Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

The influence of the coast on the dynamics of upwelling fronts: Part II. Numerical simulations

We investigated the dynamics of upwelling fronts near a coast. This work was first motivated by laboratory experiments [Bouruet-Aubertot, Linden, Dyn. Atmos. Oceans, 2002] in which the front is produced by the adjustment of a buoyant fluid initially confined within a bottomless cylinder. It was shown that cyclonic eddies consisting of coastal waters are enhanced when the front is unstable near the coast (the outer vertical boundary). The purpose of this paper is to provide further insights into this process. We reproduced the experimental configuration using a three-dimensional model of the primitive equations. We first show that for coastal fronts more potential energy, in terms of the maximum available potential energy, is released than for open-ocean fronts. Therefore, waves of larger amplitude are generated during the adjustment and the mean flow that establishes has a higher kinetic energy in the former case. Then as baroclinic instability starts and wave crests reach the boundary, cyclonic eddies are enhanced as in the laboratory experiments and in a similar way. However, in contrast to the laboratory experiments, offshore advection of cyclonic eddies can occur in two stages, depending on the spatial organization of the baroclinic wave. When the baroclinic wave consists of the sum of different modes and is thus highly asymmetric, the offshore advection of cyclonic eddies occurs just after their enhancement at the boundary, as in the laboratory experiments. By contrast, when a single-mode baroclinic wave develops, neighboring cyclonic eddies first merge before being advected offshore. Very different behavior is observed for open-ocean fronts. First a mixed baroclinic–barotropic instability grows. Then the eddies transfer their energy to the mean flow and the barotropic and baroclinic instabilities start again. An excellent agreement is obtained with the main result obtained in the laboratory experiments: the ratio between growth rates of surface cyclonic and anticyclonic vorticity increases as the instability develops nearer to the coast.     

Resilience and seismic risk perception at school: a geoethical experiment in Aiello Calabro,southern Italy

The last few years have seen the debate on the geoethics of environmental and climatic protection growing to include resilience as a central idea within this new discipline, which holds many similarities with geography. Resilience analysis often looks at the capacity to re-establish conditions of equilibrium within a system which has been hit by a serious shock, e.g. a natural or man-made disaster. Geoethics works, in tandem with geological analyses and the geography of risk, to inform a population and develop integrated risk management in such a way as to strengthen a community’s resilience. The aim of this work is to study some people’s capacity to overcome what was potentially a disastrous event and, through a process of reconstruction, turn it into an occasion for growth. The experiment, carried out in the primary and middle schools in Aiello Calabro (Calabria, southern Italy), was conducted on the basis of the belief that there is a close relationship between a population’s having a realistic understanding of the risk of such an event, e.g. an earthquake, and high levels of resilience. We also tried to gain an insight into the relationship that may exist between resilience in primary and secondary school children and methods of coping which give an appropriate management of seismic risk. To be more precise, we try to discover whether there is a link between good/appropriate resilience and good/appropriate risk management.

     

Estuarine Habitat and Demographic Factors Affect Juvenile Chinook (<Emphasis Type="Italic">Oncorhynchus tshawytscha</Emphasis>) Growth Variability in a Large Freshwater Tidal Estuary

Estuarine rearing has been shown to enhance within watershed biocomplexity and support growth and survival for juvenile salmon (Oncorhynchus sp.). However, less is known about how growth varies across different types of wetland habitats and what explains this variability in growth. We focused on the estuarine habitat use of Columbia River Chinook salmon (Oncorhynchus tshawytscha), which are listed under the Endangered Species Act. We employed a generalized linear model (GLM) to test three hypotheses: (1) juvenile Chinook growth was best explained by temporal factors, (2) habitat, or (3) demographic characteristics, such as stock of origin. This study examined estuarine growth rate, incorporating otolith microstructure, individual assignment to stock of origin, GIS habitat mapping, and diet composition along ~130 km of the upper Columbia River estuary. Juvenile Chinook grew on average 0.23 mm/day in the freshwater tidal estuary. When compared to other studies in the basin our growth estimates from the freshwater tidal estuary were similar to estimates in the brackish estuary, but ~4 times slower than those in the plume and upstream reservoirs. However, previous survival studies elucidated a possible tradeoff between growth and survival in the Columbia River basin. Our GLM analysis found that variation in growth was best explained by habitat and an interaction between fork length and month of capture. Juvenile Chinook salmon captured in backwater channel habitats and later in the summer (mid-summer and late summer/fall subyearlings) grew faster than salmon from other habitats and time periods. These findings present a unique example of the complexity of understanding the influences of the many processes that generate variation in growth rate for juvenile anadromous fish inhabiting estuaries.     

