Oxygen fugacity and geochemical variations in the martian basalts: implications for martian basalt petrogenesis and the oxidation state of the upper mantle of Mars

The oxygen fugacity of the Dar al Gani 476 martian basalt is determined to be quartz-fayalite-magnetite (QFM) −2.3 ± 0.4 through analysis of olivine, low-Ca pyroxene, and Cr-spinel and is in good agreement with revised results from Fe-Ti oxides that yield QFM −2.5 ± 0.7. This estimate falls within the range of oxygen fugacity for the other martian basalts, QFM −3 to QFM −1. Oxygen fugacity in martian basalts correlates with ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and La/Yb ratios, indicating that the mantle source of the basalts is reduced and that assimilation of crust-like material controls the oxygen fugacity. This allows constraints to be placed on the oxidation state of the martian mantle and on the nature of assimilated crustal material. The assimilated material may be the product of early and extensive hydrothermal alteration of the martian crust, or it may be amphibole- or phlogopite-bearing basaltic rock within the crust. In either case, water may play a significant role in the oxidation of basaltic magmas on Mars, although it may be secondary to assimilation of ferric iron-rich material.     

Light lithophile elements in martian basalts: Evaluating the evidence for magmatic water degassing

Whether water has played a role in the petrogenesis of martian basalts remains a subject of significant debate. Estimates of pre-eruptive water concentrations in martian magmas are impeded by the effects of degassing and shock. However, zoning trends of light lithophile elements (LLE) in pyroxene have been interpreted as evidence for the degassing of magmatic water, on the basis of the soluble behavior of these elements in hydrothermal fluids. We provide ion microprobe analyses of LLE in pyroxene in the Zagami and Shergotty martian basalts, complemented by detailed electron microprobe analyses and major-element X-ray maps, to independently verify the zoning of LLE and its relationship to texture and major-element variations. Our results corroborate previous results; specifically, that Li concentrations are lower in rims than cores of Shergotty and Zagami pyroxene. In contrast, we see no evidence for a core-to-rim decrease in B. In the absence of further data, we interpret the decrease in Li as reflecting either loss after crystallization of pyroxene cores, consistent with magmatic degassing, or the diffusive preferential loss of Li from pyroxene rims, possibly as a result of shock. Because the partitioning behavior of Li between hydrous fluid, minerals, and melt under relevant conditions of pressure, temperature, and melt composition is unknown, the viability of the water degassing hypothesis depends on experiments establishing the compatibility of Li in hydrous fluid associated with martian basaltic melt and the incompatibility of Li in pyroxene at elevated pressures.     

Moving averages for Gaussian simulation in two and three dimensions

The square-root method provides a simple and computationally inexpensive way to generate multidimensional Gaussian random fields. It is applied by factoring the multidimensional covariance operator analytically, then sampling the factorization at discrete points to compute an array of weighted averages that can be convolved with an array of random normal deviates to generate a correlated random field. In many respects this is similar to the LUdecomposition method and to the one-dimensional method of moving averages. However it has been assumed that the method of moving averages could not be used in higher dimensions, whereas direct application of the matrix decomposition approach is too expensive to be practical on large grids. In this paper, I show that it is possible to calculate the square root of many two- and three dimensional covariance operators analytically so that the method of moving averages can be applied directly to the problem of multidimensional simulation. A few numerical examples of nonconditional simulation on a 256×256 grid that show the simplicity of the method are included. The method is fast and can be applied easily to nested and anisotropic variograms.     

Petrogenesis of olivine-phyric shergottite Larkman Nunatak 06319: Implications for enriched components in martian basalts

