Recycled crust controls contrasting source compositions of Mesozoic and Cenozoic basalts in the North China Craton

We explore Fe/Mn and Nb/Ta ratios of basalts as potential tracers for differentiating melts of recycled mafic crustal lithologies from peridotitic melts. Trace elements and Fe/Mn ratios of the Mesozoic and Cenozoic basalts from East China were analyzed by ICP-MS. Low Nb/Ta ratios (15.4 ± 0.3 (2σ, n = 45)), high Nb and Ta contents (60.1 and 4.01 ppm) and high Fe/Mn ratios (64.7 ± 1.5 (2σ, n = 45)) characterize the <110 Ma basalts. Mesozoic basalts with ages >110 Ma are characterized by superchondritic Nb/Ta ratios (20.1 ± 0.3 (2σ, n = 25)), low Nb and Ta contents (10.8 and 0.54 ppm) and slightly lower Fe/Mn ratios (60.0 ± 1.1 (2σ, n = 25)). Both the Mesozoic and Cenozoic basalts have Fe/Mn ratios higher than basaltic melt formed by partial melting of peridotite at the same MgO and CaO levels. Although both the Mesozoic and Cenozoic basalts are characterized by highly fractionated REE patterns, the >110 Ma basalts have island arc-type trace element patterns (i.e., depletion in Nb and Ta), whereas OIB-type trace element patterns (e.g., no depletion in Nb and Ta) are characteristic of the <110 Ma basalts. Based on D_Fe/Mn values for olivine, clinopyroxene, orthopyroxene and garnet, high Fe/Mn ratios and negative correlations of Fe/Mn with Yb (Y) of the <110 Ma basalts suggest clinopyroxene/garnet-rich mantle sources. The lower Fe/Mn ratios and positive correlations of Fe/Mn with Y and Yb in the >110 Ma basalts suggest orthopyroxene/garnet-rich mantle sources. Combining these data with Sr-Nd isotopes, we present a conceptual model to explain the Nb/Ta ratios and PM-normalized trace element patterns of the >110 and <110 Ma basalts. Preferential melting of recycled ancient lower continental crust during Mesozoic lithospheric thinning resulted in (1) peridotite-melt/fluid reaction that formed the orthopyroxene/garnet-rich mantle sources for the >110 Ma basalts, and (2) peridotite + rutile-bearing eclogite mixing that formed the clinopyroxene/garnet-rich mantle sources for the <110 Ma basalts. The choice of models may indeed be arbitrary and non-unique, but the goal is to seek relatively simple forward models that explain the characteristics of the lavas, and the differences between the >110 and <110 Ma basalts, in a relatively consistent geodynamic framework.     

Siderophile elements in Martian meteorites and implications for core formation in Mars

Noble metals, Mo, W, and 24 other elements were determined in six SNC meteorites of presumably Martian origin. Based on element correlations, representative siderophile element concentrations for the silicate mantle of Mars were inferred. From a comparison with experimentally determined metal/silicate partition coefficients of the moderately siderophile elements: Fe, Ni, Co, W, Mo, and Ga, it is concluded that equilibrium between core forming metal and silicates in Mars has occurred at high temperatures (around 2200°C) and low pressures (<1 GPa). This suggests that metal segregation occurred concurrently with rapid accretion of Mars, which is consistent with the inference from excess ¹⁸²W in Martian meteorites (Lee and Halliday, 1997). Concentrations of Ir, Os, Ru, Pt, and Au in the analyzed Martian meteorites, except ALH84001, are at a level of approximately 10⁻²–10⁻³ × CI. The comparatively high abundances of noble metals in Martian meteorites require the addition of chondritic material after core formation. The similarity in Au/La and Pt/Ca ratios between ALH84001 and the other Martian meteorites suggests crystallization of ALH84001 after complete accretion of Mars.     

