The contribution of sulphur dioxide from ablating micrometeorites to the atmospheres of Earth and Mars

Atmospheric composition is a key control on climate and the habitability of planetary surfaces. Ablation of infalling micrometeorites has been recognised as one way in which atmospheric chemistry can be changed, especially at times in solar system history when the infall rates of exogenous material were high. Despite its potential to influence climate and habitability, extraterrestrial sulphur dioxide is currently an unquantified contribution to the atmospheres of the terrestrial planets. We have used flash pyrolysis to simulate the atmospheric entry of micrometeorites and Fourier-transform infrared spectroscopy to identify and quantify the sulphur dioxide produced from the carbonaceous meteorites Orgueil (CI1), ALH 88045 (CM1), Cold Bokkeveld (CM2), Murchison (CM2) and Mokoia (CV3). We have used this approach to understand the introduction of sulphur dioxide to the atmospheres of Earth and Mars from infalling micrometeorites. Sulphates, present in carbonaceous chondrites at a few wt.%, are resistant to thermal decomposition, limiting the yields of sulphur dioxide from unmelted micrometeorites. Infalling micrometeorites are a minor source of present-day sulphur dioxide on Earth and Mars, calculated to be up to around 2400 tonnes and about 350 tonnes, respectively. During the Late Heavy Bombardment (LHB), the much greater infall rates of micrometeoritic dust are calculated to be associated with average production rates of sulphur dioxide of around 20 Mt yr⁻¹ for the early Earth and 0.5 Mt yr⁻¹ for early Mars, for a LHB of 100 Myr. These rates of delivery of sulphur dioxide at high altitudes would have reduced the solar energy reaching the surfaces of these planets, via scattering of sunlight by stratospheric sulphate aerosols, and may have had detrimental effects on developing biospheres by promoting cooler climates and reducing the probability of liquid water on planetary surfaces.     

Record of Late Pleistocene Glaciation and Deglaciation in the Southern Cascade Range. I. Petrological Evidence from Lacustrine Sediment in Upper Klamath Lake, Southern Oregon

Petrological and textural properties of lacustrine sediments from Upper Klamath Lake, Oregon, reflect changing input volumes of glacial flour and thus reveal a detailed glacial history for the southern Cascade Range between about 37 and 15 ka. Magnetic properties vary as a result of mixing different amounts of the highly magnetic, glacially generated detritus with less magnetic, more weathered detritus derived from unglaciated parts of the large catchment. Evidence that the magnetic properties record glacial flour input is based mainly on the strong correlation between bulk sediment particle size and parameters that measure the magnetite content and magnetic mineral freshness. High magnetization corresponds to relatively fine particle size and lower magnetization to coarser particle size. This relation is not found in the Buck Lake core in a nearby, unglaciated catchment. Angular silt-sized volcanic rock fragments containing unaltered magnetite dominate the magnetic fraction in the late Pleistocene sediments but are absent in younger, low magnetization sediments. The finer grained, highly magnetic sediments contain high proportions of planktic diatoms indicative of cold, oligotrophic limnic conditions. Sediment with lower magnetite content contains populations of diatoms indicative of warmer, eutrophic limnic conditions. During the latter part of oxygen isotope stage 3 (about 37–25 ka), the magnetic properties record millennial-scale variations in glacial-flour content. The input of glacial flour was uniformly high during the Last Glacial Maximum, between about 21 and 16 ka. At about 16 ka, magnetite input, both absolute and relative to hematite, decreased abruptly, reflecting a rapid decline in glacially derived detritus. The decrease in magnetite transport into the lake preceded declines in pollen from both grass and sagebrush. A more gradual decrease in heavy mineral content over this interval records sediment starvation with the growth of marshes at the margins of the lake and dilution of detrital material by biogenic silica and other organic matter.     

A crustal suture and lineament in North Africa

A possible suture between an old craton in West Africa and the Arabian—Nubian shield is marked by a persistent zone of Phanerozoic weakness. This zone extends between the Nile and Niger deltas and passes through the Qattara embayment, along the Bahariya fault, through the Kufra basin, between the Tibesti and Jabal al Uwaynat massifs, through the Bahr el Ghazal and Lake Chad areas, and along the Benoue trough.     

