LZb–LZc boundary is readily explained by the increased incorporation of Fe+3 into the crystallizing solid including magnetite. We further demonstrate that the classic Fenner LLD, involving strong Fe enrichment at nearly constant silica, does not lead to a rise in δ56Fe toward the end stages of evolution, while a Bowen-like LLD, with little Fe enrichment and strong Si enrichment, also underestimates enrichment in heavy Fe isotopes in the ferrodiorites of UZc. A LLD following an intermediate path involving modest Fe and Si enrichment, followed by Fe depletion best explains the observations. We predict ~3.5% (by mass) residual liquid after crystallization of UZc having a composition similar to felsic segregations in pegmatitic bodies found in the intrusion. While liquid immiscibility may have been encountered within fractionating mush at the margins of the intrusion, the Fe isotope systematics do not support liquid phase separation of the bulk magma. Crustal contamination, fluid exsolution, hydrothermal alteration and thermal diffusion are also shown to have no resolvable effect on the Fe isotope composition of the gabbroic and granophyric rocks. We conclude that the Fe isotope systematics documented in the Skaergaard intrusion reflect the dominant role of fractionating Fe-rich minerals from gabbroic through ferrodioritic to rhyolitic liquids. The success of our model to account for the observed Fe isotope systematics for Skaergaard demonstrates the utility of Fe+2 and Fe+3 force constants determined at ambient conditions to model magmatic conditions and gives critical insights into plutonic processes fractionating Fe isotopes complementary to the volcanic record.

The indium isotopic composition of the bulk silicate Earth

Indium (In) behaves as a moderately volatile metal during nebular and planetary processes, and its volatility depends strongly on oxygen fugacity. The In isotopic composition of the bulk silicate Earth (BSE) could provide a critical constraint on the nature of Earth’s building blocks and mechanisms that lead to its volatile depletion. However, accurately and precisely determining the isotopic composition of In of the silicate Earth is challenging due to its low abundance in igneous rocks and the presence of significant isobaric interferences on its isotopes (e.g., 113Cd+ on 113In+ and 115Sn+ on 115In+). Here, we present a purification procedure for In from rock matrices and report the first dataset of In isotopic compositions of 30 terrestrial igneous rocks, one biotite geostandard, and one carbonaceous chondrite (Allende) measured on a Nu Sapphire collision-cell equipped multi-collector inductively-coupled-plasma mass-spectrometer (CC-MC-ICP-MS) with an external reproducibility of 0.11‰ (2SD). At this level of precision, we find no statistically significant difference in the In isotopic compositions of mid-ocean-ridge basalts (MORB), oceanic island basalts (OIB), and continental flood basalts (CFB). Furthermore, Canary Islands, Iceland and Afar lavas display no analytically resolvable In isotopic variations from basalts to rhyolites. Therefore, In isotope fractionation during igneous processes is smaller than our analytical uncertainty and the In isotopic compositions of basalts are likely to be representative samples of their mantle sources. The twenty-one terrestrial basalts from diverse geological settings have an average δ115In of 0.35 ± 0.07 ‰ (2SD). This value represents the current best estimate of the In isotopic composition of the mantle as well as of the bulk silicate Earth, assuming limited In isotope fractionation during mantle partial melting, and due to the small contribution of the continental crust to the In budget (<5%). This isotopic composition provides a baseline with which to compare with chondrites and differentiated planetary bodies in future studies.

