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.     

Intellectual property rights and low carbon technology transfer: Conflicting discourses of diffusion and development

Intellectual property rights (IPRs) and the transfer of low carbon technologies to developing countries have been the focus of sustained disagreement between many developed and developing country Parties to the United Nations Framework Convention on Climate Change (UNFCCC). We argue that this disagreement stems from two conflicting political discourses of economic development and low carbon technology diffusion which tend to underpin developing and developed countries’ respective motivations for becoming party to the Convention. We illustrate the policy implications of these discourses by examining empirical evidence on IPRs and low carbon technology transfer and highlight how the two discourses are based on an incomplete understanding of the role of technological capacity in either economic development or technology diffusion. This has important implication for the success of post-2012 international climate agreements.     

Calorimetric study of high pressure polymorphism in FeTiO3: Stability of the perovskite phase

A calorimetric study of the ilmenite and lithium niobate polymorphs of FeTiO₃ was undertaken to assess the high-pressure stabilities of these phases. Ilmenite is known to be the stable phase at ambient pressure, but the lithium niobate form may be a quench phase from a perovskite form which has been previously observed in situ at high pressure.In this study, the lithium niobate phase of FeTiO₃ was synthesized from an ilmenite starting material at 15– 16 GPa and 1473 K, using a uniaxial split-sphere high-pressure apparatus (USSA 2000). The energetics of the ilmenite to lithium niobate transformation were investigated through transposed-temperature drop calorimetry. The heat of back-transformation of lithium niobate to ilmenite was measured by dropping the sample in argon from ambient conditions to a temperature where the transformation occurs spontaneously. In drops made at 977 K, an intermediate x-ray amorphous phase was encountered. At 1273 K, the transformation went to completion. A value of -13.5±1.2 kJ/mol was obtained for the heat of transformation.     

Calorimetric study of high-pressure phase transitions among the CdGeO3 polymorphs (pyroxenoid,garnet, ilmenite,and perovskite structures)

At high pressures, CdGeO₃ pyroxenoid transforms to garnet, then to ilmenite, and finally to perovskite. Enthalpies of transition among the four phases were measured by high temperature calorimetry. The entropies of transition and slopes of the boundaries were calculated using the measured enthalpies and free energies calculated from the phase equilibrium data. Pyroxenoid and garnet are very similar energetically. However garnet is a high pressure phase because of its lower entropy and smaller volume. The pyroxenoid-garnet transition has a small positiveP-T slope. Ilmenite is intermediate in enthalpy between garnet and perovskite, but is lower in entropy than both phases. Therefore the garnet-ilmenite transition has a positivedP/dT, while a negativedP/dT is calculated for the ilmenite-perovskite transition. The thermochemical data for the CdGeO₃ phases are generally consistent with the observed high pressure phase relations. The high entropy of perovskite relative to ilmenite, observed in several ABO₃ comounds including CdGeO₃, is related to the structural features of perovskite, in which relatively small divalent cations occupy the large sites of 8–12 fold coordination. The thermochemistry of the CdGeO₃ polymorphs shows several similarities to that of the CaGeO₃ system.     

Environments of the Russian Plain during the Middle Valdai Briansk Interstade (33,000–24,000 yr B.P.) Indicated by Fossil Mammals and Plants

Abundant mammal (45 localities) and plant (52 sections) fossil data collected from the Russian Plain deposits of the Middle Valdai Briansk Interstade indicate a period of noticeable warming. These materials were jointly analyzed. The data were organized in the database software PARADOX and then moved to the GIS program ARC/INFO. Mathematical methods as well as traditional research methods were used for the analysis. The reconstructed biogeographical provinces illustrate the specific environmental and climatic conditions of the Briansk Interstade. Analogues of modern natural zones did not exist at this time on the Russian Plain. The Briansk landscapes reflect the moderate-cool climate of this period, when the majority of northern subarctic plant and mammal species extended their ranges considerably to the south to the Central Russian Plain. At the same time, steppe species penetrated farther north and west. This combination shows that the continuous forest zone was destroyed during the Briansk Inter-stade. Five biogeographical provinces have been reconstructed from the north to the south for the Russian Plain during the Briansk warming on the basis of joint analysis of mammalian and botanical data.     

