Potentiometric and F nuclear magnetic resonance spectroscopic study of fluoride substitution in the GaAl12 polyoxocation: implications for aluminum (hydr)oxide mineral surfaces

Fluoride replacement of oxygens in the GaO₄Al₁₂(OH)₂₄(H₂O)127+(aq) molecule [GaAl₁₂] was studied via ¹⁹F nuclear magnetic resonance (NMR) at 4 < pH < 5 and 278 K in order to elucidate similar reactions at the surfaces of clays. Peaks are identified in the ¹⁹F-NMR spectra that correspond to both terminal and bridging fluorides on the GaAl₁₂ molecule, with relative peak positions similar to those previously identified in fluoridated aluminum (hydr)oxide mineral surfaces (Nordin, J. P., Sullivan, D. J., Phillips, B. L., and Casey, W. H. [1999], “Mechanisms for fluoride-promoted dissolution of bayerite [β-Al(OH)₃(s)] and boehmite [γ-AlOOH(s)]-¹⁹F-NMR spectroscopy and aqueous surface chemistry,” Geochim. Cosmochim. Acta63, 3513-3524). Fluoride substitutes for oxygen at three different sites in the GaAl₁₂ molecule, but at dramatically different rates.The kinetics of fluoride substitution follow a rate law that includes parallel and reversible transfer of fluoride from nonbridging sites to the two bridging sites. The essential features of the rate law are as follows: (1) fluoride replaces bound water molecules (η-OH₂) within minutes at 278 K at rates that are quantitatively similar to fluoride uptake by Al(H₂O)63+(aq) to form AlF²⁺(aq) at similar conditions; (2) fluoride substitutes onto the two topologically distinct μ₂-OH sites at different rates, as was previously observed for oxygen exchange, but here, the reaction is complete in hours to days at 278 K. Most importantly, rates of fluoride substitution onto μ₂-OH sites are 10² times more rapid than the corresponding rates of oxygen exchange with bulk waters, indicating that fluoride considerably labilizes the molecule, as is also observed at the surfaces of minerals. The largest cause of this labilization is the reduced molecular charge on the GaAl₁₂ upon replacement of bound waters by fluoride, which for mineral surfaces corresponds to a reduction in surface charge density.     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

An efficient climate model with a 3D ocean and statistical–dynamical atmosphere*

We describe a coupled climate model of intermediate complexity designed for use in global warming experiments. The atmospheric component is a two-dimensional (zonally averaged) statistical-dynamical model based on the Goddard Institute for Space Study's atmospheric general circulation model (GCM). In contrast with energy-balance models used in some climate models of intermediate complexity, this model includes full representation of the hydrological and momentum cycles. It also has parameterizations of the main physical processes, including a sophisticated radiation code. The ocean component is a coarse resolution ocean GCM with simplified global geometry based on the Geophysical Fluid Dynamics Laboratory modular ocean model. Because of the simplified geometry the resolution in the western boundary layers can be readily increased compared to conventional coarse resolution models, without increasing the model's computational requirements in a significant way. The ocean model's efficiency is also greatly increased by using a moderate degree of asynchronous coupling between the oceanic momentum and tracer fields. We demonstrate that this still allows an accurate simulation of transient behavior, including the seasonal cycle. A 100 years simulation with the model requires less than 8 hours on a state-of the art workstation. The main novelty of the model is therefore a combination of computational efficiency, statistical-dynamical atmosphere and 3D ocean. Long-term present-day climate simulations are carried out using the coupled model with and without flux adjustments, and with either the Gent-McWilliams (GM) parametrization scheme or horizontal diffusion (HD) in the ocean. Deep ocean temperatures systematically decrease in the runs without flux adjustment. We demonstrate that the mismatch between heat transports in the uncoupled states of two models is the main cause for the systematic drift. In addition, changes in the circulation and sea-ice formation also contribute to the drift. Flux adjustments in the freshwater fluxes are shown to have a stabilizing effect on the thermohaline circulation in the model, whereas the adjustments in the heat fluxes tend to weaken the global "conveyor". To evaluate the model's response to transient external forcing global warming simulations are also carried out with the flux-adjusted version of the coupled model. The coupled model reproduces reasonably well the behavior of more sophisticated coupled GCMs for both current climate and for the global warming scenarios.     