The Fe/Mn ratio in MORB and OIB determined by ICP-MS

Variations in the abundance of iron in the mantle may have important consequences for mantle dynamics and geochemistry. The abundance of iron in lavas derived from mantle source regions varies during partial melting and subsequent fractionation, so that source heterogeneities are not easily resolved in iron abundances alone. However, manganese is a geochemically similar element, so that the planetary Fe/Mn ratio is approximately constant. Here, we report new Fe/Mn results for mid-oceanic ridge basalts (MORBs), oceanic island basalts (OIBs) and komatiites using a precise inductively coupled plasma mass spectrometric (ICP-MS) method to measure Fe/Mn to better than 0.5% (2σ). As a measure of reproducibility of Fe/Mn, five olivine and five orthopyroxene grains from a Kilbourne Hole peridotite xenolith yielded Fe/Mn 69.8 ± 0.4 and 44.3 ± 0.2, respectively. To avoid ubiquitous secondary Fe-Mn oxides, Fe/Mn ratios in Pacific, Atlantic, and Indian MORBs were determined by Laser Ablation ICP-MS. MORB Fe/Mn (53-56) corrected for crystal fractionation yielded a value of 54.0 ± 1.2 (1σ). Icelandic basalts and picrites (MgO 10-29%) had Fe/Mn ratios 56-61, with a single exception. Six relatively fresh komatiites from Belingwe (MgO 20-29%) yielded Fe/Mn values of 58.3 ± 0.2 (1σ). Basalts from Tahiti and Reunion exhibited high Fe/Mn (>65), like Hawaii. This implies that the mantle source regions of Tahiti and Reunion lavas may have been enriched in Fe relative to other mantle reservoirs (e.g., MORBs, Iceland, Belingwe). Combined with previous results for Hawaii, we now find that Fe/Mn > 65 is characteristic of at least two plumes from the Pacific Superswell. It is conceivable that this is evidence for excess Fe due to core-mantle interaction in these mantle plumes, although partial melting of secondary pyroxenites may cause similar variations in Fe/Mn. Heterogeneity of Fe/Mn in mantle-derived lavas is now clearly documented.     

Melting of the Indarch meteorite (EH4 chondrite) at 1 GPa and variable oxygen fugacity: Implications for early planetary differentiation processes

In order to derive constraints on planetary differentiation processes, and ultimately the formation of the Earth, it is required to study a variety of meteoritic materials and to investigate their melting relations and elemental partitioning at variable pressures, temperatures, and oxygen fugacities (f_O2). This study reports the first high pressure (HP) and high temperature (HT) investigation of an enstatite chondrite (Indarch). Four series of experiments exploring various f_O2 conditions have been carried out at 1 GPa in a piston-cylinder apparatus using the EH4 chondrite Indarch. We show that temperature and redox conditions have important effects on the phase equilibria of the meteorite: the solidus and liquidus temperatures of the silicate portion increase with decreasing f_O2, and the stability fields of various phases are modified. Olivine and pyroxene are stable around 1.5 log f_O2 unit below the iron-wüstite buffer (IW−1.5), whereas quartz and pyroxene is the stable assemblage under the most reducing conditions, between IW−5.0 and IW−4.0, due to reduction of the silicate. While these changes are occurring in the silicate, the metal gains Si from the silicate, (Fe, Mg, Mn, Ca, Cr)-bearing sulfides are observed at f_O2 less than IW−4, and the partitioning of Ni and Mo are both affected by the presence of Si in Fe-S-C liquids. The f_O2 has also a significant effect on the liquid metal-liquid silicate partitioning behavior of Si and S, two possible light elements in planetary cores, and of the slightly siderophile elements Cr and Mn. With decreasing f_O2, S becomes increasingly lithophile, Si becomes increasingly siderophile, and Cr and Mn both become strongly siderophile and chalcophile. The partitioning behavior of these elements places new constraints on models of core segregation for the Earth and other differentiated bodies.     

