Nitrogen functionality in “oil window” rank range vitrinite rich coals and chars

X-ray photoelectron spectroscopy (XPS) was used to characterize organic nitrogen species in coals and chars. The coals comprise a set of vitrinite-rich samples from the Penn State Coal Bank set, ranging from vitrinite reflectance (R_r) 0.42-1.60%. Chars were obtained after coal pyrolysis under an inert atmosphere at 800 °C and fast heating rate. In the coals, pyrrolic nitrogen was the predominant form, steadily decreasing with coal rank, while pyridinic and quaternary nitrogen showed pronounced variation with rank. In contrast to the coals, the chars show much less pyrrolic and pyridinic nitrogen, and more quaternary nitrogen. The chars were also characterized by having oxidized nitrogen and nitro sub-peaks, which were not observed for the coals. Apparently the occurrence of these forms is related to the decrease in the pyridinic nitrogen.     

Environmental controls on stable isotope precipitation values over Mali and Niger,West Africa

This study evaluated the effects of the environmental factors precipitation amount (P), temperature (T), and vapor pressure (V _p) on the stable isotope composition (δ) of precipitation and the excess-deuterium (d) parameter in Mali and Niger, West Africa. At both locations, δ values were greatly affected by seasonal climatic conditions and a statistically significant negative correlation was observed between δ and P. In Mali, a statistically significant negative correlation was also observed between δ and V _p. There was no statistically significant correlation between δ and T. Mean-weighting of δ values may be masking both dry-season and individual storm event precipitation phenomena, which are otherwise observed in arithmetically averaged δ values. Mean monthly d values for peak monsoonal months indicate that precipitation is first-fraction, gaining little recycled water on its journey inland from the Atlantic Ocean near the equator. Agreement between rainy-season precipitation and groundwater δ values, specifically peak monsoonal months, indicates that groundwater is being recharged by infiltration of current monsoonal rains and is not paleo-groundwater recharged under past climatic conditions. Similarity between rainy-season precipitation and groundwater d values provide another indication that monsoonal precipitation under current climatic conditions is the source of groundwater recharge. The knowledge that groundwater is recently recharged monsoonal rains, rather than paleo-groundwater, is important for evaluating groundwater sustainability and the effects that climate change will have on water resources. Understanding and predicting changes in precipitation amounts and intensities, which ultimately affect timing and amount of groundwater recharge, is critical for water resource management.     

A model for inferring dissolved organic carbon (DOC) in lakewater from visible-near-infrared spectroscopy (VNIRS) measures in lake sediment

We developed an inference model to infer dissolved organic carbon (DOC) in lakewater from lake sediments using visible-near-infrared spectroscopy (VNIRS). The inference model used surface sediment samples collected from 160 Arctic Canada lakes, covering broad latitudinal (60–83°N), longitudinal (71–138°W) and environmental gradients, with a DOC range of 0.6–39.6 mg L⁻¹. The model was applied to Holocene lake sediment cores from Sweden and Canada and our inferences are compared to results from previous multiproxy paleolimnological investigations at these two sites. The inferred Swedish and Canadian DOC profiles are compared, respectively, to inferences from a Swedish-based VNIRS-total organic carbon (TOC) model and a Canadian-based diatom-inferred (Di-DOC) model from the same sediment records. The 5-component Partial Least Squares (PLS) model yields a cross-validated (CV) R_CV² R_{CV}^{2}  = 0.61 and a root mean squared error of prediction (RMSEP _CV ) = 4.4 mg L⁻¹ (11% of DOC gradient). The trends inferred for the two lakes were remarkably similar to the VNIRS-TOC and the Di-DOC inferred profiles and consistent with the other paleolimnological proxies, although absolute values differed. Differences in the calibration set gradients and lack of analogous VNIRS signatures in the modern datasets may explain this discrepancy. Our results corroborate previous geographically independent studies on the potential of using VNIRS to reconstruct past trends in lakewater DOC concentrations rapidly.     

