Petrologic insights from the spectra of the unbrecciated eucrites: Implications for Vesta and basaltic asteroids

Abstract– We investigate the relationship between the petrology and visible–near infrared spectra of the unbrecciated eucrites and synthetic pyroxene–plagioclase mixtures to determine how spectra obtained by the Dawn mission could distinguish between several models that have been suggested for the petrogenesis of Vesta’s crust (e.g., partial melting and magma ocean). Here, we study the spectra of petrologically characterized unbrecciated eucrites to establish spectral observables, which can be used to yield mineral abundances and compositions consistent with petrologic observations. No information about plagioclase could be extracted from the eucrite spectra. In contrast, pyroxene dominates the spectra of the eucrites and absorption band modeling provides a good estimate of the relative proportions of low‐ and high‐Ca pyroxene present. Cr is a compatible element in eucrite pyroxene and is enriched in samples from primitive melts. An absorption at 0.6 μm resulting from Cr³⁺ in the pyroxene structure can be used to distinguish these primitive eucrites. The spectral differences present among the eucrites may allow Dawn to distinguish between the two main competing models proposed for the petrogenesis of Vesta (magma ocean and partial melting). These models predict different crustal structures and scales of heterogeneity, which can be observed spectrally. The formation of eucrite Allan Hills (ALH) A81001, which is primitive (Cr‐rich) and relatively unmetamorphosed, is hard to explain in the magma ocean model. It could only have been formed as a quench crust. If the magma ocean model is correct, then ALHA81001‐like material should be abundant on the surface of Vesta and the Vestoids.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Cave air and hydrological controls on prior calcite precipitation and stalagmite growth rates: Implications for palaeoclimate reconstructions using speleothems

Hourly resolved cave air P_CO2 and cave drip water hydrochemical data illustrate that calcite deposition on stalagmites can be modulated by prior calcite precipitation (PCP) on extremely short timescales. A very clear second-order covariation between cave air P_CO2 and drip water Ca²⁺ concentrations during the winter months demonstrates the effects of degassing-induced PCP on drip water chemistry. Estimating the strength of the cave air P_CO2 control on PCP is possible because the PCP signal is so clear; at our drip site a one ppm shift in Ca²⁺ concentrations requires a P_CO2 shift of between 333 and 667 ppm. This value will undoubtedly vary from site to site, depending on drip water flow rate, residence time, drip water-cave air P_CO2 differential, and availability of low P_CO2 void spaces in the vadose zone above the cave. High-resolution cave environmental measurements were used to model calcite deposition on one stalagmite in Crag Cave, SW Ireland, and modelled growth over the study period (222 μm over 171 days) is extremely similar to the amount of actual calcite growth (240 μm) over the same time interval, strongly suggesting that equations used to estimate stalagmite growth rates are valid. Although cave air P_CO2 appears to control drip water hydrochemistry in the winter, drip water dilution caused by rain events may have played a larger role during the summer, as evidenced by a series of sudden drops in Ca²⁺ concentrations (dilution) followed by much more gradual increases in drip water Ca²⁺ concentrations (slow addition of diffuse water). This research demonstrates that PCP on stalactites, cave ceilings, and void spaces within the karst above the cave partially controls drip water chemistry, and that thorough characterisation of this process at individual caves is necessary to most accurately interpret climate records from those sites.