Carbon isotope effects in the open-system Fischer-Tropsch synthesis

Carbon isotopic composition was measured for products of the Fischer-Tropsch synthesis: catalytic reaction between CO and H₂ to produce CO, CO₂, light hydrocarbons C1-C4 and “oil” fraction. Hydrogen isotopes were also measured in the oil fraction and the produced water. Experimental runs were conducted in the flow-through reactor at 260-310 °C and 30 bar using the synthesis gas composed of 5N₂ + 3H₂ + 2CO, on Fe-catalyst mixed with ZSM-5 synthetic zeolite. In the two of seven runs a Fe + Co-catalyst was used that gives a lower yield of unsaturated hydrocarbons in reaction products. The isotopic effects depended on the conversion of the carbon monoxide. Under steady-state conditions (CO conversion more than 90%) a strong kinetic fractionation was observed between CO and CO₂ (∼−10‰) and CO and hydrocarbons (∼+38‰). At low conversion a clear “inverse” isotopic trend of the depletion in ¹³C of longer hydrocarbon chains was observed. On average, Δ₁₂ = δ¹³C(CH₄) − δ¹³C(C₂H₆) correlates well with the CO conversion: the C₂H₆ is ∼6‰ isotopically lighter than CH₄ at low conversion and ∼2‰ heavier at steady-state regime. Under steady-state conditions there almost no difference was observed in the isotopic composition of methane and ethane and higher hydrocarbons. The chemical composition of light hydrocarbons in the products of flow-through, dynamic FTS is different from that found in the static FTS-type experiments with Fe-catalyst, but isotopic effects are similar. Our results suggest that the isotopic distribution of carbon found in so-called “abiogenic” hydrocarbons from some natural gases (δ¹³C1 > δ¹³C2 > δ¹³C3  >?) is somewhat similar to that at low conversion of CO, but do not resemble the distribution characteristic for the high conversion products, at least, on Fe-catalyst. Other processes (a simple mixing of two or more endmembers) or other P-T conditions of the carbon reduction could be responsible for the “inverse” isotopic trend found in meteorites and some natural gases.     

Siberian gas venting and the end-Permian environmental crisis

The end of the Permian period is marked by global warming and the biggest known mass extinction on Earth. The crisis is commonly attributed to the formation of the Siberian Traps Large Igneous Province although the causal mechanisms remain disputed. We show that heating of Tunguska Basin sediments by the ascending magma played a key role in triggering the crisis. Our conclusions are based on extensive field work in Siberia in 2004 and 2006. Heating of organic-rich shale and petroleum bearing evaporites around sill intrusions led to greenhouse gas and halocarbon generation in sufficient volumes to cause global warming and atmospheric ozone depletion. Basin scale gas production potential estimates show that metamorphism of organic matter and petroleum could have generated > 100,000 Gt CO₂. The gases were released to the end-Permian atmosphere partly through spectacular pipe structures with kilometre-sized craters. Dating of a sill intrusion by the U–Pb method shows that the gas release occurred at 252.0 ± 0.4 million years ago, overlapping in time with the end-Permian global warming and mass extinction. Heating experiments to 275 °C on petroleum-bearing rock salt from Siberia suggests that methyl chloride and methyl bromide were significant components of the erupted gases. The results indicate that global warming and ozone depletion were the two main drivers for the end-Permian environmental crisis. We demonstrate that the composition of the heated sedimentary rocks below the flood basalts is the most important factor in controlling whether a Large Igneous Provinces causes an environmental crisis or not. We propose that a similar mechanism could have been responsible for the Triassic-Jurassic (~ 200 Ma) global warming and mass extinction, based on the presence of thick sill intrusions in the evaporite deposits of the Amazon Basin in Brazil.     

Al–Mg and Pb–Pb systematics of Allende CAIs: Canonical solar initial Al/Al ratio reinstated