The Size and Shape of the Oblong Dwarf Planet Haumea

We use thermal radiometry and visible photometry to constrain the size, shape, and albedo of the large Kuiper belt object Haumea. The correlation between the visible and thermal photometry demonstrates that Haumea’s high amplitude and quickly varying optical light curve is indeed due to Haumea’s extreme shape, rather than large scale albedo variations. However, the well-sampled high precision visible data we present does require longitudinal surface heterogeneity to account for the shape of lightcurve. The thermal emission from Haumea is consistent with the expected Jacobi ellipsoid shape of a rapidly rotating body in hydrostatic equilibrium. The best Jacobi ellipsoid fit to the visible photometry implies a triaxial ellipsoid with axes of length 1,920 × 1,540 × 990 km and density $2.6$  g cm $^{-3}$ , as found by Lellouch et al. (A&A, 518:L147, 2010. doi:10.1051/0004-6361/201014648). While the thermal and visible data cannot uniquely constrain the full non-spherical shape of Haumea, the match between the predicted and measured thermal flux for a dense Jacobi ellipsoid suggests that Haumea is indeed one of the densest objects in the Kuiper belt.     

Paleomagnetic constraints on the paleogeography and oroclinal bending of the Devonian volcanic arc in Kazakhstan

Numerical modelling, incorporating coupling between surface processes and induced flow in the lower continental crust, is used to address the Quaternary evolution of the Gulf of Corinth region in central Greece. The post-Early Pleistocene marine depocentre beneath this Gulf overlies the northern margin of an older (Early Pleistocene and earlier) lacustrine basin, the Proto Gulf of Corinth Basin or PGCB. In the late Early Pleistocene, relief in this region was minimal but, subsequently, dramatic relief has developed, involving the creation of  900 m of bathymetry within the Gulf and the uplift by many hundreds of metres of the part of the PGCB, south of the modern Gulf, which forms the Gulf's main sediment supply. It is assumed that, as a result of climate change around 0.9 Ma, erosion of this sediment source region and re-deposition of this material within the Gulf began, both processes occurring at spatial average rates of  0.2 mm a^− 1. Modelling of the resulting isostatic response indicates that the local effective viscosity of the lower crust is  4 × 10¹⁹ Pa s, indicating a Moho temperature of  560 °C. It predicts that the  10 mm a^− 1 of extension across this  70 km wide model region, at an extensional strain rate of  0.15 Ma^− 1, is partitioned with  3 mm a^− 1 across the sediment source,  2 mm a^− 1 across the depocentre, and  5 mm a^− 1 across the ‘hinge zone’ in between, the latter value being an estimate of the extension rate on normal faults forming the major topographic escarpment at the southern margin of the Gulf. This modelling confirms the view, suggested previously, that coupling between this depocentre and sediment source by lower-crustal flow can explain the dramatic development in local relief since the late Early Pleistocene. The effective viscosity of the lower crust in this region is not particularly low; the strong coupling interpreted between the sediment source and depocentre results instead from their close proximity. In detail, the effective viscosity of the lower crust is expected to decrease northward across this model region, due to the northward increase in exposure of the base of the continental lithosphere to the asthenosphere; in the south the two are separated by the subducting Hellenic slab. The isostatic consequences of such a lateral variation in viscosity provide a natural explanation for why, since  0.9 Ma, the modern Gulf has developed asymmetrically over the northern part of the PGCB, leaving the rest of the PGCB to act as its sediment source.     

Characterization of mesostasis regions in lunar basalts: Understanding late‐stage melt evolution and its influence on apatite formation

Recent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile‐bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk‐rock basaltic composition and that of bulk‐mesostasis regions, indicating that bulk‐rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late‐stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO₂ abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite‐melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.     

The effects of meteorite impacts on the availability of bioessential elements for endolithic organisms

Abstract– Meteorite impacts, one of the most ubiquitous processes in the solar system, have the ability to destroy as well as create habitats for life. The impact process can increase the translucency and porosity of the target substrate, as well as mobilize biologically relevant elements within the substrate. For endolithic organisms, this process has important implications, especially in extreme environments where they are forced to seek refuge in the interior of rocks. Here, we show that unshocked target rocks and rocks that have experienced pressures up to about 80 GPa from the Haughton impact structure, Devon Island, Canada, possess a small, but discernible change in bulk chemistry within the major oxide analysis. However, changes in the distribution of elements did occur with increasing shock level for both the sedimentary and crystalline target. Both the crystalline and sedimentary target rocks contain significant amounts of glasses at higher shock levels (up to about 95% by volume), which would improve the availability of these elements to potential microbial endoliths as glasses are more easily dissolved by organic acids. The implication that impact events do not impoverish their capacity to serve as a “substrate” through volatilization is important with respect to analogous impact structures on Mars. After the deleterious effects of the direct meteorite impact, any microorganisms on Mars would have benefited from the input of heat, the mobilization of a possible frozen groundwater system, as well as increased translucency, porosity, and trace nutrient availability of the target substrate.