A Bayesian approach to inverse modelling of stratigraphy, part 1: method

The inference of ancient environmental conditions from their preserved response in the sedimentary record still remains an outstanding issue in stratigraphy. Since the 1970s, conceptual stratigraphic models (e.g. sequence stratigraphy) based on the underlying assumption that accommodation space is the critical control on stratigraphic architecture have been widely used. Although these methods considered more recently other possible parameters such as sediment supply and transport efficiency, they still lack in taking into account the full range of possible parameters, processes, and their complex interactions that control stratigraphic architecture. In this contribution, we present a new quantitative method for the inference of key environmental parameters (specifically sediment supply and relative sea level) that control stratigraphy. The approach combines a fully non‐linear inversion scheme with a ‘process–response’ forward model of stratigraphy. We formulate the inverse problem using a Bayesian framework in order to sample the full range of possible solutions and explicitly build in prior geological knowledge. Our methodology combines Reversible Jump Markov chain Monte Carlo and Simulated Tempering algorithms which are able to deal with variable‐dimensional inverse problems and multi‐modal posterior probability distributions, respectively. The inverse scheme has been linked to a forward stratigraphic model, BARSIM (developed by Joep Storms, University of Delft), which simulates shallow‐marine wave/storm‐dominated systems over geological timescales. This link requires the construction of a likelihood function to quantify the agreement between simulated and observed data of different types (e.g. sediment age and thickness, grain size distributions). The technique has been tested and validated with synthetic data, in which all the parameters are specified to produce a ‘perfect’ simulation, although we add noise to these synthetic data for subsequent testing of the inverse modelling approach. These tests addressed convergence and computational‐overhead issues, and highlight the robustness of the inverse scheme, which is able to assess the full range of uncertainties on the inferred environmental parameters and facies distributions.     

A Bayesian approach to inverse modelling of stratigraphy, part 2: Validation tests

A novel inverse modelling method is applied to the problem of constraining the environmental parameters (e.g. relative sea level, sediment supply) that control stratigraphic architecture. This technique links forward modelling of shallow-marine wave/storm-dominated stratigraphy to a combination of inverse methods formulated in a Bayesian framework. We present a number of examples in which relative sea-level and sediment-supply curves were inferred from synthetic vertical successions of grain size (e.g. wells) and synthetic thickness curves (e.g. seismically derived isopachs) extracted from a forward model simulation. These examples represent different scenarios that are designed to test the impact of data distribution, quantity and quality on the uncertainty of the inferred parameters. The inverse modelling approach successfully reproduces the gross stratigraphic architectures and relative sea level and sediment-supply histories of the synthetic forward model simulation, within the constraints of the modelled data quality. The relative importance of the forcing parameters can be evaluated by their sensitivity and impact on the inverted data. Of equal importance, the inverse results allow complete characterisation of the uncertainties inherent to the stratigraphic modelling tool and to the data quality, quantity and distribution. The numerical scheme also successfully deals with the problem of non-uniqueness of the solution of the inverse problem. These preliminary results suggest that the inverse method is a powerful tool in constraining stratigraphic architecture for hydrocarbon reservoir characterisation and modelling, and it may ultimately provide a process-based geological complement to standard geostatistical tools.     

A Raman spectroscopic study of H/D isotopically substituted hydrous aluminosilicate glasses

We have obtained high quality Raman spectra for two H/D isotopically substituted hydrous aluminosilicate glasses with compositions along the NaAlSi₃O₈-SiO₂ join. Consistent with the results of previous studies, the isotope shift for the band near 900 cm^–1, whose intensity grows with increasing water content, is extremely small: v _h /v _d = 1.004 ± 0.004. The lack of a definite H/D isotope shift for this band does not, however, preclude its association with a vibration of a hydrous species in the glass, because of likely strong coupling between different vibrational modes of hydrated framework species. The 900 cm^–1 band could well be due to a T — OH (T = Si, Al) stretching or bending vibration in the hydrous glass, as required by the presence of a combination band near 4500 cm^–1 in near-infrared spectra.     

Comparison of isoleucine epimerization in a model dipeptide and fossil protein

The dipeptide isoleucyl-glycine in aqueous solution has activation energies for isoleucine epimerization and hydrolysis of 23.1 and 20.9 kcal mol^?1, respectively. The activation energy for epimerization of NH₂-terminal isoleucine is 5–8 kcal mol^?1 less than activation energies reported for epimerization of isoleucine in the free state or in various protein systems. Furthermore, the rate of isoleucine epimerization in the NH₂-terminal position exceeds the rate of hydrolysis at temperatures between 0 and 152°C. Consequently, a high rate of epimerization in fossils should only occur when isoleucine is in the terminal position. Partially epimerized isoleucine will be converted through hydrolysis from the terminal form to the slower epimerizing free isoleucine. Over the course of the total isoleucine epimerization reaction, either in dipeptides or proteins, the activation energy will increase and the reaction rate will decrease as terminal isoleucine is converted to free isoleucine. This process may explain the non-linear kinetics observed for isoleucine epimerization in carbonate fossils.The degree of isoleucine epimerization is low in different molecular weight fractions of a fossil protein from Mercenaria in all fractions greater than 500 mol. wt, where most isoleucine is likely to be in the interior position. In the less than 500 mol. wt peptide fraction, where a considerable portion of the isoleucine is likely to be in the terminal position, the degree of epimerization is significantly greater. These analytical results from fossil protein support the interpretation of isoleucine kinetics obtained by study of dipeptides.     

Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.