Visible and near-infrared reflectance spectra of igneous rocks and their powders

Most solid planetary bodies in the solar system are covered by a layer of fine particles and the topic of light scattering by small particles has been thoroughly studied in the past decades. In contrast, light reflection from intact rocks has received much less attention, though the spectral features of fresh rocks are more diagnostic than that of highly space-weathered regolith grains. As high spatial-resolution spectral images obtained by modern space-borne and in-situ sensors have become available, it is important to understand the spectral feature links between rocks and powders made by crushing the rocks. In this work, we selected 13 terrestrial igneous rocks with a 1 μm absorption feature and measured the visible and near-infrared reflectance spectra of their slabs and powders in three size fractions, 0-45 μm, 90-125 μm, and 450-900 μm. We have found that the spectral characteristics of these samples can be divided into two groups. For slabs with reflectance lower than 0.1 at 0.5 μm, they have less pronounced 1 μm absorption feature. For slabs with reflectance higher than 0.1, they have pronounced 1 μm feature, consistent with that of their powdered counterparts. By using the equivalent-slab and the Hapke model, we obtained the optical constants and single scattering albedo values of the samples. The dependence of single scattering albedo on effective absorption thickness indicates that the differences between the spectral characteristics of rock slabs and powdered samples are likely controlled by the degree of weak surface scattering contributions. We reconstructed the spectrum of a powdered lunar meteorite which best matches the Chang'E-4 rock and found that the reconstructed rock spectra are very close to the rock spectrum observed in-situ by Chang'E-4.

Primordial neon in high-3He/4He Baffin Island olivines

Paleocene basaltic lavas exposed on Baffin Island have the highest 3He/4He found in any terrestrial igneous rocks and potentially contain the most pristine primordial mantle material exposed on Earth's surface. By vacuum-crushing large (1–3 g) olivine mineral separates, we extracted enough magmatic gas to obtain the first coupled helium, neon, and argon isotopic compositions of Baffin Island lavas. The five Baffin Island olivine samples have 3He/4He ranging from 36.2 ± 0.6 to 48.6 ± 1.3 (1σ) times the atmospheric ratio (Ra), overlapping with the highest known mantle values. Neon isotopic results fall on a mixing line between atmosphere and a high 20Ne/22Ne mantle endmember (with a maximum 20Ne/22Ne of 12.2). The slope of this mixing line is indistinguishable from that in subglacial Holocene glass from Iceland, but distinct from other hotspots and mid-ocean ridge basalt trends. This result supports the hypothesis that Baffin Island and Iceland lavas share a common high-3He/4He mantle component, despite the fact that recent paleogeographic reconstructions place the Iceland hotspot far from Baffin Island at the time of eruption (61 Ma). Our results also demonstrate that high-3He/4He mantle reservoirs have 3He/22Ne variability that either reflects ancient mantle heterogeneity or helium addition in the upper or lower mantle.

Chondritic mercury isotopic composition of Earth and evidence for evaporative equilibrium degassing during the formation of eucrites

Variations in the abundances of moderately volatile elements (MVE) are one of the most fundamental geochemical differences between the terrestrial planets. Whether these variations are the consequence of nebular processes, planetary volatilization, differentiation or late accretion is still unresolved. The element mercury is the most volatile of the MVE and is a strongly chalcophile element. It is one of the few elements that exhibit large mass-dependent (MDF) and mass-independent (MIF) isotopic fractionations for both odd (odd-MIF, Δ199Hg and Δ201Hg) and even (even-MIF, Δ200Hg) Hg isotopes in nature, which is traditionally used to trace Hg biogeochemical cycling in surface environments. However, the Hg isotopic composition of Earth and meteorites is not well constrained. Here, we present Hg isotopic data for terrestrial basaltic, trachytic and granitic igneous samples. These rocks are isotopically lighter (δ202Hg = −3.3 ± 0.9‰; 1 standard deviation) than sedimentary rocks that have previously been considered to represent the terrestrial Hg isotope composition (δ202Hg=−0.7±0.5‰; 1 standard deviation). We show degassing during magma emplacement induces MIF that are consistent with kinetic fractionation in these samples. Also presented is a more complete dataset for chondritic (carbonaceous, ordinary and enstatite) meteorites, which are consistent with previous work for carbonaceous chondrites (positive odd-MIF) and ordinary chondrites (no MIF), and demonstrate that some enstatite chondrites exhibit positive odd-MIF, similar to carbonaceous chondrites. The terrestrial igneous rocks fall within the range of chondritic compositions for both MIF and MDF. Given the fact that planetary differentiation (core formation, evaporation) would contribute to Hg loss from the silicate portion of Earth and would likely fractionate Hg isotopes from chondritic compositions, we suggest that the budget of the mantle Hg is dominated by late accretion of chondritic materials to Earth, as also suggested for other volatile chalcophile elements (S, Se, Te). Considering the Hg isotopic signatures, materials with compositions similar to CO chondrites or ordinary chondrites are the most likely late accretion source candidates. Finally, eucrite meteorites, which are highly depleted in volatile elements, are isotopically heavier than chondrites and exhibit negative odd-MIF. The origin of volatile depletion in eucrites has been vigorously debated. We show that Δ199Hg versus Δ201Hg relationships point toward an equilibrium nuclear field shift effect, suggesting that volatile loss occurred during a magma ocean phase at the surface of the eucrite parent body, likely the asteroid 4-Vesta.

