Outgassing of ordinary chondritic material and some of its implications for the chemistry of asteroids, planets, and satellites

We used chemical equilibrium calculations to model thermal outgassing of ordinary chondritic material as a function of temperature, pressure, and bulk composition and use our results to discuss outgassing on asteroids and the early Earth. The calculations include ∼1000 solids and gases of the elements Al, C, Ca, Cl, Co, Cr, F, Fe, H, K, Mg, Mn, N, Na, Ni, O, P, S, Si, and Ti. The major outgassed volatiles from ordinary chondritic material are CH₄, H₂, H₂O, N₂, and NH₃ (the latter at conditions where hydrous minerals form). Contrary to widely held assumptions, CO is never the major C-bearing gas during ordinary chondrite metamorphism. The calculated oxygen fugacity (partial pressure) of ordinary chondritic material is close to that of the quartz-fayalite-iron (QFI) buffer. Our results are insensitive to variable total pressure, variable volatile element abundances, and kinetic inhibition of C and N dissolution in Fe metal. Our results predict that Earth's early atmosphere contained CH₄, H₂, H₂O, N₂, and NH₃; similar to that used in Miller—Urey synthesis of organic compounds.     

Foraminiferal changes and geochemical profiles across the Cenomanian/Turonian boundary in central and south-east Poland

Two sections of the Upper Cenomanian and Lower Turonian in central and south-east Poland were investigated for foraminifers, CaCO₃content, carbon content insoluble in HCl (C_org) and in the carbonates (C_carb), carbon and oxygen isotopic composition of bulk-rock carbonates and elemental abundances. The Cenomanian/Turonian boundary interval is characterized by the appearance of more marly facies, a δ¹³C and δ¹⁸O stable isotope anomaly, a considerable increase in C_org content and decrease in C_carb content and substantial changes in the foraminiferal assemblages. A major carbon stable isotope excursion with a shift of +2 (PDB) occurs in the lowermost Whiteinella archaeocretacea Zone. The late Cenomanian δ¹³C anomaly is associated with heavy δ¹⁸O values. The peak value of δ¹³C corresponds to the minima in P/B ratio and in diversity of foraminiferal assemblages. A late Cenomanian anoxic event is thought to be responsible for changes in foraminiferal assemblages. However, elemental abundance analyses do not show changes in the concentrations of trace elements. This may be explained by the long distance between studied area and a source of enrichment which was probably located in the western hemisphere.     

Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges

Estimation of Fe³⁺/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe³⁺/ΣFe ratio in silicates using Fe L_2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe³⁺/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe³⁺ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L₃-edge. This method allows mapping of Fe³⁺/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L₂ maximum for Fe³⁺, which is compared to the total integral intensity of the Fe L₂-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe³⁺/ΣFe ratios at the submicrometre scale in geological samples.     

Microplankton provide 9 Ma age for sediment in the Macquarie Island ophiolite complex

Macquarie Island in the southwest Pacific Ocean (55°S) is unique as an exposed location for studying oceanic crust generated by slow seafloor spreading—regions where rocks are difficult to date using radiometric methods. Bolboforms, an extinct group of poorly known microplankton, in sediment intercalated with pillow lavas yield tight constraints (9.01–8.78 Ma) on the age of formation of the dominantly seafloor volcanic sequence constituting the south of the island. The occurrence of Bolboforma metzmacheri extends the known geographic range of this Late Miocene zonal marker species in the southwest Pacific. A monospecific calcareous nannoplankton flora (Reticulofenestra perplexa) accompanied by the foraminifer Neogloboquadrina pachyderma in sediment from the north part of the island indicates a slightly older age (9.5–9.3 Ma), consistent with a radiometric date (9.2 ± 0.4 Ma) from nearby volcanics. The new age data indicate that the ocean floor volcanic sequence formed early in the Late Miocene, possibly along short segments of a slow-spreading mid-ocean ridge. Bolboforms have potential to provide fine-scale dating in other similarly complex ridge systems that are difficult to date by other means.     

Influence of the natural oxidation of the leachate organic fraction from a landfill on groundwater quality, Belo Horizonte: Minas Gerais, south-eastern Brazil

The objective of this work was to evaluate the influence of the natural degradation of the leachate organic fraction from the Belo Horizonte landfill on groundwater chemical evolution. The work focused on the modifications introduced by redox reactions in the presence of terminal electron acceptors. Twenty-one sampling points distributed along 13 monitoring wells were selected for the analysis of the chemical indicators of interest (TDS, SO ₄ ^?2 , Fe⁺², Ba, pH and Eh). The behaviour of the variables involved in the alteration of the water quality was assessed by the spatial distribution of target parameters, elaboration of redox diagrams and chemical modelling that focused on the determination of mineral saturation indexes. The study showed a trend toward pyrite precipitation, which leads to the removal of chemical species such as divalent iron and sulphur as sulphide from the system. This removal disturbs the chemical equilibrium, typically by moving the reactions to replenish the sulphate concentration present in the groundwater. This process occurs primarily through the dissolution of compounds that have sulphate in their chemical composition, such as barite, suggesting that part of the barium concentration in the subsurface can be of geogenic origin. This study demonstrated the importance of knowing the nature of the geochemical processes in groundwater contaminated by urban solid waste.