Crystallization of authigenic carbonates in mud volcanoes at Lake Baikal

This paper presents data on authigenic siderite first found in surface sediments from mud volcanoes in the Central (K-2) and Southern (Malen’kii) basins of Lake Baikal. Ca is the predominant cation, which substitutes Fe in the crystalline lattice of siderite. The enrichment of the carbonates in the ¹³C isotope (from +3.3 to +6.8‰ for the Malen’kii volcano and from +17.7 to +21.9‰ for K-2) results from the crystallization of the carbonates during methane generation via the bacterial destruction of organic matter (acetate). The overall depletion of the carbonates in ¹⁸O is mainly inherited from the isotopic composition of Baikal water.     

Late Palaeozoic hydrocarbon migration through the Clair field, West of Shetland, UK Atlantic margin

Geochemical analysis of bitumen- and hydrocarbon-bearing fluid inclusions from the Devonian-Carboniferous Clair field indicates that the reservoirs contain a mixture of oils from different marine and lacustrine sources. Reconstruction of the Clair field oil-charge history using fluid inclusion petrography show that oil-charging occurred at times of K-feldspar, quartz and calcite cementation. Temperature–composition–time data yielded from the integration of fluid inclusion microthermometry with high-resolution Ar–Ar dating, date hydrocarbon-bearing K-feldspar overgrowths at 247 ± 3.3 Ma. These data show that in order for oil to be trapped within primary fluid inclusions in K-feldspar overgrowths, hydrocarbon migration throughout the UK Atlantic margin must have been taking place during the Late Palaeozoic and as such, current industry oil-play models based solely on oil charging from Jurassic-Cretaceous marine sources are clearly incomplete and need revision. Apatite fission track analysis and vitrinite reflectance data were used to reconstruct thermal burial histories and assess potential oil generation from Middle Devonian lacustrine source rocks. Thermal history data from wells along The Rona Ridge adjacent to the Clair field show that the Palaeozoic section was heated to greater than 100 °C at some time between 270 and 230 Ma, confirming that Devonian source rocks were mature and expelling oil during the Late Palaeozoic at the time that authigenic K-feldspar overgrowths were growing in the Clair field.     

Quantitative textural analysis of packings of elongate crystals

The spatial distribution of grains in a solidifying igneous rock controls the physical properties of the crystal mush, and in turn is controlled by the rate of crystal growth and accumulation. A predominant non-spherical habit for igneous minerals brings into question the use of spherical particles in reference packings used for quantification of spatial distribution. Furthermore, variations of crystal clustering/ordering with length scale require spatial statistics which take into account the distribution of particles beyond nearest neighbours. Using random close packings of spherocylinders, we demonstrate the importance of aspect ratio for the aggregation index (usually known as R) and show that packings of spherical particles have more structure than packings of rods. The spatial distribution functions demonstrate that the plagioclase grains in the colonnade from the Holyoke basalt are clustered on a length scale of 0.5 mm. Understanding the controls on grain spatial distribution in igneous rocks will depend on the application of these techniques to well-understood environments.     

Zircon coronas around Fe–Ti oxides: a physical reference frame for metamorphic and metasomatic reactions

Ilmenite in coronitic gabbros from the Bamble and Kongsberg sectors, southern Norway, is surrounded by zircons ranging in diameters from a fraction of a micrometer to 10 μm across. The zircons are inert during subsequent metamorphism (amphibolite- to pumpellyite–prehnite facies) and metasomatism (scapolitization and albitization) and can be found as trails in silicates (phlogopite, talc, chlorite, amphibole, albite, and tourmaline) in the altered rocks. The trails link up to form polygons outlining the former oxide grain boundary. This 3-dimensional framework of zircons is used to (a) recognize metasomatic origin of rocks, (b) quantify the mobility of elements during mineral replacement, (c) establish the growth direction of reaction fronts and to identify the reaction mechanism as dissolution–reprecipitation. Zircon coronas on Fe–Ti oxides have been described from a number of terrains and appear to be common in mafic rocks (gabbros and granulites) providing a tool for a better understanding of metasomatic and metamorphic reactions.     