Titanium isotopic fractionation during magmatic differentiation

To better investigate the behavior of titanium (Ti) isotopes during magmatic processes, we report high-precision Ti isotope compositions for 60 terrestrial igneous rocks from different geological settings worldwide. Based on their major element compositions and petrographic descriptions, these samples can be subdivided into two groups: Fe-Ti oxide unsaturated and Fe-Ti oxide saturated. The Fe-Ti oxide unsaturated group samples show a narrow δ49/47Ti (δ49/47Ti = [(49Ti/47Ti)sample/(49Ti/47Ti)OL-Ti] × 1000) range (− 0.036 ± 0.043‰ to 0.082 ± 0.021 ‰), and no correlation between δ49/47Ti and the degree of differentiation is observed. By contrast, Fe-Ti oxide saturated group samples show a remarkable δ49/47Ti variation, ranging from 0.005 ± 0.018‰ to 1.914 ± 0.006 ‰, which are positively correlated with SiO2 contents, and negatively correlated with MgO contents. In particular, multiple SiO2 vs. δ49/47Ti trends are observed in Fe-Ti oxide saturated group, which are controlled by crystal fractionation degrees, magma SiO2 compositions, and Fe-Ti oxide compositions during magma differentiation.

Retrieving magma composition from TIR spectra: implications for terrestrial planets investigations

Emissivity and reflectance spectra have been investigated on two series of silicate glasses, having compositions belonging to alkaline and subalkaline series, covering the most common terrestrial igneous rocks. Glasses were synthesized starting from natural end-members outcropping at Vulcano Island (Aeolian Islands, Italy) and on Snake River Plain (USA). Results show that the shift of the spectra, by taking Christiansen feature (CF) as a reference point, is correlated with SiO2 content, the SCFM factor and/or the degree of polymerization state via the NBO/T and temperature. The more evolved is the composition, the more polymerized the structure, the shorter the wavelength at which CF is observable. CF shift is also dependent on temperature. The shape of the spectra discriminates alkaline character, and it is related to the evolution of Qn structural units. Vulcano alkaline series show larger amount of Q4 and Q3 species even for mafic samples compared to the subalkaline Snake River Plain series. Our results provide new and robust insights for the geochemical characterization of volcanic rocks by remote sensing, with the outlook to infer origin of magmas both on Earth as well as on terrestrial planets or rocky bodies, from emissivity and reflectance spectra.

Fe isotopic composition of the Quaternary Red Clay in subtropical Southeast China: Redoxic Fe mobility and its paleoenvironmental implications

To probe Fe isotopic signatures of the Quaternary Red Clay (QRC) in subtropical southeastern China, two QRC profiles located in southern Anhui Province, Southeast China, were studied. The whole profiles were generally in a narrow range in δ56Fe of −0.040 ± 0.061‰—0.117 ± 0.048‰. The Yellow-brown Earth (YBE) and Uniform Red Clay (URC) of the upper profiles were similar in δ56Fe to the Xiashu Loess along the Yangtze River, Southeast China, and the loess, paleosols and Tertiary red clay in the Chinese Loess Plateaus, Northwest China, as well as the baseline of terrestrial igneous rocks. The slight variation of δ56Fe from the YBE to the URC suggests that the chemical weathering and rubification on the aerobic surface did not fractionate Fe isotopes significantly. The Reticulate Red Clay (RRC) underlying the YBE and URC fluctuated in δ56Fe to some extent. The white veins separated from the lower RRC were depleted of Fe oxides and heavier in Fe isotopes, and the red veins, on the contrary, were isotopically lighter in Fe. δ56Fe of the white veins, 0.345 ± 0.053‰ on average, was significantly higher than the bulk samples, 0.033 ± 0.044‰ on average, and the red veins, −0.021 ± 0.046‰ on average. This suggests that the reticulate textures of the RRC were formed by the reductive removal/re-precipitation of Fe due to the cyclical changes of redoxic conditions. Fe isotopic composition of the QRC was dominantly controlled by the redoxic mobility of Fe, rather than the degree of weathering. δ56Fe of the profiles was not correlated with the paleoclimatic events, and thus cannot be used as a paleoclimatic proxy. The fractionation of Fe isotopes in the lower RRC, however, indicated the occurrence of over-humid paleoclimate with alternations between drought and wetness in Southern China during the Pleistocene.