Evidence for high-pressure core-mantle differentiation from the metal-silicate partitioning of lithophile and weakly-siderophile elements

Liquid Fe metal-liquid silicate partition coefficients for the lithophile and weakly-siderophile elements Ta, Nb, V, Cr, Si, Mn, Ga, In and Zn have been measured in multianvil experiments performed from 2 to 24 GPa, 2023-2873 K and at oxygen fugacities of −1.3 to −4.2 log units relative to the iron-wüstite buffer. Compositional effects of light elements dissolved in the metal liquid (S, C) have been examined and experiments were performed in both graphite and MgO capsules, specifically to address the effect of C solubility in Fe-metal on siderophile element partitioning. The results were used to examine whether there is categorical evidence that a significant portion of metal-silicate equilibration occurred under very high pressures during core-mantle fractionation on Earth. Although the depletion of V from the mantle due to core formation is significantly greater than that of Nb, our results indicate that both elements have similar siderophile tendencies under reducing conditions at low pressures. With increasing pressure, however, Nb becomes less siderophile than V, implying that average metal-silicate equilibration pressures of at least 10-40 GPa are required to explain the Nb/V ratio of the mantle. Similarly the moderately-siderophile, volatile element ratios Ga/Mn and In/Zn are chondritic in the mantle but both volatility and core-mantle equilibration at low pressure would render these ratios strongly sub-chondritic. Our results indicate that pressures of metal-silicate partitioning exceeding 30-60 GPa would be required to render these element ratios chondritic in the mantle. These observations strongly indicate that metal-silicate equilibration must have occurred at high pressures, and therefore support core-formation models that involve deep magma oceans. Moreover, our results allow us to exclude models that envisage primarily low-pressure (<1 GPa) equilibration in relatively small planetary bodies. We also argue that the core cannot contain significant U as this would require metal-silicate equilibration at oxygen fugacities low enough for significant amounts of Ta to have also been extracted from the mantle. Likewise, as In is more siderophile than Pb but similarly volatile and also quite chalcophile it would have been difficult for Pb to enter the core without reversing the relative depletions of these elements in the mantle unless metal-silicate equilibration occurred at high pressures >20 GPa.     

Evidence from polymict ureilite meteorites for a disrupted and re-accreted single ureilite parent asteroid gardened by several distinct impactors

Ureilites are ultramafic achondrites that exhibit heterogeneity in mg# and oxygen isotope ratios between different meteorites. Polymict ureilites represent near-surface material of the ureilite parent asteroid(s). Electron microprobe analyses of >500 olivine and pyroxene clasts in several polymict ureilites reveal a statistically identical range of compositions to that shown by unbrecciated ureilites, suggesting derivation from a single parent asteroid. Many ureilitic clasts have identical compositions to the anomalously high Mn/Mg olivines and pyroxenes from the Hughes 009 unbrecciated ureilite (here termed the “Hughes cluster”). Some polymict samples also contain lithic clasts derived from oxidized impactors. The presence of several common distinctive lithologies within polymict ureilites is additional evidence that ureilites were derived from a single parent asteroid.In situ oxygen three isotope analyses were made on individual ureilite minerals and lithic clasts, using a secondary ion mass spectrometer (SIMS) with precision typically better than 0.2-0.4‰ (2SD) for δ¹⁸O and δ¹⁷O. Oxygen isotope ratios of ureilitic clasts fall on a narrow trend along the CCAM line, covering the range for unbrecciated ureilites, and show a good anti-correlation with mineral mg#. SIMS analysis identifies one ferroan lithic clast as an R-chondrite, while a second ferroan clast is unlike any known meteorite. An exotic enstatite grain is derived from an enstatite chondrite or aubrite, and another pyroxene grain with Δ¹⁷O of −0.4 ± 0.2‰ is unrelated to any known meteorite type.Ureilitic olivine clasts with mg#s < 85 are much more common than those with mg# > 85 which include the melt-inclusion-bearing “Hughes cluster” ureilites. Thus melt was present in regions of the parent ureilite asteroid with a bulk mg# > 85 when the asteroid was disrupted by impact, giving rise to two types of ureilites: common ferroan ones that were residual after melting and less common magnesian ones that were still partially molten when disruption occurred. One or more daughter asteroids re-accreted from the remnants of the mantle of the proto-ureilite asteroid. Polymict ureilite meteorites represent regolith that subsequently formed on the surface of a daughter asteroid, including impact-derived material from at least six different meteoritic sources.     