The precise knowledge of the initial ²⁶Al/²⁷Al ratio [(²⁶Al/²⁷Al)₀] is crucial if we are to use the very first solid objects formed in our Solar System, calcium–aluminum-rich inclusions (CAIs) as the “time zero” age-anchor and guide future work with other short-lived radio-chronometers in the early Solar System, as well as determining the inventory of heat budgets from radioactivities for early planetary differentiation. New high-precision multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS) measurements of ²⁷Al/²⁴Mg ratios and Mg-isotopic compositions of nine whole-rock CAIs (six mineralogically characterized fragments and three micro-drilled inclusions) from the CV carbonaceous chondrite, Allende yield a well-defined ²⁶Al–²⁶Mg fossil isochron with an (²⁶Al/²⁷Al)₀ of (5.23 ± 0.13) × 10^− 5. Internal mineral isochrons obtained for three of these CAIs (A44A, AJEF, and A43) are consistent with the whole-rock CAI isochron. The mineral isochron of AJEF with (²⁶Al/²⁷Al)₀ = (4.96 ± 0.25) × 10^− 5, anchored to our precisely determined absolute ²⁰⁷Pb–²⁰⁶Pb age of 4567.60 ± 0.36 Ma for the same mineral separates, reinstate the “canonical” (²⁶Al/²⁷Al)₀ of 5 × 10^− 5 for the early Solar System. The uncertainty in (²⁶Al/²⁷Al)₀ corresponds to a maximum time span of ± 20 Ka (thousand years), suggesting that the Allende CAI formation events were culminated within this time span. Although all Allende CAIs studied experienced multistage formation history, including melting and evaporation in the solar nebula and post-crystallization alteration likely on the asteroidal parent body, the ²⁶Al–²⁶Mg and U–Pb-isotopic systematics of the mineral separates and bulk CAIs behaved largely as closed-system since their formation. Our data do not support the “supra-canonical” ²⁶Al/²⁷Al ratio of individual minerals or their mixtures in CV CAIs, suggesting that the supra-canonical ²⁶Al/²⁷Al ratio in the CV CAIs may have resulted from post-crystallization inter-mineral redistribution of Mg isotopes within an individual inclusion. This redistribution must be volumetrically minor in order to satisfy the mass balance of the precisely defined bulk CAI and bulk mineral data obtained by MC-ICP-MS.The radiogenic ²⁰⁸Pb/²⁰⁶Pb ratio obtained as a by-product from the Pb–Pb age dating is used to estimate time-integrated ²³²Th/²³⁸U ratio (κ value) of CAIs. Limited κ variations among the minerals within a single CAI, contrasted by much larger variations among the bulk CAIs, suggest Th/U fractionation occurred prior to crystallization of igneous CAIs. If interpreted as primordial heterogeneity, the κ value can be used to calculate the mean age of the interstellar dust from which the CAIs condensed.     

The effect of mantle composition on density in the extending lithosphere

The density distribution of the lithosphere is non-linear and discontinuous due to complex mineralogy and, most importantly, phase transitions. We evaluate the influence of changes in mantle composition on lithospheric density and its evolution during horizontal stretching, using thermodynamic calculations of the density as a function of pressure, temperature and composition. We also develop a simple parameterization based on end-member mineral reactions and geometric relationships between the geotherm and the phase boundary for comparison. The garnet–spinel peridotite transition leads to a moderate decrease in density of the mantle part of the lithospheric column at the initial stages of stretching. When the crust is sufficiently thinned and temperature is relatively high, plagioclase peridotite becomes stable in the upper part of the mantle. The density reduction due to the plagioclase-in reaction is controlled by bulk Al₂O₃ in the mantle and by the depth of the plagioclase-in reaction, which is mainly governed by the Na₂O/Al₂O₃ ratio. Since Na₂O and Al₂O₃ increase with the fertility of the mantle the phase transition effect is most pronounced for relatively fertile mantle (and strong extension) and can lead to 2.3% density reduction. This is equivalent to heating the entire lithosphere by 700 °C if only the effect of thermal expansion on density is taken into account. The formation of plagioclase peridotite can explain syn-rift uplift in sedimentary basins that experienced large mantle stretching without invoking an unrealistically strong increase in temperature. It might also be responsible for the break-up unconformity observed at continental margins.     

Correlation between foam-bubble size and drag coefficient in hurricane conditions

A recently proposed model of foam impact on the air–sea drag coefficient C _d has been employed for the estimation of the effective foam-bubble radius R _b variation with wind speed U₁₀ in hurricane conditions. The model relates C _d (U₁₀) with the effective roughness length Z _eff (U₁₀) represented as a sum of aerodynamic roughness lengths of the foam-free and foam-covered sea surfaces Z _w (U₁₀) and Z _f (U₁₀) weighted with the foam coverage coefficient α _f (U₁₀). This relation is treated for known phenomenological distributions C _d (U₁₀), Z _w (U₁₀), and α _f (U₁₀) at strong wind speeds as an inverse problem for the effective roughness parameter of foam-covered sea surface Z _f (U₁₀). The present study is aimed at the estimation of the effective roughness of the sea surface assuming that the measurement data for the effective drag coefficient are known. The effective foam-bubble size is found as a function of the wind speed.