We report on the petrography and geochemistry of the newly discovered olivine-phyric shergottite Larkman Nunatak (LAR) 06319. The meteorite is porphyritic, consisting of megacrysts of olivine (?2.5 mm in length, Fo_77-52) and prismatic zoned pyroxene crystals with Wo₃En₇₁ in the cores to Wo_8-30En_23-45 at the rims. The groundmass is composed of finer grained olivine (<0.25 mm, Fo_62-46), Fe-rich augite and pigeonite, maskelynite and minor quantities of chromite, ulvöspinel, magnetite, ilmenite, phosphates, sulfides and glass. Oxygen fugacity estimates, derived from the olivine-pyroxene-spinel geo-barometer, indicate that LAR 06319 formed under more oxidizing conditions (QFM -1.7) than for depleted shergottites. The whole-rock composition of LAR 06319 is also enriched in incompatible trace elements relative to depleted shergottites, with a trace-element pattern that is nearly identical to that of olivine-phyric shergottite NWA 1068. The oxygen isotope composition of LAR 06319 (Δ¹⁷O = 0.29 ±0.03) confirms its martian origin.Olivine megacrysts in LAR 06319 are phenocrystic, with the most Mg-rich megacryst olivine being close to equilibrium with the bulk rock. A notable feature of LAR 06319 is that its olivine megacryst grains contain abundant melt inclusions hosted within the forsterite cores. These early-trapped melt inclusions have similar trace element abundances and patterns to that of the whole-rock, providing powerful evidence for closed-system magmatic behavior for LAR 06319. Calculation of the parental melt trace element composition indicates a whole-rock composition for LAR 06319 that was controlled by pigeonite and augite during the earliest stages of crystallization and by apatite in the latest stages. Crystal size distribution and spatial distribution pattern analyses of olivine indicate at least two different crystal populations. This is most simply interpreted as crystallization of megacryst olivine in magma conduits, followed by eruption and subsequent crystallization of groundmass olivine.LAR 06319 shows close affinity in mineral and whole-rock chemistry to olivine-phyric shergottite, NWA 1068 and the basaltic shergottite NWA 4468. The remarkable features of these meteorites are that they have relatively similar quantities of mafic minerals compared with olivine-phyric shergottites (e.g., Y-980459, Dho 019), but flat and elevated rare earth element patterns more consistent with the LREE-enriched basaltic shergottites (e.g., Shergotty, Los Angeles). This relationship can be interpreted as arising from partial melting of an enriched mantle source and subsequent crystal-liquid fractionation to form the enriched olivine-phyric and basaltic shergottites, or by assimilation of incompatible-element enriched martian crust. The similarity in the composition of early-trapped melt inclusions and the whole-rock for LAR 06319 indicates that any crustal assimilation must have occurred prior to crystallization of megacryst olivine, restricting such processes to the deeper portions of the crust. Thus, we favor LAR06319 forming from partial melting of an “enriched” and oxidized mantle reservoir, with fractional crystallization of the parent melt upon leaving the mantle.     

Mineralogical characterization of acid weathered phyllosilicates with implications for secondary martian deposits

The detection of phyllosilicates and sulfates on Mars has revealed a complex aqueous history which suggests distinct geochemical environments separated temporally and spatially. Recent observations by MRO CRISM in Mawrth Vallis have shown that phyllosilicate deposits exhibit a specific stratigraphy, which remains incompletely understood. Moreover, MER Spirit has evidenced association between phyllosilicates, amorphous silica and sulfates. We investigated the hypothesis that these parageneses resulted from the acidic weathering of older phyllosilicate deposits. We exposed nontronite (Fe-rich smectite), montmorillonite (Al-rich smectite) and kaolinite to H₂SO₄ solutions at pH 0, 2 and 4, and at a temperature of 60 °C. After the acid treatment, a combination of mineralogical techniques was used to assess the degree of alteration of the three phyllosilicate minerals. XRF, XRD and ESEM measurements show that nontronite was the most unstable when acid leached, followed by montmorillonite and then kaolinite. Progressive acidic leaching of nontronite leads to alteration of the phyllosilicate to amorphous silica, along with Fe-sulfate and anatase, and the formation of an acidic Al,Fe-rich solution. Alteration of montmorillonite resulted in the formation of Fe-, Al-, Ca- and Mg-sulfates, and a Al-rich leaching solution. Comparatively, leaching of kaolinite resulted in the formation of Al-sulfates and a Al-rich solution as well, with only slight alteration of the primary mineralogical features. The effects of acid leaching of the phyllosilicates were also observed in NIR reflectance spectra, allowing a comparison with CRISM spectra from Mawrth Vallis. Based on our results, we propose a new model where acid leaching of mixed phyllosilicate deposits leads to kaolinite overlaying montmorillonite, which in turn caps Fe,Mg-smectites. Leaching of cations and subsequent evaporation leads to sulfate deposits, as supported by geochemical modeling, while amorphous silica remains as a residue. Depending on the intensity (pH) and length of exposure of acidic leaching, our model can explain the stratigraphic distribution of phyllosilicates, and the association of sulfates, silica and smectites.     

