Surface and interstitial Ti diffusion at the rutile TiO2(110) surface

Diffusion of Ti through the TiO2 (110) rutile surface plays a key role in the growth and reactivity of TiO2. To understand the fundamental aspects of this important process, we present an analysis of the diffusion of Ti adspecies at the stoichiometric TiO2(110) surface using complementary computational methodologies of density functional theory corrected for on-site Coulomb interactions (DFT+U) and a charge equilibration (QEq) atomistic potential to identify minimum energy pathways. We find that diffusion of Ti from the surface to subsurface (and vice versa) follows an intersticialcy exchange mechanism, involving exchange of surface Ti with the 6-fold coordinated Ti below the bridging oxygen rows. Diffusion in the subsurface between layers also follows an interstitialcy mechanism. The diffusion of Ti is discussed in light of continued attempts to understand the re-oxidation of non-stoichiometric TiO2(110) surfaces.

Analysis of diffusion tensor magnetic resonance imaging data using principal component analysis

An analysis method for diffusion tensor (DT) magnetic resonance imaging data is described, which, contrary to the standard method (multivariate fitting), does not require a specific functional model for diffusion-weighted (DW) signals. The method uses principal component analysis (PCA) under the assumption of a single fibre per pixel. PCA and the standard method were compared using simulations and human brain data. The two methods were equivalent in determining fibre orientation. PCA-derived fractional anisotropy and DT relative anisotropy had similar signal-to-noise ratio (SNR) and dependence on fibre shape. PCA-derived mean diffusivity had similar SNR to the respective DT scalar, and it depended on fibre anisotropy. Appropriate scaling of the PCA measures resulted in very good agreement between PCA and DT maps. In conclusion, the assumption of a specific functional model for DW signals is not necessary for characterization of anisotropic diffusion in a single fibre.

A traceable physical calibration of the vertical advection-diffusion equation for modelling ocean heat uptake

The classic vertical advection-diffusion (VAD) balance is a central concept in studying the ocean heat budget, in particular in simple climate models (SCMs). Here we present a new framework to calibrate the parameters of the VAD equation to the vertical ocean heat balance of two fully-coupled climate models that is traceable to the models’ circulation as well as to vertical mixing and diffusion processes. Based on temperature diagnostics, we derive an effective vertical velocity w∗ and turbulent diffusivity k∗ for each individual physical process. In steady-state, we find that the residual vertical velocity and diffusivity change sign in mid-depth, highlighting the different regional contributions of isopycnal and diapycnal diffusion in balancing the models’ residual advection and vertical mixing. We quantify the impacts of the time-evolution of the effective quantities under a transient 1%CO2 simulation and make the link to the parameters of currently employed SCMs.

DIFFUSION OF MAGNETIC FIELD AND REMOVAL OF MAGNETIC FLUX FROM CLOUDS VIA TURBULENT RECONNECTION

The diffusion of astrophysical magnetic fields in conducting fluids in the presence of turbulence depends on whether magnetic fields can change their topology via reconnection in highly conducting media. Recent progress in understanding fast magnetic reconnection in the presence of turbulence reassures that the magnetic field behavior in computer simulations and turbulent astrophysical environments is similar, as far as magnetic reconnection is concerned. This makes it meaningful to perform MHD simulations of turbulent flows in order to understand the diffusion of magnetic field in astrophysical environments. Our studies of magnetic field diffusion in turbulent medium reveal interesting new phenomena. First of all, our three-dimensional MHD simulations initiated with anti-correlating magnetic field and gaseous density exhibit at later times a de-correlation of the magnetic field and density, which corresponds well to the observations of the interstellar media. While earlier studies stressed the role of either ambipolar diffusion or time-dependent turbulent fluctuations for de-correlating magnetic field and density, we get the effect of permanent de-correlation with one fluid code, i.e., without invoking ambipolar diffusion. In addition, in the presence of gravity and turbulence, our three-dimensional simulations show the decrease of the magnetic flux-to-mass ratio as the gaseous density at the center of the gravitational potential increases. We observe this effect both in the situations when we start with equilibrium distributions of gas and magnetic field and when we follow the evolution of collapsing dynamically unstable configurations. Thus, the process of turbulent magnetic field removal should be applicable both to quasi-static subcritical molecular clouds and cores and violently collapsing supercritical entities. The increase of the gravitational potential as well as the magnetization of the gas increases the segregation of the mass and magnetic flux in the saturated final state of the simulations, supporting the notion that the reconnection-enabled diffusivity relaxes the magnetic field + gas system in the gravitational field to its minimal energy state. This effect is expected to play an important role in star formation, from its initial stages of concentrating interstellar gas to the final stages of the accretion to the forming protostar. In addition, we benchmark our codes by studying the heat transfer in magnetized compressible fluids and confirm the high rates of turbulent advection of heat obtained in an earlier study.