Time Transfer for TAI Using a Geodetic Receiver: An Example with the Ashtech ZXII-T

The International Atomic Time scale (TAI) is computed by the Bureau International des Poids et Mesures (BIPM) from a set of atomic clocks distributed in about 40 time laboratories around the world. The time transfer between these remote clocks is mostly performed by the so-called GPS common view method: The clocks are connected to a GPS time receiver whose internal software computes the offsets between the remote clocks and GPS time. These data are collected in a standard formal called CCTF. In the present study we develop both the procedure and the software tool that allows us to generate the CCTF files needed for time transfer to TAI, using RINEX files produced by geodetic receivers driven by an external frequency. The CCTF files are then generated from the RINEX observation files. The software is freely available at ftp://omaftp.oma.be/dist/astro/time/RINEX_CCTF. Applied to IGS (International GPS Service) receivers, this procedure will provide a direct link between TAI and the IGS clock combination. We demonstrate here the procedure using the RINEX files from the Ashtech Metronome (ZXII-T) GPS receiver, to which we apply the conventional analysis to compute the CCTF data. We compared these results with the CCTF files produced by a time receiver R100-30T from 3S-Navigation. We also used this comparison with the results of a calibrated time receiver to determine the hardware delay of the geodetic receiver. ? 2001 John Wiley & Sons, Inc.     

A Measurement of Omega from the North American Test Flight of Boomerang

We use the angular power spectrum of the cosmic microwave background, measured during the North American test flight of the Boomerang experiment, to constrain the geometry of the universe. Within the class of cold dark matter models, we find that the overall fractional energy density of the universe Omega is constrained to be 0.85相似文献   

The LMDZ4 general circulation model: climate performance and sensitivity to parametrized physics with emphasis on tropical convection

The LMDZ4 general circulation model is the atmospheric component of the IPSL–CM4 coupled model which has been used to perform climate change simulations for the 4th IPCC assessment report. The main aspects of the model climatology (forced by observed sea surface temperature) are documented here, as well as the major improvements with respect to the previous versions, which mainly come form the parametrization of tropical convection. A methodology is proposed to help analyse the sensitivity of the tropical Hadley–Walker circulation to the parametrization of cumulus convection and clouds. The tropical circulation is characterized using scalar potentials associated with the horizontal wind and horizontal transport of geopotential (the Laplacian of which is proportional to the total vertical momentum in the atmospheric column). The effect of parametrized physics is analysed in a regime sorted framework using the vertical velocity at 500 hPa as a proxy for large scale vertical motion. Compared to Tiedtke’s convection scheme, used in previous versions, the Emanuel’s scheme improves the representation of the Hadley–Walker circulation, with a relatively stronger and deeper large scale vertical ascent over tropical continents, and suppresses the marked patterns of concentrated rainfall over oceans. Thanks to the regime sorted analyses, these differences are attributed to intrinsic differences in the vertical distribution of convective heating, and to the lack of self-inhibition by precipitating downdraughts in Tiedtke’s parametrization. Both the convection and cloud schemes are shown to control the relative importance of large scale convection over land and ocean, an important point for the behaviour of the coupled model.     

Impact of different convective cloud schemes on the simulation of the tropical seasonal cycle in a coupled ocean–atmosphere model

The simulation of the mean seasonal cycle of sea surface temperature (SST) remains a challenge for coupled ocean–atmosphere general circulation models (OAGCMs). Here we investigate how the numerical representation of clouds and convection affects the simulation of the seasonal variations of tropical SST. For this purpose, we compare simulations performed with two versions of the same OAGCM differing only by their convection and cloud schemes. Most of the atmospheric temperature and precipitation differences between the two simulations reflect differences found in atmosphere-alone simulations. They affect the ocean interior down to 1,000 m. Substantial differences are found between the two coupled simulations in the seasonal march of the Intertropical Convergence Zone in the eastern part of the Pacific and Atlantic basins, where the equatorial upwelling develops. The results confirm that the distribution of atmospheric convection between ocean and land during the American and African boreal summer monsoons plays a key role in maintaining a cross equatorial flow and a strong windstress along the equator, and thereby the equatorial upwelling. Feedbacks between convection, large-scale circulation, SST and clouds are highlighted from the differences between the two simulations. In one case, these feedbacks maintain the ITCZ in a quite realistic position, whereas in the other case the ITCZ is located too far south close to the equator.