The geochemistry of the volatile trace elements As, Cd, Ga, In and Sn in the Earth’s mantle: New evidence from in situ analyses of mantle xenoliths

The abundances of 30 trace elements, including the volatile chalcophile/siderophile elements As, Cd, Ga, In and Sn were determined by laser ablation ICP-MS in minerals of 19 anhydrous and 5 hydrous spinel peridotite xenoliths from three continents. The majority of samples were fertile lherzolites with more than 5% clinopyroxene; several samples have major element compositions close to estimates of the primitive mantle. All samples have been previously analysed for bulk-rock major, minor and lithophile trace elements. They cover a wide range of equilibration temperatures from about 850 to 1250 °C and a pressure range from 0.8 to 3.0 GPa. A comparison of results from bulk-rock analyses with concentrations obtained from combining silicate and oxide mineral data with modal mineralogy, gave excellent agreement, with the exception of As. Arsenic is the only element analysed that has high concentrations in sulphides. For all other elements sulphides can be neglected as host phases in these mantle rocks. The major host phase for Cd, In and Sn is clinopyroxene and if present, amphibole. Cadmium and In appear to behave moderately incompatibly during mantle melting similar to Yb.The data yield new and more reliable mantle abundances for Cd (35 ± 7 ppb), In (18 ± 3 ppb) and Sn (91 ± 28 ppb). The In value is similar to the Mg and CI-normalized Zn abundance of the mantle, although In is cosmochemically more volatile than Zn. The high In content suggests a high content of volatile elements in general in proto-Earth material. The lower relative abundances of volatile chalcophile elements such as Cd, S, Se and Te might be explained by sulphide segregation during core formation. The very low relative abundances of volatile and highly incompatible lithophile elements such as Br, Cl and I, and also C, N and rare gases, imply loss during Earth accretion, arguably by collisional erosion from differentiated planetesimals and protoplanets.     

Mn-Cr systematics of carbonates in CM chondrites: Implications for the timing and duration of aqueous alteration

CM chondrites contain carbonates and other secondary minerals such as phyllosilicates, sulfides, sulfates, oxides and hydroxides that are believed to have formed by aqueous alteration reactions on their parent asteroid. We report in situ Mn-Cr isotope measurements in the highly aqueously altered CM2.1 chondrites QUE 93005 and ALH 83100 using secondary ion mass spectrometry (Cameca ims-1270 ion microprobe). The ⁵³Cr excesses are correlated with the ⁵³Mn/⁵⁵Mn ratio and result from the in situ decay of ⁵³Mn, a short-lived radioisotope with a half-life of 3.7 Ma. If we assume that carbonate grains in samples QUE 93005 and ALH 83100 are cogenetic, then the excesses define initial ⁵³Mn/⁵⁵Mn ratios ((⁵³Mn/⁵⁵Mn)₀) of (4.1 ± 1.2) × 10⁻⁶ and (5.1 ± 1.7) × 10⁻⁶, respectively. These values are comparable to those in carbonates from other CM chondrites as reported in the literature. Initial ⁵³Mn/⁵⁵Mn ratios for calculated model isochrones for individual carbonate grains range from (3.8 ± 1.4) × 10⁻⁶ to (4.8 ± 2.1) × 10⁻⁶ for QUE 93005 and from (3.1 ± 1.6) × 10⁻⁶ to (1.3 ± 0.5) × 10⁻⁵ for ALH 83100. A possible interpretation for the ranges in (⁵³Mn/⁵⁵Mn)₀ could be that alteration in individual CM chondrites was episodic and occurred over an extended period of time. However, isochrones based on the entire set of carbonate grains in each of the CM chondrites imply that the degree of aqueous alteration is roughly correlated with the age of carbonate formation in CM chondrites of different subtypes and that alteration on the CM parent asteroid started contemporaneously with or shortly after CAI formation and lasted at least 4 Ma.     