Seismic activity triggered by water wells in the Parana Basin, Brazil

Triggered seismicity is commonly associated with deep water reservoirs or injection wells where water is injected at high pressure into the reservoir rock. However, earth tremors related solely to the opening of groundwater wells are extremely rare. Here we present a clear case of seismicity induced by pore-pressure changes following the drilling of water wells that exploit a confined aquifer in the intracratonic Parana Basin of southeastern Brazil. Since 2004, shallow seismic activity, with magnitudes up to 2.9 and intensities V MM, has been observed near deep wells (120-200 m) that were drilled in early 2003 near the town of Bebedouro. The wells were drilled for irrigation purposes, cross a sandstone layer about 60-80 m thick and extract water from a confined aquifer in fractured zones between basalt flow layers. Seismic activity, mainly event swarms, has occurred yearly since 2004, mostly during the rainy season when the wells are not pumped. During the dry season when the wells are pumped almost continuously, the activity is very low. A seismographic network, installed in March 2005, has located more than 2000 microearthquakes. The events are less than 1 km deep (mostly within the 0.5 km thick basalt layer) and cover an area roughly 1.5 km x 5 km across. The seismicity generally starts in a small area and expands to larger distances with an equivalent hydraulic diffusivity ranging from 0.06 to 0.6 m(2)/s. Geophysical and geothermal logging of several wells in the area showed that water from the shallow sandstone aquifer enters the well at the top and usually forms waterfalls. The waterfalls flow down the sides of the wells and feed the confined, fractured aquifer in the basalt layer at the bottom. Two seismic areas are observed: the main area surrounds several wells that are pumped continuously during the dry season, and a second area near another well (about 10 km from the first area) that is not used for irrigation and not pumped regularly. The main area displays cyclic annual activity, but the second area does not. We explain the earthquake swarms as being triggered by pore pressure diffusion in the fractured basalt layer due to additional pressure from the newly connected surface aquifer. This reaches critically prestressed areas up to a few kilometers away from the wells. During periods of continuous pumping, the reduction of pore pressure in the confined aquifer stops the seismic activity. Our study suggests that this kind of activity may be more common than previously thought and implies that many other cases of small tremors associated with the drilling of water wells may have gone unnoticed.

CHARGED PARTICLE DYNAMICS IN TIME DEPENDENT MAGNETIC FIELDS

In this work we study the behavior of charged particles immersed in a peculiar configuration of magnetic fields, which has a main constant field B(0) and a superimposed, transversal perturbation field B(1) sin(omega(p)t), with B(1) << B(0). By taking Cartesian coordinates and placing B(0) along the z axis and B(1) sin (omega(p)t) on the x axis, an analytical solution for y(t) may be obtained by solving an integrodifferential equation. Besides, the solution z(t) also exhibits a very interesting dynamics, and the entire system is conditioned by resonances between the particle orbit frequencies and the frequency of the magnetic transversal perturbation, omega(p). In this work we also discuss numerical simulations for the related particle trajectories, as well as potential applications in the context of separation phenomena.