Nature of magnetic grains in basalts and implications for palaeomagnetism

Journal of Earth System Science - Investigations involving temperature dependence of low-field susceptibility and of low- and high-field hysteresis have been carried out on more than one thousand...     

Sulphur solubility in andesitic to basaltic melts: implications for Hekla volcano

The solubility of sulphur in sulphide-saturated, H₂O-bearing basaltic–andesitic and basaltic melts from Hekla volcano (Iceland) has been determined experimentally at 1,050°C, 300 and 200 MPa, and redox conditions with oxygen fugacity (logfO₂) between QFM−1.2 and QFM+1.1 (QFM is a quartz–fayalite–magnetite oxygen buffer) in the systems containing various amounts of S and H₂O. The S content of the H₂O-rich glasses saturated with pyrrhotite decreases from 2,500 ppm in basalt to 1,500 ppm in basaltic andesite at the investigated conditions. Furthermore, the reduction of water content in the melt at pyrrhotite saturation and fixed T, P and redox conditions leads to a decrease in S concentration from 2,500 to 1,400 ppm for basaltic experiments (for H₂O decrease from 7.8 to 1.4 wt%) and from 1,500 to 900 ppm (for H₂O decrease from 6.7 to 1.7 wt%) for basaltic andesitic experiments. Our experimental data, combined with silicate melt inclusion investigations and the available models on sulphide saturation in mafic magmas, indicate that the parental basaltic melts of Hekla were not saturated with respect to sulphide. During magmatic differentiation, the S content in the residual melts increased and might have reached sulphide saturation with 2,500 ppm dissolved S. With further magma crystallization, the S concentration in the melt was controlled by the sulphide saturation of the magma, decreasing from ~2,500 to 900 ppm S.     

Bacterial mineralization patterns in basaltic aquifers: implications for possible life in martian meteorite ALH84001

To explore the formation and preservation of biogenic features in igneous rocks, we have examined the organisms in experimental basaltic microcosms using scanning and transmission electron microscopy. Four types of microorganisms were recognized on the basis of size, morphology, and chemical composition. Some of the organisms mineralized rapidly, whereas others show no evidence of mineralization. Many mineralized cells are hollow and do not contain evidence of microstructure. Filaments, either attached or no longer attached to organisms, are common. Unattached filaments are mineralized and are most likely bacterial appendages (e.g., prosthecae). Features similar in size and morphology to unattached, mineralized filaments are recognized in martian meteorite ALH84001.     

Systematics of modal phenocryst assemblages in submarine basalts: Petrologic implications

Phenocryst assemblages in ocean-ridge basalts generally show an increasing proportion of plagioclase as the total amount of phenocrysts increases. The variations in phase assemblages, as well as most crystal-liquid K_d's, are similar to variations (equimodal trends) predicted by low-pressure laboratory experiments, suggesting that many of these basalts have experienced varying degrees of low-pressure cyrstallization prior to quenching, with little sorting of crystals and liquid. Important exceptions include moderately to highly phyric basalts enriched either in plagioclase or olivine which lie well off the experimental trends. In these basalts, megacrysts and xenocrysts usually cited as evidence for magma mixing commonly represent a small proportion of the total crystalline phase assemblage. However, phase proportions for many of these basalts lie well outside the range that could be produced by simple mixing; selective gravitative sorting either prior or subsequent to mixing appears to be the likely explanation for these phyric basalts. A relation between spreading rate and phase proportions is neither supported nor refuted by the data, which as yet do not adequately represent fast-spreading ridges. Pyroxene-phyric varieties are especially common among LIL-element enriched (Group 2) basalts, and these basalts also show the greatest abundance of olivine-enriched (picritic) samples. Selective enrichment in plagioclase is more common among LIL-element depleted (Group 1) basalts, and pyroxene appears in Group 1 basalts only at relatively high degrees of crystallinity. These differences are consistent with expected compositional effects (including volatiles) on phase boundaries, as well as likely differences in depth (pressure) of mantle melting and magma fractionation. Sparsely to moderately phyric basalts tend to contain only olivine (±spinel) as phenocrysts, and lie in the olivine field in the projection from plagioclase in the CMAS tetrahedron. This is consistent with the concept that these magmas approach low-pressure equilibrium by olivine fractionation from a more picritic parent. The origin of these basalts, and relationships between them, remains an important fundamental problem. Phenocryst phase assemblages are consistent with the low-pressure phase saturation indicated by the projected positions of the associated glasses in CMAS. It is suggested that, in contrast to the classical practice of classifying basalts according to phase proportions, a classification based on presence and/or first appearance of each crystalline phase is both practical and petrogenetically significant for water-quenched submarine basalts.     