Nanostructure, composition and mechanisms of bivalve shell growth

Freshwater and marine cultured pearls form via identical processes to the shells of bivalves and can therefore serve as models for the biomineralization of bivalve shells in general. Their nanostructure consists of membrane-coated granules (vesicles) which contain amorphous calcium carbonate (ACC) at the beginning of the biomineralization sequence, preceding the crystallization of aragonite and vaterite. In contrast to the commonly accepted view, crystallization of ACC occurs rapidly and within the granular nano-compartments mediated by organic molecules much earlier than platelet formation. The interlamellar organic sheets in nacre that form the platelet structure of nacre themselves form by self-organization after the crystallization process of CaCO₃ is completed and, thus, cannot serve as a nucleation template for aragonite. Pores in the organic sheets are postulated to be a result of this process rather than to represent the pathways for CaCO₃ through pre-existing interlamellar sheets. The amorphous phase has the highest concentrations of Mg (5.8 mol%), Mn (6.6 mol%), S (4.7 mol%) and P (1 mol%) of the three CaCO₃-polymorphs. Mg/Ca and Mn/Ca ratios are found to decrease in the order ACC > vaterite > aragonite, corresponding to decreasing organic content in the different phases. This, as well as an observed enrichment of Mg in the organic-rich growth-banding of the pearls, suggests an at least partially organic speciation of Mg and Mn in bivalves and may be responsible for the observed physiological influence on Mg/Ca and Mn/Ca ratios in bivalves as a proxy for environmental parameters.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (∼50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ²⁵Mg and δ²⁶Mg values of the bulk flow are −0.138 ± 0.021‰ and −0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ⁵⁶Fe and δ⁵⁷Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.     

Atmospheric sources and sinks of volcanogenic elements in a basaltic volcano (Etna, Italy)

This study reports on the first quantitative assessment of the geochemical cycling of volcanogenic elements, from their atmospheric release to their deposition back to the ground. Etna’s emissions and atmospheric depositions were characterised for more than 2 years, providing data on major and trace element abundance in both volcanic aerosols and bulk depositions. Volcanic aerosols were collected from 2004 to 2007, at the summit vents by conventional filtration techniques. Precipitation was collected, from 2006 to 2007, in five rain gauges, at various altitudes around the summit craters. Analytical results for volcanic aerosols showed that the dominant anions were S, Cl, and F, and that the most abundant metals were K, Ca, Mg, Al, Fe, and Ti (1.5-50 μg m⁻³). Minor and trace element concentrations ranged from about 0.001 to 1 μg m⁻³. From such analysis, we derived an aerosol mass flux ranging from 3000 to 8000 t a⁻¹. Most analysed elements had higher concentrations close to the emission vent, confirming the prevailing volcanic contribution to bulk deposition. Calculated deposition rates were integrated over the whole Etna area, to provide a first estimate of the total deposition fluxes for several major and trace elements. These calculated deposition fluxes ranged from 20 to 80 t a⁻¹ (Al, Fe, Si) to 0.01-0.1 t a⁻¹ (Bi, Cs, Sc, Th, Tl, and U). Comparison between volcanic emissions and atmospheric deposition showed that the amount of trace elements scavenged from the plume in the surrounding of the volcano ranged from 0.1% to 1% for volatile elements such as As, Bi, Cd, Cs, Cu, Tl, and from 1% to 5% for refractory elements such as Al, Ba, Co, Fe, Ti, Th, U, and V. Consequently, more than 90% of volcanogenic trace elements were dispersed further away, and may cause a regional scale impact. Such a large difference between deposition and emission fluxes at Mt. Etna pointed to relatively high stability and long residence time of aerosols in the plume.     