The vanadium isotopic composition of lunar basalts

We present the first high-precision vanadium (V) isotope data for lunar basalts. Terrestrial magmatic rock measurements can display significant V isotopic fractionation (particularly during (Fe,Ti)oxide crystallisation), but the Earth displays heavy V (i.e. higher 51V/50V) isotopic compositions compared to meteorites. This has been attributed to early irradiation of meteorite components or nucleosynthetic heterogeneity. The Moon is isotopically-indistinguishable from the silicate Earth for many refractory elements and is expected to be similar in its V isotopic composition.Vanadium isotope ratios and trace element concentrations were measured for 19 lunar basalt samples. Isotopic compositions are more variable (∼2.5‰) than has been found thus far for terrestrial igneous rocks and extend to lighter values. Magmatic processes do not appear to control the V isotopic composition, despite the large range in oxide proportions in the suite. Instead, the V isotopic compositions of the lunar samples are lighter with increasing exposure age (te). Modelling nuclear cross-sections for V production and burnout demonstrates that cosmogenic production may affect V isotope ratios via a number of channels but strong correlations between V isotope ratios and te⁎[Fe]/[V] implicate Fe as the primary target element of importance. Similar correlations are found in the latest data for chondrites, providing evidence that most V isotope variation in chondrites is due to recent cosmogenic production via Fe spallation. Contrary to previous suggestions, there is no evidence for resolvable differences between the primary V isotopic compositions of the Earth, Moon, chondrites and Mars.

High-precision zirconium stable isotope measurements of geological reference materials as measured by double-spike MC-ICPMS

Zirconium plays a major role in geochemistry as it is the major cation of zircons - the oldest preserved minerals on Earth. While Zr isotopic anomalies in meteorites have been widely studied, mass dependant Zr stable isotope fractionation during geological processing has been untouched. Here, we report Zr stable isotopic data for terrestrial igneous rocks and present a novel method for the determination of Zr stable isotope ratios within natural geological materials using ion exchange, double-spike, multiple-collector inductively coupled mass spectrometry (MC-ICPMS). Zirconium is isolated from the rock matrix via a chromatographic separation protocol using a first pass column with AG1-X8 anion exchange resin, and a second pass column containing Eichrom® DGA resin. A 91Zr–96Zr double-spike was created from enriched single 91Zr and 96Zr isotope spikes. Samples were combined with the Zr double-spike at a 43:57 spike:sample [Zr] ratio, prior to dissolution and column chemistry. After column chemistry the purified sample solutions were analysed on a Thermo Scientific Neptune Plus MC-ICPMS and the data was reduced using IsoSpike, with the final Zr isotope data being reported as the per mil deviation of the 94Zr/90Zr from the IPGP-Zr standard (δ94/90ZrIPGP-Zr). The δ94/90ZrIPGP-Zr of six igneous standard reference materials: two basalts (BHVO-2 and JB-2), one andesite (AGV-2), two granites (GA and GS-N) and a serpentinite (UB-N) as well as one individual zircon grain (Plešovice zircon), are presented using this method. Sample measurements are presented with an analytical uncertainty of ±~0.05‰ (2sd) for δ94/90ZrIPGP-Zr and these rocks exhibit isotopic variations of ~0.15‰ for δ94/90ZrIPGP-Zr. These results demonstrate that natural variations of Zr isotopes occur within terrestrial igneous rocks, and are resolvable with this method. Finally the variation of δ94/90ZrIPGP-Zr values observed within the magmatic rock reference materials is correlated (R2 = 0.78; n = 5) with SiO2, suggesting that Zr isotopes could serve as a sensitive tracer of magmatic processes.