Long-term change in eelgrass distribution at Bahía San Quintín,Baja California,Mexico, using satellite imagery

Seagrasses are critically important components of many marine coastal and estuarine ecosystems, but are declining worldwide. Spatial change in distribution of eelgrass,Zostera marina L., was assessed at Bahía San Quintín, Baja California, Mexico, using a map to map comparison of data interpreted from a 1987 Satellite Pour l'Observation de la Terre multispectral satellite image and a 2000 Landsat Enhanced Thematic Mapping image. Eelgrass comprised 49% and 43% of the areal extent of the bay in 1987 and 2000, respectively. Spatial extent of eelgrass was 13% less (−321 ha) in 2000 than in 1987 with most losses occurring in subtidal areas. Over the 13-yr study period, there was a 34% loss of submerged eelgrass (−457 ha) and a 13% (+136 ha) gain of intertidal eelgrass. Within the two types of intertidal eelgrass, the patchy cover class (<85% cover) expanded (+250 ha) and continuous cover class (≥85% cover) declined (−114 ha). Most eelgrass losses were likely the result of sediment loading and turbidity caused by a single flooding event in winter of 1992–1993. Recent large-scale agricultural development of adjacent uplands may have exacerbated the effects of the flood. Oyster farming was not associated with any detectable losses in eelgrass spatial extent, despite the increase in number of oyster racks from 57 to 484 over the study period.     

Thermochemistry of carbonate-pyroxene equilibria

The enthalpies of drop solution of calcite, magnesite, dolomite, wollastonite and diopside have been measured in a lead borate solvent at 977 K in a Calvettype microcalorimeter. The carbonate calorimetry was done under flowing gas atmosphere. Both natural and synthetic samples were used. From these calorimetric data, the enthalpies of several reactions of carbonate with quartz were calculated. The enthalpies of these reactions (kJ/mol) at 298 K are: calcite+quartzwollastonite+CO₂, 92.3±1.0; magnesite+quartzenstatite+CO₂, 82.9±2.8; dolomite+quartzdiopside+CO₂, 163.0±1.9. These values generally are in agreement with those calculated from Robie et al., Helgeson et al., Berman and Holland and Powell. The enthalpy of dolomite-quartz reaction overlaps marginally with those from Berman and Holland and Powell. The enthalpy of formation of dolomite from magnesite and calcite (-11.1±2.5 kJ/mol) was also derived from the measured enthalpies, and this value is consistent with that from acid solution calorimetric measurements as shown by Navrotsky and Capobianco, but different from values in the earlier literature. These results support the premise that drop-solution of carbonates into molten lead borate results in a well-defined final state consisting of dissolved oxide and evolved CO₂. This was also confirmed by weight change experiments. Thus, oxide melt calorimetry is applicable to carbonates.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Marine organic geochemistry of the Eastern Mediterranean: 1. Aliphatic and polyaromatic hydrocarbons in Cretan Sea surficial sediments

As part of a lipid biogeochemical study, aliphatic and polyaromatic hydrocarbons were determined in surficial sediments from the Cretan Sea (South Aegean Sea) in the Eastern Mediterranean. Total concentrations of both aliphatic (AHC) and polyaromatic (PAH) hydrocarbons were low (562–5697 and 14.6–158.5 ng/g, respectively) with respect to other coastal sediments worldwide and compare with concentrations found in open sea areas. The composition of AHC was dominated by unresolved complex mixture (UCM) indicating the presence of petroleum-related hydrocarbon inputs as confirmed by the detection of specific α,β-hopanes. PAH consisted mainly of pyrolytic four- to five-ring compounds. UCM and PAH amounts revealed that Cretan Sea receives low supply of anthropogenic material compared to NW Mediterranean. The spatial distributions of AHC and PAH indicated that urban run-off and transport from the continental self are the major input pathway of anthropogenic and biogenic hydrocarbons from terrestrial sources in the near shore area, whereas atmospheric transport might be the significant source of hydrocarbons in the deep area.