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Basaltic explosive volcanism: Constraints from deposits and models

Basaltic pyroclastic volcanism takes place over a range of scales and styles, from weak discrete Strombolian explosions (～10²–10³ kg s^?1) to Plinian eruptions of moderate intensity (10⁷–10⁸ kg s^?1). Recent well-documented historical eruptions from Etna, Kīlauea and Stromboli typify this diversity. Etna is Europe's largest and most voluminously productive volcano with an extraordinary level and diversity of Strombolian to subplinian activity since 1990. Kīlauea, the reference volcano for Hawaiian fountaining, has four recent eruptions with high fountaining (>400 m) activity in 1959, 1960, 1969 (–1974) and 1983–1986 (–2008); other summit (1971, 1974, 1982) and flank eruptions have been characterized by low fountaining activity. Stromboli is the type location for mildly explosive Strombolian eruptions, and from 1999 to 2008 these persisted at a rate of ca. 9 per hour, briefly interrupted in 2003 and 2007 by vigorous paroxysmal eruptions. Several properties of basaltic pyroclastic deposits described here, such as bed geometry, grain size, clast morphology and vesicularity, and crystal content are keys to understand the dynamics of the parent eruptions.The lack of clear correlations between eruption rate and style, as well as observed rapid fluctuations in eruptive behavior, point to the likelihood of eruption style being moderated by differences in the fluid dynamics of magma and gas ascent and the mechanism by which the erupting magma fragments. In all cases, the erupting magma consists of a mixture of melt and gaseous bubbles. The depth and rate of degassing, melt rheology, bubble rise and coalescence rates, and extent of syn-eruptive microlite growth define complex feedbacks that permit reversible shifts between fragmentation mechanisms and in eruption style and intensity. However, many basaltic explosive eruptions end after an irreversible shift to open-system outgassing and microlite crystallization in melt within the conduit.Clearer understanding of the factors promoting this diversity of basaltic pyroclastic eruptions is of fundamental importance in order to improve understanding of the range of behaviors of these volcanoes and assess hazards of future explosive events at basaltic volcanoes. The three volcanoes used for this review are the sites of large and growing volcano-tourism operations and there is a public need both for better knowledge of the volcanoes’ behavior and improved forecasting of the likely course of future eruptions.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Microbial release of potassium from K-bearing minerals by thermophilic fungus Aspergillus fumigatus

A strain of thermophilic fungus Aspergillus fumigatus was cultured with K-bearing minerals to determine if microbe-mineral interactions enhance the release of mineralic potassium. Experiments were carried out in two settings, one with the mineral grains and the fungal cells in direct contact, and the other employing a membrane (pore size 0.22 μm) to separate the two. Measurements over a period of 30 days showed that, irrespective of the experimental setup, the concentration of free K in the culture was drastically higher than those in any of the control experiments where no living organism was present. Moreover, the occurrence of mineral-cell physical contact enhanced potassium release by an additional factor of 3 to 4 in comparison to the separation experiments. For contact experiments, Electron Probe Microanalysis revealed the formation of mycelium-mineral aggregates, and Atomic Force Microscopy imaging further indicated the possible ingestion of mineral particles by the fungus cells. Contrasting to what was observed and expected in control experiments, the potassium solubilization rate showed a positive dependence upon pH when fungi and minerals were mixed directly, and exhibited no correlations with solution acidity if cell-rock contact was restrained. These results appear to suggest that A. fumigatus promoted potassium release by means of at least three likely routes, one through the complexation of soluble organic ligands, another appealing to the immobile biopolymers such as the insoluble components of secretion, and the third related to the mechanical forces in association with the direct physical contact between cells and mineral particles.     