The influence of diet on comparative trace metal cadmium,copper and zinc accumulation in Thais clavigera (Gastropoda: Muricidae) preying on intertidal barnacles or mussels

The influence of diet on comparative metal accumulation was investigated using a predatory muricid gastropod Thais clavigera. Individuals were fed for up to 56 days on either barnacles, i.e., Tetraclita squamosa, or mussels, i.e., Perna viridis, collected from metal-contaminated and clean sites. Barnacles and mussels have contrasting metal handling strategies and, therefore, different body concentrations, intracellular distributions and detoxification systems. Field collection of prey items that accumulated body metal concentrations over a lifetime of exposure allowed bioavailability to the predator, T. clavigera, to be assessed naturally, which may not be the case for prey exposed to metals for a short time in the laboratory. T. clavigera that was fed cadmium- and copper-contaminated barnacles or mussels ingested significantly greater amounts compared to those fed conspecifics collected from clean locations. T. clavigera body cadmium and copper concentrations were not, however, significantly different between individuals fed either contaminated or clean prey. Amount of zinc ingested was similar in mussels collected from clean and contaminated environments but much less when compared to the barnacle prey. The body concentrations of zinc in T. clavigera fed mussels collected from both sites fell. In contrast, the amount of zinc ingested from barnacle prey was significantly greater from those collected from the metal-contaminated site as compared to the clean one. This was reflected as significantly greater body zinc concentrations in T. clavigera fed contaminated barnacles compared to those fed clean individuals. Copper and zinc accumulation from prey was, therefore, complex. It varied between metal and between prey type, but appeared to be related to the amount ingested and the metal handling strategy of the prey.     

Wide-Field Camera for Gravitational Microlensing Survey: MOA-cam2

We have constructed a large, mosaic CCD camera called MOA-cam2 which has 4096 × 6144-pixelsto search for gravitational microlensing events. MOA-cam2 has three4096 × 2048-pixel SITe CCD chips, which have a very high quantum efficiency (nearly 80% in the wave region 500 to 800 nm),and three buttable sides. We have placed the threechips side by side with 100 m dead space. MOA-cam2 has been installed on the 61 cm Boller and Chivens telescope of the MOA collaboration at the Mt. John University Observatory (MJUO) in NewZealand since July 1998. The field coverage is 0.92° × 1.38° per exposure. The technical details of MOA-cam2 and the first images obtained with the Boller and Chivens telescope are presented. MOA-cam2 introduces a second phase of research on gravitational microlensing by the MOA collaboration.     

The Consistency of IPCC's SRES Scenarios to 1990–2000 Trends and Recent Projections

The greenhouse gas emissions scenarios published by the IPCC in the Special Report on Emission Scenarios (SRES) continue to serve as a primary basis for assessing future climate change and possible response strategies. These scenarios were developed between 1996 and 1999 and sufficient time has now passed to make it worth examining their consistency with more recent data and projections. The comparison performed in this paper includes population, GDP, energy use, and emissions of CO₂, non-CO₂ gases and sulfur. We find the SRES scenarios to be largely consistent with historical data for the 1990–2000 period and with recent projections. Exceptions to this general observation include (1) in the long-term, relatively high population growth assumptions; in some regions, particularly in the A2 scenario; (2) in the medium-term, relatively high economic growth assumptions in the LAM (Latin America, Africa and Middle East) region in the A1 scenario; (3) in the short-term, CO₂ emissions projections in A1 that are somewhat higher than the range of current scenarios; and (4) substantially higher sulfur emissions in some scenarios than in historical data and recent projections. In conclusion, given the relatively small inconsistencies for use as global scenarios there seems to be no immediate need for a large-scale IPCC-led update of the SRES scenarios that is solely based on the SRES scenario performance vis-a-vis data for the 1990–2000 period and/or more recent projections. Based on reported findings, individual research teams could make, and in some cases already have made, useful updates of the scenarios.     

Mistreatment of the economic impacts of extreme events in the Stern Review Report on the Economics of Climate Change

The Stern Review on the Economics of Climate Change has focused debate on the costs and benefits of alternative courses of action on climate change. This refocusing has helped to move debate away from science of the climate system and on to issues of policy. However, a careful examination of the Stern Review's treatment of the economics of extreme events in developed countries, such as floods and tropical cyclones, shows that the report is selective in its presentation of relevant impact studies and repeats a common error in impacts studies by confusing sensitivity analyses with projections of future impacts. The Stern Review's treatment of extreme events is misleading because it overestimates the future costs of extreme weather events in developed countries by an order of magnitude. Because the Stern Report extends these findings globally, the overestimate propagates through the report's estimate of future global losses. When extreme events are viewed more comprehensively the resulting perspective can be used to expand the scope of choice available to decision makers seeking to grapple with future disasters in the context of climate change. In particular, a more comprehensive analysis underscores the importance of adaptation in any comprehensive portfolio of responses to climate change.