Rubidium isotopic composition of the Earth, meteorites, and the Moon: Evidence for the origin of volatile loss during planetary accretion

Understanding the origin of volatile element variations in the inner Solar System has long been a goal of cosmochemistry, but many early studies searching for the fingerprint of volatile loss using stable isotope systems failed to find any resolvable variations.An improved method for the chemical purification of Rb for high-precision isotope ratio measurements by multi-collector inductively-coupled-plasma mass-spectrometry. This method has been used to measure the Rb isotopic composition for a suite of planetary materials, including carbonaceous, ordinary, and enstatite chondrites, as well as achondrites (eucrite, angrite), terrestrial igneous rocks (basalt, andesite, granite), and Apollo lunar samples (mare basalts, alkali suite). Volatile depleted bodies (e.g. HED parent body, thermally metamorphosed meteorites) are enriched in the heavy isotope of Rb by up to several per mil compared to chondrites, suggesting volatile loss by evaporation at the surface of planetesimals. In addition, the Moon is isotopically distinct from the Moon in Rb. The variations in Rb isotope compositions in the volatile-poor samples are attributed to volatile loss from planetesimals during accretion. This suggests that either the Rb (and other volatile elements) were lost during or following the giant impact or by evaporation earlier during the accretion history of Theia.

Coupled extremely light Ca and Fe isotopes in peridotites

Large metal stable isotopic variations have been observed in both extraterrestrial and terrestrial samples. For example, Ca exhibits large mass-dependent isotopic variation in terrestrial igneous rocks and mantle minerals (on the order of ∼2‰ variation in 44Ca/40Ca). A thorough assessment and understanding of such isotopic variations in peridotites provides important constraints on the evolution and compositon of the Earth’s mantle. In order to better understand the Ca and Fe isotopic variations in terrestrial silicate rocks, we report Ca isotopic compositions in a set of peridotitic xenoliths from North China Craton (NCC), which have been studied for Fe isotopes. These NCC peridotites have large Ca and Fe isotopic variations, with δ44/40Ca ranging from −0.08 to 0.92 (delta value relative to SRM915a) and δ57/54Fe (delta value relative to IRMM-014) ranging from −0.61 to 0.16, and these isotopic variations are correlated with large Mg# (100×Mg/(Mg+Fe) molar ratio) variation, ranging from 80 to 90. Importantly, NCC Fe-rich peridotites have the lowest 44Ca/40Ca and 57Fe/54Fe ratios in all terrestrial silicate rocks. In contrast, although ureilites, mantle rocks from a now broken differentiated asteroid(s), have large Mg# variation, from 70 to 92, they have very limited δ57Fe/54Fe variation (0.03–0.21, delta value relative to IRMM-014). Our model calculations show that the coupled extremely light Ca-Fe isotopic signatures in NCC Fe-rich peridotites most likely reflect kinetic isotopic fractionation during melt-peridotite reaction on a timescale of several to 104 years. In addition, our new data and compiled literature data show a possible compositional effect on the inter-mineral Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene pairs.

Tungsten stable isotope compositions of terrestrial samples and meteorites determined by double spike MC-ICPMS

Tungsten stable isotopes hold great potential to examine a variety of physical and chemical processes operating during the accretion and differentiation of asteroids and terrestrial planets, such as core formation and mantle–crust differentiation. To assess the magnitude and origin of W isotope fractionations, we determined the W stable isotopic compositions of six USGS geological reference materials, a NIST steel, and 24 iron meteorites and chondrites. The W isotope data were obtained using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) and using a 180W–183W double spike. Chondrites and iron meteorites exhibit a very narrow range in W stable isotope compositions, resulting in a mean δ184/183W=0.027±0.007‰ (95% conf.) relative to the NIST 3163 W standard. This value represents a good estimate for the W stable isotope composition of bulk planetary bodies from the inner solar system. The δ184/183W of some iron meteorites slightly deviates from this value, most likely due to W isotope fractionations induced during crystallization of the metal cores of iron meteorite parent bodies. The investigated terrestrial silicate rocks exhibit a narrow range in δ184/183W, which for most samples is indistinguishable from the mean value of chondrites and iron meteorites. However, felsic samples tend to be isotopically lighter than mafic samples, indicating that magmatic processes on Earth induced W isotope fractionations. These fractionations are possibly related to the fluid-mobility of W in subduction zones, but more data are needed to test this hypothesis. Given that most terrestrial igneous rocks are isotopically indistinguishable from chondrites and iron meteorites, core formation on Earth does not seem to have induced a measurable isotopic fractionation for W. However, more data are needed to firmly arrive at this conclusion.

