Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength (I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.     

A scenario based analysis of land competition between food and bioenergy production in the US

Greenhouse gas abatement policies will increase the demand for renewable sources of energy, including bioenergy. In combination with a global growing demand for food, this could lead to a food-fuel competition for bio-productive land. Proponents of bioenergy have suggested that energy crop plantations may be established on less productive land as a way of avoiding this potential food-fuel competition. However, many of these suggestions have been made without any underlying economic analysis. In this paper, we develop a long-term economic optimization model (LUCEA) of the U.S. agricultural and energy system to analyze this possible competition for land and to examine the link between carbon prices, the energy system dynamics and the effect of the land competition on food prices. Our results indicate that bioenergy plantations will be competitive on cropland already at carbon taxes about US $20/ton C. As the carbon tax increases, food prices more than double compared to the reference scenario in which there is no climate policy. Further, bioenergy plantations appropriate significant areas of both cropland and grazing land. In model runs where we have limited the amount of grazing land that can be used for bioenergy to what many analysts consider the upper limit, most of the bioenergy plantations are established on cropland. Under the assumption that more grazing land can be used, large areas of bioenergy plantations are established on grazing land, despite the fact that yields are assumed to be much lower (less than half) than on crop land. It should be noted that this allocation on grazing land takes place as a result of a competition between food and bioenergy production and not because of lack of it. The estimated increase in food prices is largely unaffected by how much grazing land can be used for bioenergy production.     

Downscaling projections of climate change in Sao Tome and Principe Islands,Africa

Sao Tome and Principe is a small insular African country extremely vulnerable to rising sea levels and impacts such as inundation, shore line change, and salt water intrusion into underground aquifers. Projections of climate change have considered coarse model resolutions. The objective of this work is to dynamically downscale the global model projections to 4-km resolution and to assess the climate change in the Sao Tome and Principe islands. The global climate projections are provided by the Canadian Earth System Model under two Representative Concentration Pathways greenhouse gas scenarios, RCP4.5 and RCP8.5. The downscaling is produced by the Eta regional climate model. The baseline period is taken between 1971 and 2000, and the future climate period is taken between 2041 and 2070. The 2-m temperature simulations show good agreement with station data. The model simulates temperature more accurately than precipitation. The precipitation simulations systematically show underestimation and delay of the rainy and the dry seasons by about 1 month, a feature inherited from the global climate model. In the middle of the 21st century, projections show the strongest warming in the elevated parts of the Sao Tome Island, especially in February under RCP8.5. Warmer nights and warmer days become more frequent in the islands when compared with those in the present. While under RCP4.5, precipitation increases in the islands; under RCP8.5, it decreases everywhere in both islands. Heavy precipitation rates should increase, especially in the south-southwestern parts of the Sao Tome islands. Detailed spatial variability of the temperature and precipitation changes in the islands can only be revealed at very high spatial model resolution. Implications for the potential energy production from two major river basins are assessed in this work.