Experimental solidification of anhydrous latitic and trachytic melts at different cooling rates: The role of nucleation kinetics

Two sets of cooling experiments were run at atmospheric conditions for two anhydrous starting latitic and trachytic melts: 1) five cooling rates (25, 12.5, 3, 0.5, and 0.125 °C/min) between 1300° and 800 °C, and 2) a 0.5 °C/min cooling rate from 1300 °C with quench temperatures at 1200°, 1100°, 1000° and 900 °C. Trachytic run-products are invariably glassy. Nucleation is also suppressed in the latitic run-products at the three highest cooling rates. Conversely, in the 0.5 and 0.125 °C/min runs, latites have a crystal content of  90 vol.%. The phases are: plagioclase, clinopyroxene, glass and iron-bearing oxide (in order of abundance). The variable quench temperatures, investigated by coupling experiments with Pt wire and Pt capsule sample containers in set 2, again did not produce crystallization of trachyte, whereas latitic samples are characterized by  10 vol.% of oxides, pyroxenes and plagioclase (in order of appearance), at temperature < 1000 °C. Effects of (preferential) heterogeneous nucleation on sample holders, of superheating degree, and chemical species loss during cooling are absent for both melt compositions. The difference of solidification paths between these two silicate melts can be ascribed only to their small chemical differences. In comparison with calculated equilibrium conditions all the experimental latitic and trachytic run-products revealed strong kinetic effects, interpretable in the light of the nucleation theory. The glass-forming ability (GFA) of trachyte is higher, whereas their critical cooling rate (Rc) is lower (< 0.125 °C/min), in comparison to latitic melts (Rc > 0.5 °C/min). The experimental results carried out in this study can be applied to lava flows and domes; trachytic lavas are able to flow for longer period with respect to latitic ones in a metastable condition. Glass-rich terrestrial lavas, i.e. obsidians, can be the result of sluggish nucleation kinetics due to the relative high polymerisation of evolved silicate melts.     

Elemental and isotopic variations in subduction related basalts: evidence for a three component model

Subduction related basalts display wide ranges in large ion lithophile element ratios (e.g., Rb/Ba and Rb/ Sr) which are unlikely to result from mixing, but suggest a role for small degree partial melting of a relatively Rb-poor mantle wedge source. However, these variations do not correlate with other trace element criteria, such as the depletions of high field strength elements (HFSE) and light rare earth elements (LREE) relative to the LILE, which characterise subduction related magmatism. Integration of radiogenic isotope and trace element data demonstrates that the elemental enrichment cannot be simply related to two component mixtures inferred from isotopic variations. Thus a minimum of three components is required to describe the geochemistry of subduction zone basalts. Two are subduction related: high Sr/Nd material is derived from the dehydration of subducted basaltic ocean crust, and a low Sr/Nd component is thought to be from subducted terrigenous sediment. The third component is in the mantle wedge, it is usually similar to the source of MORB, particularly in its isotopic composition. However, in some cases, notably continental areas, more enriched mantle wedge material with relatively high ⁸⁷Sr/⁸⁶Sr, low ¹⁴³Nd/¹⁴⁴Nd and elevated incompatible trace element contents may be involved Mixing of these three components is capable of producing both the entire range of Sr, Nd and Pb isotope signatures observed in destructive margin basalts, and their distinctive trace element compositions. The isotope differences between Atlantic and Pacific island arc basalts are attributed to the isotope compositions of sediments in the two oceans.     

Electrical conductivity of hydrous basaltic melts: implications for partial melting in the upper mantle