Halogen and Cl isotopic systematics in Martian phosphates: Implications for the Cl cycle and surface halogen reservoirs on Mars

The Cl isotopic compositions and halogen (Cl, F, Br, and I) abundances in phosphates from eight Martian meteorites, spanning most rock types and ages currently available, have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Likewise, the distribution of halogens has been documented by x-ray mapping. Halogen concentrations range over several orders of magnitude up to some of the largest concentrations yet measured in Martian samples or on the Martian surface, and the inter-element ratios are highly variable. Similarly, Cl isotope compositions exhibit a larger range than all pristine terrestrial igneous rocks. Phosphates in ancient (>4 Ga) meteorites (orthopyroxenite ALH 84001 and breccia NWA 7533) have positive δ37Cl anomalies (+1.1 to +2.5‰). These samples also exhibit explicit whole rock and grain scale evidence for hydrothermal or aqueous activity. In contrast, the phosphates in the younger basaltic Shergottite meteorites (<600 Ma) have negative δ37Cl anomalies (−0.2 to −5.6‰). Phosphates with the largest negative δ37Cl anomalies display zonation in which the rims of the grains are enriched in all halogens and have significantly more negative δ37Cl anomalies suggestive of interaction with the surface of Mars during the latest stages of basalt crystallization. The phosphates with no textural, major element, or halogen enrichment evidence for mixing with this surface reservoir have an average δ37Cl of −0.6‰, supporting a similar initial Cl isotope composition for Mars, the Earth, and the Moon. Oxidation and reduction of chlorine are the only processes known to strongly fractionate Cl isotopes, both positively and negatively, and perchlorate has been detected in weight percent concentrations on the Martian surface. The age range and obvious mixing history of the phosphates studied here suggest perchlorate formation and halogen cycling via brines, which have been documented on the Martian surface, has been active throughout Martian history.

Evidence against an ancient non-chondritic mantle source for North Atlantic Igneous Province lavas

North Atlantic Igneous Province (NAIP) lavas host olivine with the highest 3He/4He ever measured for terrestrial igneous rocks (up to 50 RA, or 4He/3He=~15,300). The relationship of high-3He/4He with Pb isotope compositions close to the terrestrial geochron and 143Nd/144Nd plausibly consistent with supra-chondritic mantle Sm/Nd in Baffin Island and West Greenland lavas has been interpreted to reflect an ancient ‘non-chondritic’ mantle source signature. Alternatively, assimilation of continental crustal rocks with unradiogenic Pb isotope compositions and low 143Nd/144Nd, into magmas with high-3He/4He, and derived from variably depleted mantle sources, could impart similar geochemical signatures. Radiogenic and stable isotope data for NAIP lavas are consistent with origins as melts from upper mantle sources that contain low-18O/16O recycled lithosphere and/or hydrothermally altered crust, or that have experienced pervasive contamination by crustal gneisses. Olivines from NAIP lavas with 3He/4He spanning from 8 to 48 RA have δ18O ranging from 3.5 to 5.5‰. These compositions are consistent with sources of ambient mantle and low-δ18O recycled lithosphere, or with concomitant crustal assimilation and He-loss during fractional crystallization. Limited assimilation (≤1%) of incompatible element rich crustal gneisses with low 206Pb/204Pb and 143Nd/144Nd by melts from variably depleted mantle sources can explain Nd-Pb isotope compositions of Baffin Island and West Greenland picrites. Icelandic lavas provide supporting evidence that the ancestral mantle plume responsible for generating NAIP magmatism sampled variably enriched and depleted mantle, with no evidence for ancient non-chondritic mantle sources. Pervasive crustal contamination and partial melting of heterogeneous mantle sources, generated by plate tectonic processes, can account for the compositions of continental flood basalts (CFB), without the requirement of a non-chondritic terrestrial reservoir. Combined with evidence that the 142Nd/144Nd composition of the bulk silicate Earth is due to nucleosynthetic S-process deficits in chondrite meteorites, these observations cast doubt that NAIP lavas sampled a non-chondritic mantle source with Sm/Nd higher than in chondrites. If short-lived radiogenic (e.g., 146Sm-142Nd, 182Hf-182W) isotope anomalies are found in CFB, they must either reflect assimilation of isotopically anomalous crustal materials, or partial melting of early-formed mantle heterogeneities produced by differentiation and late accretion.

