Edaphic influences on plant community adaptation in the Chiquibul forest of Belize

Edaphic variables figure significantly in plant community adaptations in tropical ecosystems but are often difficult to resolve because of the confounding influence of climate. Within the Chiquibul forest of Belize, large areas of Ultisols and Inceptisols occur juxtaposed within a larger zone of similar climate, permitting unambiguous assessment of edaphic contributions to forest composition. Wet chemical analyses, X-ray diffraction and X-ray fluorescence spectroscopy were employed to derive chemical (pH, exchangeable cations, CEC, total and organic C, total trace elements) and physical (texture, mineralogy) properties of four granite-derived Ustults from the Mountain Pine Ridge plateau and four limestone-derived Ustepts from the San Pastor region. The soils of these two regions support two distinct forests, each possessing a species composition reflecting the many contrasting physicochemical properties of the underlying soil. Within the Mountain Pine Ridge forest, species abundance and diversity is constrained by nutrient deficiencies and water-holding limitations imposed by the coarse textured, highly weathered Ultisols. As a consequence, the forest is highly adapted to seasonal drought, frequent fires and the significant input of atmospherically derived nutrients. The nutrient-rich Inceptisols of the San Pastor region, conversely, support an abundant and diverse evergreen forest, dominated by Sabal mauritiiformis, Cryosophila stauracantha and Manilkara spp. Moreover, the deep, fine textured soils in the depressions of the karstic San Pastor landscape collect and retain during the wet season much available water, thereby serving as refugia during particularly long periods of severe drought. To the extent that the soils of the Chiquibul region promote and maintain forest diversity, they also confer redundancy and resilience to these same forests and, to the broader ecosystem, of which they are a central part. (C) 2005 Elsevier B.V. All rights reserved.

Palladium-coated nickel nanoclusters: new Hiyama cross-coupling catalysts

The advantages of bimetallic nanoparticles as C - C coupling catalysts are discussed, and a simple, bottom- up synthesis method of core - shell Ni - Pd clusters is presented. This method combines electrochemical and 'wet chemical' techniques, and enables the preparation of highly monodispersed structured bimetallic nanoclusters. The double- anode electrochemical cell is described in detail. The core - shell Ni - Pd clusters were then applied as catalysts in the Hiyama cross- coupling reaction between phenyltrimethoxysilane and various haloaryls. Good product yields were obtained with a variety of iodo- and bromoaryls. We found that, for a fixed amount of Pd atoms, the core - shell clusters outperform both the monometallic Pd clusters and the alloy bimetallic Ni - Pd ones. THF is an excellent solvent for this process, with less than 2% homocoupling by-product. The roles of the stabiliser and the solvent are discussed.

Development of a methodology to investigate the importance of chemical speciation on the bioavailability of contaminants to Eisenia andrei

The uptake of metals by earthworms occurs predominantly via the soil pore water, or via an uptake route which is related to the soil pore water metal concentration. However, it has been suggested that the speciation of the metal is also important. A novel technique is described which exposes Eisenia andrei Bouche to contaminant bearing solutions in which the chemical factors affecting its speciation may be individually and systematically manipulated. In a preliminary experiment, the LC50 for copper nitrate was 0.046 mg l(-1) (95 % confidence intervals: 0.03 and 0.07 mg l(-1)). There was a significant positive correlation between earthworm mortality and bulk copper concentration in solution (R-2 = 0.88, P less than or equal to 0.001), and a significant positive increase in earthworm tissue copper concentration with increasing copper concentration in solution (R-2 = 0.97, P less than or equal to 0.001). It is anticipated that quantifying the effect of soil solution chemical speciation on copper bioavailability will provide an excellent aid to understanding the importance of chemical composition and the speciation of metals, in the calculation of toxicological parameters.

Time-resolved gas-phase kinetic and quantum chemical studies of reactions of silylene with chlorine-containing species. 1. HCl

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with HCL The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas, at five temperatures in the range of 296-611 K. The second-order rate constants fitted the Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-11.51 +/- 0.06) + (1.92 +/- 0.47 kJ mol(-1))/RTIn10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range of 10-100 Torr, but showed small decreases in value of no more than 20% ( +/- 10%) at I Toff, at both the highest and lowest temperatures. The data are consistent with formation of an initial weakly bound donor-acceptor complex, which reacts by two parallel pathways. The first is by chlorine-to-silicon H-shift to make vibrationally excited chlorosilane, SiH3Cl*, which yields HSiCl by H-2 elimination from silicon. In the second pathway, the complex proceeds via H-2 elimination (4-center process) to make chlorosilylene, HSiCl, directly. This interpretation is supported by ab initio quantum calculations carried out at the G3 level which reveal the direct H-2 elimination route for the first time. RRKM modeling predicts the approximate magnitude of the pressure effect but is unable to determine the proportions of each pathway. The experimental data agree with the only previous measurements at room temperature. Comparisons with other reactions of SiH2 are also drawn.

Chemical and aerosol characterisation of the troposphere over West Africa during the monsoon period as part of AMMA

During June, July and August 2006 five aircraft took part in a campaign over West Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detail in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of ozone-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the southern hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μg m−3 with a median concentration of 1.07 μg m−3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8 km (and only there). Very low concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs.

A step toward the wet surface chemistry of glycine and alanine on Cu{110}: destabilization and decomposition in the presence of near-ambient water vapor

The coadsorption of water with organic molecules under near-ambient pressure and temperature conditions opens up new reaction pathways on model catalyst surfaces that are not accessible in conventional ultrahigh-vacuum surfacescience experiments. The surface chemistry of glycine and alanine at the water-exposed Cu{110} interface was studied in situ using ambient-pressure photoemission and X-ray absorption spectroscopy techniques. At water pressures above 10-5 Torr a significant pressure-dependent decrease in the temperature for dissociative desorption was observed for both amino acids, accompanied by the appearance of a newCN intermediate, which is not observed for lower pressures. The most likely reaction mechanisms involve dehydrogenation induced by O and/or OH surface species resulting from the dissociative adsorption of water. The linear relationship between the inverse decomposition temperature and the logarithm of water pressure enables determination of the activation energy for the surface reaction, between 213 and 232 kJ/mol, and a prediction of the decomposition temperature at the solidliquid interface by extrapolating toward the equilibrium vapor pressure. Such experiments near the equilibrium vapor pressure provide important information about elementary surface processes at the solidliquid interface, which can be retrieved neither under ultrahigh vacuum conditions nor from interfaces immersed in a solution.