Isotope geochemistry of caliche developed on basalt

Enormous variations in oxygen and carbon isotopes occur in caliche developed on < 3 Ma basalts in 3 volcanic fields in Arizona, significantly extending the range of δ¹⁸O and δ¹³C observed in terrestrial caliche. Within each volcanic field, δ¹⁸O is broadly co-variant with δ¹³C and increases as δ¹³C increases. The most ¹⁸O and ¹³C enriched samples are for subaerial calcite developed on pinnacles, knobs, and flow lobes that protrude above tephra and soil. The most ¹⁸O and ¹³C depleted samples are for pedogenic carbonate developed in soil atmospheres. The pedogenic caliche has δ¹⁸O fixed by normal precipitation in local meteoric waters at ambient temperatures and has low δ¹³C characteristic of microbial soil CO₂. Subaerial caliche has formed from ¹⁸O-rich evapoconcentrated meteoric waters that dried out on surfaces after local rains. The associated ¹³C enrichment is due either to removal of ¹²C by photosynthesizers in the evaporating drops or to kinetic isotope effects associated with evaporation. Caliche on basalt lava flows thus initially forms with the isotopic signature of evaporation and is subsequently over-layered during burial by calcite carrying the isotopic signature of the soil environment. The large change in carbon isotope composition in subsequent soil calcite defines an isotopic biosignature that should have developed in martian examples if Mars had a “warm, wet” early period and photosynthesizing microbes were present in the early soils. The approach can be similarly applied to terrestrial Precambrian paleocaliche in the search for the earliest record of life on land. Large variations reported for δ¹⁸O of carbonate in Martian meteorite ALH84001 do not necessarily require high temperatures, playa lakes, or flood runoff if the carbonate is an example of altered martian caliche.     

Evidence for fullerenes in solid bitumen from pillow lavas of Proterozoic age from Mítov (Bohemian Massif, Czech Republic)

Andesitic pillow lavas containing biogenic, solid bitumen (SB) are a constituent of a Neoproterozoic volcanosedimentary sequence (Teplá-Barrandian unit, Bohemian Massif) in the Mítov area of the Czech Republic. A black shale formation that is crosscut by these andesitic basalts is 565 Ma old. Carbon disulfide extracts of two powdered samples of SB contain 0.2 and 0.3 ppm of C₆₀, respectively, as determined by high-pressure liquid chromatography. The peak assignment based on retention time is fully supported by high-resolution electron ionization mass spectrometry (EI-MS). No C₇₀ was detected, nor was C₆₀ found in two other SB samples from this locality. Other investigated carbonaceous samples from Bohemia (coals and anthracites of Upper Paleozoic age and anthraxolite, graphitoids, and graphite of Upper Proterozoic age) did not contain fullerenes at concentrations above the detection limit of 0.01 ppm. The absence of C₆₀ in these samples was confirmed by EI-MS. The proposed mechanism of fullerene formation involves a primary algal phase, generation of a hydrocarbonaceous mixture in the course of thermal evolution of the sedimentary series, and their high-temperature transformation related to the extrusion of basalt. An important feature for fullerene conservation was the enclosure of fullerenes in SB with a structure similar to glasslike carbon, where the fullerene was protected against oxidation.     

Simulation of normal distributed smooth fields by Karhunen-Loéve expansion in combination with kriging

Simulation of multigaussian stochastic fields can be made after a Karhunen-Loéve expansion of a given covariance function. This method is also called simulation by Empirical Orthogonal Functions. The simulations are made by drawing stochastic coefficients from a random generator. These numbers are multiplied with eigenfunctions and eigenvalues derived from the predefined covariance model. The number of eigenfunctions necessary to reproduce the stochastic process within a predefined variance error, turns out to be a cardinal question. Some ordinary analytical covariance functions are used to evaluate how quickly the series of eigenfunctions can be truncated. This analysis demonstrates extremely quick convergence to 99.5% of total variance for the 2nd order exponential (‘gaussian’) covariance function, while the opposite is true for the 1st order exponential covariance function. Due to these convergence characteristics, the Karhunen-Loéve method is most suitable for simulating smooth fields with ‘gaussian’ shaped covariance functions. Practical applications of Karhunen-Loéve simulations can be improved by spatial interpolation of the eigenfunctions. In this paper, we suggest interpolation by kriging and limits for reproduction of the predefined covariance functions are evaluated.     

Influence of the zone of weakness on dip angle and shear heating of subducted slabs

We study the importance of the zones of weakness and the pattern of downgoing flow in steady-state models of subducting lithosphere, which interacts mechanically and thermally with the ambient mantle. The non-linear system of governing equations consists of (i) the momentum equation in stream function formulation and (ii) the steady-state heat transfer equation including conduction and advection of heat and dissipation. A finite element method has been applied to this system. We consider the viscosity to be a non-linear function of both the temperature and the stream function. In steady-state two-dimensional (2D) flow, the stream function isolines follow material trajectories. They are used to follow the top of the subducting slab, which because of its possible increase in water content, is assumed to have a lower viscosity. The zone of weakness has been thus obtained in the self-consistent fashion since the stream function as well as the temperature are the output from our modeling and no a priori assumptions about the shape of the bending lithosphere are taken into account. It was shown that several orders decrease of viscosity in the zone of weakness is required to obtain the dip angle of about 45°. If the decrease of viscosity is not sufficient enough, the subducted slab either sinks almost vertically or does not exhibit a plate-like behavior. We have also demonstrated that shear heating can unrealistically increase at the zone of weakness for fast subductions if decrease of viscosity is underestimated.     

Tetrahedral Plots of the Phase Relations for Basalts

The phase relations of quaternary systems are generally represented by projections onto ternary compositional planes. Such projections often obscure relationships that would only be evident in a three-dimensional tetrahedral plot. The tetrahedral plot requires that compositions of the minerals and melts be transformed into Cartesian coordinates. It is shown here how this transformation is carried out. The application is demonstrated by tetrahedral plots of experimental melt compositions of partially molten lherzolite. Furthermore, the plot can be used to evaluate whether or not a particular basaltic composition represents a primary melt. The methods are applicable to any four-component system.     

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ⁵⁶Fe and δ³⁰Si with increasing silica content as well as a systematic increase in δ⁵⁶Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ⁵⁶Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ⁵⁶Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ⁵⁶Fe = +0.05 ± 0.02 ‰; δ³⁰Si = ?0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.