Configuration-Dependent Diffusion Dynamics of Downhill and Two-State Protein Folding

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The aggregation process in tetraethoxysilane-derived sonogels as an analogy to the critical phenomenon

The structural evolution in silica sols prepared from tetraethoxysilane (TEOS) sonohydrolysis was studied 'in situ' using small-angle x-ray scattering (SAXS). The structure of the gelling system can be reasonably well described by a correlation function given by gamma(r) similar to (1/R(2))(1/r) exp(- r/xi), where xi is the structure correlation length and R is a chain persistence length, as an analogy to the Ornstein-Zernike theory in describing critical phenomenon. This approach is also expected for the scattering from some linear and branched molecules as polydisperse coils of linear chains and random f-functional branched polycondensates. The characteristic length. grows following an approximate power law with time t as xi similar to t(1) (with the exponent quite close to 1) while R remains undetermined but with a constant value, except at the beginning of the process in which the growth of. is slower and R increases by only about 15% with respect to the value of the initial sol. The structural evolution with time is compatible with an aggregation process by a phase separation by coarsening. The mechanism of growth seems to be faster than those typically observed for pure diffusion controlled cluster-cluster aggregation. This suggests that physical forces (hydrothermal forces) could be actuating together with diffusion in the gelling process of this system. The data apparently do not support a spinodal decomposition mechanism, at least when starting from the initial stable acid sol studied here.

SAXS measurements of the porosity in Cu(II)-doped SnO2 xerogels during crystallization

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The significance of root growth on cotton nutrition in an acidic low-P soil

Toxic levels of Al and low availability of Ca have been shown to decrease root growth, which can also be affected by P availability. In the current experiment, initial plant growth and nutrition of cotton (Gossypium hirsutum var. Latifolia) were studied as related to its root growth in response to phosphorus and lime application. The experiment was conducted in Botucatu, Sao Paulo, Brazil, in pots containing a Dark Red Latosol (Acrortox, 20% clay, 72% sand). Lime was applied at 0.56, 1.12 and 1.68 g kg -1 and phosphorus was applied at 50, 100 and 150 mg kg -1. Two cotton (cv. IAC 22) plants were grown per pot for up to 42 days after plant emergence. There was no effect of liming on shoot dry weight, root dry matter yield, root surface and length, but root diameter was decreased with the increase in soil Ca. Shoot dry weight, as well as root length, surface and dry weight were increased with soil P levels up to 83 mg kg -1. Phosphorus concentration in the shoots was increased from 1.6 to 3.0 g kg -1 when soil P was increased from 14 to 34 mg kg -1. No further increases in P concentration were observed with higher P rates. The shoot/root ratio was also increased with P application as well as the amount of nutrients absorbed per unit of root surface. In low soil P soils the transport of the nutrient to the cotton root surface limits P uptake. In this case an increase in root growth rate due to P fertilisation does not compensate for the low P diffusion in the soil.

Electrochemical determination of antimalarial drug amodiaquine in maternal milk using a hemin-based electrode

Voltammetric analysis of amodiaquine using a hemin biosensor revealed a well-defined peak at 0.14 V (vs. Ag/AgCl), corresponding to the oxidation of amodiaquine at pH 7.0. The electrodic behavior indicated that the oxidation process was irreversible, and that it was controlled by diffusion. In addition to advantages such as high selectivity and sensitivity, the method developed could be used for the analysis of breast milk containing amodiaquine without any need for prior sample treatment, an important consideration in routine analysis laboratories. Measurements of the drug contained in breast milk were used to validate the technique. The detection limit for standard solutions was 3.30 mg L-1, and the quantification limit was 11.0 mg L-1. ©The Electrochemical Society.