The Earth’s uppermost asthenosphere is generally associated with low seismic wave velocity and high electrical conductivity. The electrical conductivity anomalies observed from magnetotelluric studies have been attributed to the hydration of mantle minerals, traces of carbonatite melt, or silicate melts. We report the electrical conductivity of both H₂O-bearing (0–6 wt% H₂O) and CO₂-bearing (0.5 wt% CO₂) basaltic melts at 2 GPa and 1,473–1,923 K measured using impedance spectroscopy in a piston-cylinder apparatus. CO₂ hardly affects conductivity at such a concentration level. The effect of water on the conductivity of basaltic melt is markedly larger than inferred from previous measurements on silicate melts of different composition. The conductivity of basaltic melts with more than 6 wt% of water approaches the values for carbonatites. Our data are reproduced within a factor of 1.1 by the equation log σ = 2.172 − (860.82 − 204.46 w ^0.5)/(T − 1146.8), where σ is the electrical conductivity in S/m, T is the temperature in K, and w is the H₂O content in wt%. We show that in a mantle with 125 ppm water and for a bulk water partition coefficient of 0.006 between minerals and melt, 2 vol% of melt will account for the observed electrical conductivity in the seismic low-velocity zone. However, for plausible higher water contents, stronger water partitioning into the melt or melt segregation in tube-like structures, even less than 1 vol% of hydrous melt, may be sufficient to produce the observed conductivity. We also show that ~1 vol% of hydrous melts are likely to be stable in the low-velocity zone, if the uncertainties in mantle water contents, in water partition coefficients, and in the effect of water on the melting point of peridotite are properly considered.     

The solution behavior of H2O in peralkaline aluminosilicate melts at high pressure with implications for properties of hydrous melts

Solubility and solution mechanisms of H₂O in depolymerized melts in the system Na₂O-Al₂O₃-SiO₂ were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na₂Si₄O₉-Na₂(NaAl)₄O₉] with Al/(Al+Si) = 0.00-0.25. The H₂O solubility was fitted to the expression, X_H2O=0.20+0.0020f_H2O-0.7X_Al+0.9(X_Al)², where X_H2O is the mole fraction of H₂O (calculated with O = 1), f_H2O the fugacity of H₂O, and X_Al = Al/(Al+Si). Partial molar volume of H₂O in the melts, , calculated from the H₂O-solulbility data assuming ideal mixing of melt-H₂O solutions, is 12.5 cm³/mol for Al-free melts and decreases linearly to 8.9 cm³/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H₂O, , increases with Al/(Al+Si).Solution mechanisms of H₂O were obtained by combining Raman and ²⁹Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H₂O content. The rate of NBO/T-change with H₂O is negatively correlated with H₂O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q⁴-species to form Q² species. Steric hindrance appears to restrict bonding of H⁺ with nonbridging oxygen in Q³ species. The presence of Al³⁺ does not affect the water solution mechanisms significantly.     

Dynamic crystallization of shock melts in Allan Hills 77005: Implications for melt pocket formation in Martian meteorites

A series of crystallization experiments have been performed on synthetic glasses matching the composition of a melt pocket found in Allan Hills (ALH) 77005 in order to evaluate the heterogeneous nucleation potential of the melt and the effect of oxygen fugacity on crystallization. The starting temperature of the experiments varied from superliquidus, liquidus and subliquidus temperatures. Each run was then cooled at rates of 10, 500 and 1000 °C/h at FMQ. The results of this study constrain the heating and cooling regime for a microporphyritic melt pocket. Within the melt pocket, strong thermal gradients existed at the onset of crystallization, giving rise to a heterogeneous distribution of nucleation sites resulting in gradational textures of olivine and chromite. Skeletal olivine in the melt pocket center crystallized from a melt containing few nuclei cooled at a fast rate. Nearer to the melt pocket margin elongate skeletal shapes progress to hopper and equant euhedral, reflecting an increase in nuclei in the melt at the initiation of crystallization and growth at low degrees of supercooling. Cooling from post-shock temperatures took place on the order of minutes.An additional series of experiments were conducted for a melt temperature of 1510 °C and a cooling rate of 500 °C/h at the FMQ buffer, as well as 1 and 2 log units above and below FMQ. Variation in chromite stability in these experiments is reflected in crystal shapes and composition, and place constraints on the oxygen fugacity of crystallization of the melt pocket. We conclude that the oxygen fugacity of the melt pocket was set by the Fe³⁺/Fe²⁺ ratio imparted by melting of the host rock, rather than external factors such as incorporation of CO₂-rich Martian atmosphere, or melting and injection of oxidized surface (e.g., regolith) material.Comparison with previous crystallization experiments on melt pockets in Martian basalts indicate that the predominance of dendritic crystal shapes reflects the likelihood that those melt pockets with lower liquidus temperatures will be more completely melted, destroying most or all nuclei in the melt. In this case, crystal growth takes place at high degrees of supercooling, yielding dendritic shapes. It appears as though the melting process is just as important as cooling rate in determining the final texture of the melt pocket, as this process controls elimination or preservation of nuclei at the onset of cooling and crystallization.     