Parentage Identification of Differentiated Achondritic Meteorites by Hand‐held Energy Dispersive X‐Ray Fluorescence Spectrometry

We evaluate the potential of a hand‐held energy dispersive XRF spectrometer for the preliminary classification of non‐chondritic differentiated meteorites. The studied achondrites include nine lunar meteorites, seventeen Martian meteorites, five angrites and eighteen meteorites from asteroid 4 Vesta. Analytical precision and accuracy was tested on thirty‐nine terrestrial igneous rock slabs with a wide range of composition. Replicate analyses, performed on the studied meteorites, show that Fe/Mn values together with Si and Ca/K ratio can be used in the discrimination of different achondrite groups. Fusion crust's Fe/Mn values of meteorites from Vesta and Mars are indistinguishable from those of the interior implying that even measurements on the fusion‐crusted external surface could be sufficient to pigeonhole non‐chondritic meteorites. Hand‐held energy dispersive XRF spectrometer is a non‐destructive but very effective technique for preliminary classification of achondrites in the field and in laboratory and for the identification of mislabelled meteorites in museum collections.     

Abundance and fractionation of Al,Fe and trace metals following tidal inundation of a tropical acid sulfate soil

Tidal inundation was restored to a severely degraded tropical acid sulfate soil landscape and subsequent changes in the abundance and fractionation of Al, Fe and selected trace metals were investigated. After 5 a of regular tidal inundation there were large decreases in water-soluble and exchangeable Al fractions within former sulfuric horizons. This was strongly associated with decreased soil acidity and increases in pH, suggesting pH-dependent immobilisation of Al via precipitation as poorly soluble phases. The water-soluble fractions of Fe, Zn, Ni and Mn also decreased. However, there was substantial enrichment (2–5×) of the reactive Fe fraction (Fe_R; 1 M HCl extractable) near the soil surface, plus a closely corresponding enrichment of 1 M HCl extractable Cr, Zn, Ni and Mn. Surficial accumulations of Fe(III) minerals in the inter-tidal zone were poorly crystalline (up to 38% Fe_R) and comprised mainly of schwertmannite (Fe₈O₈(OH)₆SO₄) with minor quantities of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). These Fe (III) mineral accumulations provide an effective substrate for the adsorption/co-precipitation and accumulation of trace metals. Arsenic displayed contrary behaviour to trace metals with peak concentrations (∼60 μg g⁻¹) near the redox minima. Changes in the abundance and fractionation of the various metals can be primarily explained by the shift in the geochemical regime from oxic–acidic to reducing-circumneutral conditions, combined with the enrichment of reactive Fe near the soil surface. Whilst increasing sequestration of trace metals via sulfidisation is likely to occur over the long-term, the current abundance of reactive Fe near the sediment–water interface favours a dynamic environment with respect to metals in the tidally inundated areas.     

Interindividual variability and ontogenetic effects on Mg and Sr incorporation in the planktonic foraminifer Globigerinoides sacculifer

In order to investigate the interindividual and ontogenetic effects on Mg and Sr incorporation, magnesium/calcium (Mg/Ca) and strontium/calcium (Sr/Ca) ratios of cultured planktonic foraminifera have been determined. Specimens of Globigerinoides sacculifer were grown under controlled physical and chemical seawater conditions in the laboratory. By using this approach, we minimised the effect of potential environmental variability on Mg/Ca and Sr/Ca ratios. Whereas temperature is the overriding control of Mg/Ca ratios, the interindividual variability observed in the Mg/Ca values contributes 2-3 °C to the apparent temperature variance. Interindividual variability in Sr/Ca ratios is much smaller than that observed in Mg/Ca values. The variability due to ontogeny corresponds to −0.43 mmol/mol of Mg/Ca ratio per chamber added. This translates into an apparent decrease of ∼1 °C in Mg/Ca-based temperature per ontogenetic (chamber) stage. No significant ontogenetic effect is observed on Sr incorporation. We conclude that the presence of a significant ontogenetic effect on Mg incorporation can potentially offset Mg/Ca-based temperature reconstructions. We propose two new empirical Mg/Ca-temperature equation based on Mg/Ca measurements of the last four ontogenetic (chamber) stages and whole foraminiferal test: Mg/Ca = (0.55(±0.03) − 0.0002(±4 × 10⁻⁵) MSD) e^0.089T and, Mg/Ca = (0.55(±0.03) − 0.0001(±2 × 10⁻⁵) MSD) e^0.089T, respectively, where MSD corresponds to the maximum shell diameter of the individual.     