Fast kimberlite ascent rates estimated from hydrogen diffusion profiles in xenolithic mantle olivines from southern Africa

Fourier transform infrared spectrometry (FTIR) analyses of olivines from peridotite xenoliths found in southern African kimberlites indicate 0 to 80 ppm H₂O concentrations. OH absorbance profiles across olivine grains show homogeneous H contents from core to edge for most samples. In one sample the olivines are H-free, while another has olivines characterized by lower H contents at the grain edges compared to the cores, indicating H loss during transport of the xenolith to the surface. Flat or near-flat H profiles place severe constraints on the duration of H loss from olivine grains, with implications for kimberlite magma ascent rates. Diffusion equations were used to estimate times of H loss of about 4 h for the sample with heterogeneous olivine H contents. Resulting kimberlite ascent rates are calculated to be 5-37 m s⁻¹ minimum, although these estimates are highly dependent on volatile contents and degassing behavior of the host kimberlite magma. Xenolithic olivines from alkali basalts generally have lower H contents and more pronounced H diffusion profiles than do those from kimberlites. This difference is likely caused by higher magma temperatures and lower ascent rates of alkali basalts compared to kimberlites.     

A depleted, not ideally chondritic bulk Earth: The explosive-volcanic basalt loss hypothesis

It has long been customary to assume that in the bulk composition of the Earth, all refractory-lithophile elements (including major oxides Al₂O₃ and CaO, all of the REE, and the heat-producing elements Th and U) occur in chondritic, bulk solar system, proportion to one another. Recently, however, Nd-isotopic studies (most notably Boyet M. and Carlson R. W. (2006) A new geochemical model for the Earth’s mantle inferred from ¹⁴⁶Sm-¹⁴²Nd systematics. Earth Planet. Sci. Lett.250, 254-268) have suggested that at least the outer portion of the planet features a Nd/Sm ratio depleted to ∼0.93 times the chondritic ratio. The primary reaction to this type of evidence has been to invoke a “hidden” reservoir of enriched matter, sequestered into the deepest mantle as a consequence of primordial differentiation. I propose a hypothesis that potentially explains the evidence for Nd/Sm depletion in a very different way. Among the handful of major types of differentiated asteroidal meteorites, two (ureilites and aubrites) are ultramafic restites so consistently devoid of plagioclase that meteoriticists were once mystified as to how all the complementary plagioclase-rich matter (basalt) was lost. The explanation appears to be basalt loss by graphite-fueled explosive volcanism on roughly 100-km sized planetesimals; with the dispersiveness of the process dramatically enhanced, relative to terrestrial experience, because the pyroclastic gases expand into vacuous space (Wilson L. and Keil K. (1991) Consequences of explosive eruptions on small Solar System bodies: the case of the missing basalts on the aubrite parent body. Earth Planet. Sci. Lett.104, 505-512). By analogy with lunar pyroclastic products, the typical size of pyroclastic melt/glass droplets under these circumstances will be roughly 0.1 mm. Once separated from an asteroidal or planetesimal gravitational field, droplets of this size will generally spiral toward the Sun, rather than reaccrete, because drag forces such the Poynting-Robertson effect quickly modify their orbits (the semimajor axis, in a typical scenario, is reduced by several hundred km during the first trip around the Sun). Assuming a similar process occurred on many of the Earth’s precursor planetesimals while they were still roughly 100 km in diameter, the net effect would be a depleted composition for the final Earth. I have modeled the process of trace-element depletion in the planetesimal mantles, assuming the partial melting was nonmodal and either batch or dynamic in terms of the melt-removal style. Assuming the process is moderately efficient, typical final-Earth Nd/Sm ratios are 0.93-0.96 times chondritic. Depletion is enhanced by a relatively low assumed residual porosity in batch-melting scenarios, but dampened by a relatively high value for “continuous” residue porosity in dynamic melting scenarios. Pigeonite in the source matter has a dampening effect on depletion. There are important side effects to the Nd/Sm depletion. The heat-producing elements, Th, U and K, might be severely depleted. The Eu/Eu^∗ ratio of the planet is unlikely to remain precisely chondritic. One of the most inevitable side effects, depletion of the Al/Ca ratio, is consistent with an otherwise puzzling aspect of the composition of the upper mantle. A perfectly undepleted composition for the bulk Earth is dubious.