On the formation of continental silicic melts in thermochemical mantle convection models: implications for early Earth

Seafloor magnetotelluric (MT) data were collected at seven sites across the Hawaiian hot spot swell, spread approximately evenly between 120 and 800 km southwest of the Hawaiian-Emperor island chain. All data are consistent with an electrical strike direction of 300°, aligned along the seamount chain, and are well fit using two-dimensional (2D) inversion. The major features of the 2D electrical model are a resistive lithosphere underlain by a conductive lower mantle, and a narrow, conductive, ‘plume’ connecting the surface of the islands to the lower mantle. This plume is required; without it the swell bathymetry produces a large divergence of the along-strike and across-strike components of the MT fields, which is not seen in the data. The plume radius appears to be less than 100 km, and its resistivity of around 10 Ωm, extending to a depth of 150 km, is consistent with a bulk melt fraction of 5–10%.A seismic low velocity region (LVR) observed by Laske et al. [Laske, G., Phipp Morgan, J., Orcutt, J.A., 1999. First results from the Hawaiian SWELL experiment, Geophys. Res. Lett. 26, 3397–3400] at depths centered around 60 km and extending 300 km from the islands is not reflected in our inverse model, which extends high lithospheric resistivities to the edge of the conductive plume. Forward modeling shows that resistivities in the seismic LVR can be lowered at most to 30 Ωm, suggesting a maximum of 1% connected melt and probably less. However, a model of hot subsolidus lithosphere of 10² Ωm (1450–1500 °C) within the seismic LVR increasing to an off-swell resistivity of >10³ Ωm (<1300 °C) fits the MT data adequately and is also consistent with the 5% drop in seismic velocities within the LVR. This suggests a ‘hot, dry lithosphere’ model of thermal rejuvination, or possibly underplated lithosphere depleted in volatiles due to melt extraction, either of which is derived from a relatively narrow mantle plume source of about 100 km radius. A simple thermal buoyancy calculation shows that the temperature structure implied by the electrical and seismic measurements is in quantitative agreement with the swell bathymetry.     

Highly depleted isotopic compositions evident in Iapetus and Rheic Ocean basalts: implications for crustal generation and preservation

Subduction of both the Iapetus and Rheic oceans began relatively soon after their opening. Vestiges of both the Iapetan and Rheic oceanic lithospheres are preserved as supra-subduction ophiolites and related mafic complexes in the Appalachian–Caledonian and Variscan orogens. However, available Sm–Nd isotopic data indicate that the mantle source of these complexes was highly depleted as a result of an earlier history of magmatism that occurred prior to initiation of the Iapetus and Rheic oceans. We propose two alternative models for this feature: either the highly depleted mantle was preserved in a long-lived oceanic plateau within the Paleopacific realm or the source for the basalt crust was been recycled from a previously depleted mantle and was brought to an ocean spreading centre during return flow, without significant re-enrichment en-route. Data from present-day oceans suggest that such return flow was more likely to have occurred in the Paleopacific than in new mid-ocean ridges produced in the opening of the Iapetus and Rheic oceans. Variation in crustal density produced by Fe partitioning rendered the lithosphere derived from previously depleted mantle more buoyant than the surrounding asthenosphere, facilitating its preservation. The buoyant oceanic lithosphere was captured from the adjacent Paleopacific, in a manner analogous to the Mesozoic–Cenozoic “capture” in the Atlantic realm of the Caribbean plate. This mechanism of “plate capture” may explain the premature closing of the oceans, and the distribution of collisional events and peri-Gondwanan terranes in the Appalachian–Caledonian and Variscan orogens.     

Activated release of alkalis during the vesiculation of molten basalts under high vacuum: implications for lunar volcanism