Zn/Fe systematics in mafic and ultramafic systems: Implications for detecting major element heterogeneities in the Earth’s mantle

Oceanic basalts, such as mid-ocean ridge basalts (MORB) and ocean island basalts (OIB), are characterized by large isotopic and trace element variability that is hard to reconcile with partial melting of a peridotitic mantle alone. Their variability has been attributed to the presence of heterogeneities within the mantle, such as recycled crust, metasomatized material or outer core contribution. There have been few attempts to constrain the major element composition of those heterogeneities, most studies focusing on incompatible trace elements and radiogenic isotopes. Here, we report Zn, Mn and Fe systematics in mafic and ultramafic systems (whole-rocks and minerals) and we explore their use for detecting lithological heterogeneities that deviate from peridotitic mantle dominated by olivine and orthopyroxene. We suggest that Zn/Fe ratio is a particularly promising proxy. Zn/Fe fractionates equally between olivine, orthopyroxene and melt (e.g. the inter-mineral exchange coefficients  ∼  is ∼0.9-1), and the distribution of Zn/Fe between minerals appears to be temperature-independent within error. In contrast, clinopyroxene and garnet are characterized by low Zn/Fe ratios compared to co-existing melt, olivine and orthopyroxene, that is, and are both <<1. These partitioning behaviors imply that Zn/Fe ratios are minimally fractionated during partial melting of peridotite and differentiation of primitive basalts, if differentiation is dominated by olivine control. Thus, the Zn/Fe ratios of primitive basalts preserve the Zn/Fe ratio of the primary parental magma, providing insight into the signature of the mantle source region. We also infer that Zn/Fe ratios in melts are unlikely to be fractionated by modal variations in peridotitic material but are highly fractionated if garnet and/or clinopyroxene are the main phases in the source during melting. Similar Zn/Fe ratios between MORB and average upper mantle confirm the lack of fractionation during peridotite melting. However, high Zn/Fe ratios of some OIB cannot be explained by peridotite melting alone, but instead require the presence of high Zn/Fe lithologies or lithologies that have bulk exchange coefficients  < 1. All garnet-bearing or clinopyroxene-bearing lithologies, such as eclogites and garnet pyroxenites, fit the latter requirement.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

The origin of iron silicides in ureilite meteorites

Ureilite meteorites contain iron silicide minerals including suessite (Fe,Ni)₃Si, hapkeite (Fe₂Si) and xifengite (Fe₅Si₃). Despite occurring mostly in brecciated varieties presumed to be derived from the regolith of the ureilite parent asteroid, suessite has also been confirmed in one lithology of a dimict ureilite (NWA 1241). In contrast, Si-bearing Fe-metals occur in both brecciated and unbrecciated ureilites, implying that they were formed throughout the ureilite parent asteroid. We examined major, minor and trace element data of Fe-metals in seven brecciated ureilites (DaG 319, DaG 999, DaG 1000, DaG 1023, DaG 1047, EET 83309, and EET 87720) in addition to the dimict ureilite NWA 1241.In this study we show that the silicides and Si-bearing metals in ureilites have similar siderophile trace element patterns; therefore, the precursors to the silicides were indigenous to the ureilite parent body. Si-free kamacite grains in brecciated ureilites show flatter, more chondritic siderophile element patterns. They may also be derived from the interior of the ureilite parent body, but some may be of exogenous origin (impactor debris), as are rare taenite grains.On Earth, iron silicides are often formed under high-temperature and strongly reducing conditions (e.g. blast furnaces, lightning strikes). On the Moon, hapkeite (Fe₂Si) and other silicides have been found in the regolith where they were formed by impact-induced space weathering. In the Stardust aerogel, iron silicides derived from comet Wild2 were also formed by an impact-related reduction process. Silicides in ureilite regolith breccias may have formed by similar processes but ureilites additionally contain abundant elemental carbon which probably acted as a reducing agent, thus larger and more abundant silicide grains were formed than in the lunar regolith or cometary material. The origin of suessite in NWA 1241 may be analogous to that of reduced lithologies in the terrestrial mantle, although a regolith origin may also be possible since this sample is shown here to be a dimict breccia.     