Atmospheric contamination of the primary Ne and Ar signal in mid-ocean ridge basalts and its implications for ocean crust formation

Both, terrestrial and extra-terrestrial applications of noble gases have demonstrated their importance as tracers for source identification, process characterisation and mass and heat flux quantification. However, the interpretation of noble gas isotope data from terrestrial igneous rocks is often complicated by the ubiquitous presence of heavy noble gases (Ne, Ar, Kr, Xe) with an atmospheric origin. Up to now there has been no consensus on how atmospheric noble gases are entrained into igneous rocks. Suggested processes range from contamination during sample preparation to mantle recycling through subduction. Here we present Ne, Ar, Mg, K, and Cl data of fresh glasses from the Mid-Atlantic Ridge north and south of the Ascension Fracture Zone which show that incorporation of atmospheric noble gases into igneous rocks is in general a two-step process: (1) magma contamination by assimilation of altered oceanic crust results in the entrainment of noble gases from air-equilibrated seawater; (2) atmospheric noble gases are adsorbed onto grain surfaces during sample preparation. This implies, considering the ubiquitous presence of the contamination signal, that magma contamination by assimilation of a seawater-sourced component is an integral part of mid-ocean ridge basalt evolution. Combining the results obtained from noble gas and Cl/K data with estimates of crystallisation pressures for the sample suite shows that the magma contamination must have taken place at a depth between 9 and 13km. Taking thickness estimates for the local oceanic crust into account, this implies that seawater penetration in this area reaches lower crustal levels, indicating that hydrothermal circulation might be an effective cooling mechanism even for the deep parts of the oceanic crust.

Rare earth element geochemistry of the Permo-Carboniferous clastic sedimentary rocks from the Spiti Region, Tethys Himalaya: significance of Eu and Ce anomalies

Siliciclastic sedimentary rocks, including sandstones and associated shales, from the Permo-Carboniferous Kanawar Group of NW Tethys Himalaya, Spiti Region, India were examined geochemically to monitor the evolutionary changes in the upper continental crust in the Himalaya. The rocks are characterized by consistent rare earth element (REE) patterns with light REE enrichment (LaN/YbN = 5.3–28.2) and flat heavy REE patterns. The ∑REE values are high (up to 281 ppm) with large negative Eu anomalies (avg. Eu/Eu* = 0.57). The REE characteristics of the sediments are similar to those of post-Archean Australian shales and North American shale composite. La/Th values (avg. 2.34) correspond to a relatively felsic composition of the terrestrial igneous rocks standard (La/Th of G-1 = 2.3). The evolved felsic composition of the sediments probably relates to widespread acidic activity in the source. The REE patterns and Th/U values seem to have been affected by the sedimentary environment as well as by the provenance. The presence of positive Ce anomalies in some sediments may be the result of post-depositional processes. Moreover, the Permo-Carboniferous sediments indicate that hydraulic sorting, even over short transport distances, is capable of concentrating enough accessory phases to influence REE composition and to develop negative Eu anomalies. High ∑REE, La/Yb, and Th/U contents and large negative Eu anomalies reveal that the sediments were deposited in an oxidizing environment, suggesting the surficial environment became oxidizing around the Carboniferous-Permian boundary in the Indian craton.