Knudsen cell-quadrupole mass spectrometry was used to study the high-temperature vaporization of Hawaiian basalts, plagioclase, tektites, and samples from the Allende meteorite. Procedures are described by which mass loss rates and vapor pressures of Na and K were measured quantitatively.Gas-rich glassy basalts were observed to vesiculate under vacuum over the 900–1000°C region and simultaneously evaporate alkalis in nonequilibrium fashion at rates (units of μg/g/hr) of approximately 200–300 Na and 75–250 K. Degassed residues of the same basalts demonstrated equilibrium evaporation rates (over the same temperature range) of 60–120 Na and 30–60 K. The gas-deficient plagioclase and tektite sample showed only equilibrium vaporization with rates of 60 Na, 10 K (plagioclase) and 10 Na, 5K (tektites) at 900–1000°C. The Allende meteorite vaporized at rates of 2400 Na and 200 K at 900–1000°C, possibly by the reaction of Na₂O and K₂O with C or S₂, or by the thermal decomposition of nepheline or sodalite.The nonequilibrium vaporization of alkalis from the gas-rich basalts is attributed to vigorous agitation of the melt during its vesiculation by a gas phase composed principally of SO₂, CO₂, H₂O, CO, and H₂S. The major gases released from the Allende meteorite at 900–1000°C are, in order of decreasing abundance, CO, S₂, CO₂, H₂O, SO₂, and H₂S.It is proposed that nonequilibrium vaporization of alkalis during the vesiculation of lunar lavas was responsible for the production of alkali-rich vapors which subsequently deposited plagioclase crystals in the vugs of lunar rocks. The vesiculative, nonequilibrium vaporization of Na and K during a lunar volcanic eruption should be expected to occur at a high rate upon initial extrusion of the lava into vacuum but then decrease by a factor of approximately three when degassing is nearing completion. Vaporization losses remain inadequate to explain the uniformly low alkali concentrations in lunar basalts.     

Dissolution rates of metals in Fe oxides: implications for sampling ferruginous materials with significant relict Fe oxides

A study of the pattern of dissolution of synthetic and natural Fe oxides in 6 M HCl indicates that the rate of element release from synthetic Fe oxides is strongly influenced by mineralogy and the level of element incorporation. Synthetic maghemite (γ-Fe₂O₃) samples are subject to much more rapid dissolution than goethite (FeOOH) and hematite (α-Fe₂O₃). In samples dominated by hematite and maghemite, Cu, Zn and particularly Pb, in comparison to Fe, are preferentially released during the early stages of dissolution. Similar patterns are apparent from the dissolution of hematite- and maghemite-dominated samples derived from natural gossan. Comparison of XRD scans with data from the dissolution of natural gossan samples transformed by incremental heating to hematite- and maghemite-dominated assemblages suggests that the degree of crystallinity may also be a significant factor in the release of elements incorporated in the Fe oxides. Ferruginous materials made up of varying proportions of goethite, hematite, maghemite, kaolinite and quartz are important sampling materials in a range of regolith environments. These are products of complex chemical and mechanical mobilization over long periods of geological time. If the patterns of Fe oxide dissolution in 6 M HCl and the release of incorporated metals reflect stability in such weathering regimes, knowledge of the retention characteristics of incorporated metals in different Fe oxide phases, as indicated by this study, will be useful in the planning and interpretation of geochemical surveys in such regions.     

Geochemistry of the Emeishan flood basalts at Yangliuping, Sichuan, SW China: implications for sulfide segregation

A well-developed, 1,000 m thick basaltic sequence in the Yangliuping region, northern part of the Emeishan basalt province, includes the Lower and Middle Units of tholeiitic basalts and an Upper Unit of both tholeiites and subalkalic basalts. The basalts contain 42–55 wt% SiO₂ and 4.1–8.3 wt% MgO. Most of these lavas have Gd/Yb > 2.0, Zr/Nb < 12, and ɛ_{Nd(260 Ma)} values from +2.5 to +4.7. The platinum-group elements (PGE) are very mildly depleted in most of the basalts which contain 8–19 ppb Pt and 7–27 ppb Pd. However, a significant proportion of the Middle Unit basalts are strongly depleted in PGE with some samples having concentrations lower than detection limits. They have extremely high Zr/Nb ratios (up to 14.5) and low ɛ_{Nd(260 Ma)} values (+3.21 to +0.65), features of extensive lower crustal contamination. Some samples in this unit have high Ni/Pd (3,965–61,198) and low Pd/Cr (410,000–3,930,000) ratios, indicating sulfide segregation and PGE depletion prior to eruption. The primary magmas were S-undersaturated and derived from partial melting at variable depths in the upper mantle. The early and late stage magmas, as represented by the Lower and Upper Units, underwent AFC processes which induced mild S-saturation and PGE depletion in some of the basalts, whereas the magmas represented by the Middle Unit experienced more extensive crustal contamination resulting in stronger S-saturation and in most cases significant PGE depletion.