Formation and evolution of carbonate chimneys at the Lost City Hydrothermal Field

The Lost City Hydrothermal Field at 30°N, near the Mid-Atlantic Ridge, is an off-axis, moderate temperature, high-pH (9-10.8), serpentinite-hosted vent system. The field is hosted on ∼1.5 Ma crust, near the summit of the Atlantis Massif. Within the field, actively venting carbonate chimneys tower up to 60 m above the seafloor, making them the tallest vent structures known. The chemistry of the chimneys and vent fluids is controlled by serpentinization reactions between seawater and underlying peridotite. Mixing of <40-91 °C calcium-rich vent fluids with seawater results in the precipitation of variable mixtures of aragonite, calcite, and brucite. The resultant deposits range from tall, graceful pinnacles to fragile flanges and delicate precipitates that grow outward from fissures in the bedrock. In this study, mineralogy, petrographic analyses, major and trace element concentrations, and Sr isotopic compositions are used to propose a model for the growth and chemical evolution of carbonate chimneys in a serpentinite-hosted environment. Our results show that nascent chimneys are characterized by a porous, interlacing network of aragonite, and brucite minerals that form extremely fragile structures. The chemistry of these young deposits is characterized by ∼10 wt% Ca and up to 27 wt% Mg, extremely low trace metal concentrations, and ⁸⁷Sr/⁸⁶Sr isotope ratios near 0.70760. During aging of the chimneys, progressive reactions with seawater result in the dissolution of brucite, the conversion of aragonite to calcite, and infilling of pore spaces with calcite. The oldest chimneys are dominated by calcite, with bulk rock values of up to 36 wt% Ca and <1 wt% Mg. These older structures contain higher concentrations of trace metals (e.g., Mn and Ti), and have Sr isotope ratios near seawater values (0.70908). Exposed ultramafic rocks are prevalent along the Mid-Atlantic, Arctic, and Indian Ocean ridge networks and it is likely that other Lost City-type systems exist.     

Metal-silicate partitioning and constraints on core composition and oxygen fugacity during Earth accretion

We present the results of new partitioning experiments between metal and silicate melts for a series of elements normally regarded as refractory lithophile and moderately siderophile and volatile. These include Si, Ti, Ni, Cr, Mn, Ga, Nb, Ta, Cu and Zn. Our new data obtained at 3.6 and 7.7 GPa and between 2123 and 2473 K are combined with literature data to parameterize the individual effects of oxygen fugacity, temperature, pressure and composition on partitioning. We find that Ni, Cu and Zn become less siderophile with increasing temperature. In contrast, Mn, Cr, Si, Ta, Nb, Ga and Ti become more siderophile with increasing temperature, with the highly charged cations (Nb, Ta, Si and Ti) being the most sensitive to variations of temperature. We also find that Ni, Cr, Nb, Ta and Ga become less siderophile with increasing pressure, while Mn becomes more siderophile with increasing pressure. Pressure effects on the partitioning of Si, Ti, Cu and Zn appear to be negligible, as are the effects of silicate melt composition on the partitioning of divalent cations. From the derived parameterization, we predict that the silicate Earth abundances of the elements mentioned above are best explained if core formation in a magma ocean took place under increasing conditions of oxygen fugacity, starting from moderately reduced conditions and finishing at the current mantle-core equilibrium value.