Effective tooth-bleaching protocols capable of reducing H2O2 diffusion through enamel and dentine

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A theoretical characterization of scaling properties in a bouncing ball system

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Chemistry and Chemical Education Through Text and Image: Analysis of Twentieth Century Textbooks Used in Brazilian Context

Assuming that textbooks give literary expression to cultural and ideological values of a nation or group, we propose the analysis of chemistry textbooks used in Brazilian universities throughout the twentieth century. We analyzed iconographic and textual aspects of 31 textbooks which had significant diffusion in the context of Brazilian universities at that period. As a result of the iconographic analysis, nine categories of images were proposed: (1) laboratory and experimentation, (2) industry and production, (3) graphs and diagrams, (4) illustrations related to daily life, (5) models, (6) illustrations related to the history of science, (7) pictures or diagrams of animal, vegetable or mineral samples, (8) analogies and (9) concepts of physics. The distribution of images among the categories showed a different emphasis in the presentation of chemical content due to a commitment to different conceptions of chemistry over the period. So, we started with chemistry as an experimental science in the early twentieth century, with an emphasis change to the principles of chemistry from the 1950s, culminating in a chemistry of undeniable technological influence. Results showed that reflections not only on the history of science, but on the history of science education, may be useful for the improvement of science education.

Bioremediation of PAHs - Limitations and soultions

Introduction 1.1 Occurrence of polycyclic aromatic hydrocarbons (PAH) in the environment Worldwide industrial and agricultural developments have released a large number of natural and synthetic hazardous compounds into the environment due to careless waste disposal, illegal waste dumping and accidental spills. As a result, there are numerous sites in the world that require cleanup of soils and groundwater. Polycyclic aromatic hydrocarbons (PAHs) are one of the major groups of these contaminants (Da Silva et al., 2003). PAHs constitute a diverse class of organic compounds consisting of two or more aromatic rings with various structural configurations (Prabhu and Phale, 2003). Being a derivative of benzene, PAHs are thermodynamically stable. In addition, these chemicals tend to adhere to particle surfaces, such as soils, because of their low water solubility and strong hydrophobicity, and this results in greater persistence under natural conditions. This persistence coupled with their potential carcinogenicity makes PAHs problematic environmental contaminants (Cerniglia, 1992; Sutherland, 1992). PAHs are widely found in high concentrations at many industrial sites, particularly those associated with petroleum, gas production and wood preserving industries (Wilson and Jones, 1993). 1.2 Remediation technologies Conventional techniques used for the remediation of soil polluted with organic contaminants include excavation of the contaminated soil and disposal to a landfill or capping - containment - of the contaminated areas of a site. These methods have some drawbacks. The first method simply moves the contamination elsewhere and may create significant risks in the excavation, handling and transport of hazardous material. Additionally, it is very difficult and increasingly expensive to find new landfill sites for the final disposal of the material. The cap and containment method is only an interim solution since the contamination remains on site, requiring monitoring and maintenance of the isolation barriers long into the future, with all the associated costs and potential liability. A better approach than these traditional methods is to completely destroy the pollutants, if possible, or transform them into harmless substances. Some technologies that have been used are high-temperature incineration and various types of chemical decomposition (for example, base-catalyzed dechlorination, UV oxidation). However, these methods have significant disadvantages, principally their technological complexity, high cost , and the lack of public acceptance. Bioremediation, on the contrast, is a promising option for the complete removal and destruction of contaminants. 1.3 Bioremediation of PAH contaminated soil & groundwater Bioremediation is the use of living organisms, primarily microorganisms, to degrade or detoxify hazardous wastes into harmless substances such as carbon dioxide, water and cell biomass Most PAHs are biodegradable unter natural conditions (Da Silva et al., 2003; Meysami and Baheri, 2003) and bioremediation for cleanup of PAH wastes has been extensively studied at both laboratory and commercial levels- It has been implemented at a number of contaminated sites, including the cleanup of the Exxon Valdez oil spill in Prince William Sound, Alaska in 1989, the Mega Borg spill off the Texas coast in 1990 and the Burgan Oil Field, Kuwait in 1994 (Purwaningsih, 2002). Different strategies for PAH bioremediation, such as in situ , ex situ or on site bioremediation were developed in recent years. In situ bioremediation is a technique that is applied to soil and groundwater at the site without removing the contaminated soil or groundwater, based on the provision of optimum conditions for microbiological contaminant breakdown.. Ex situ bioremediation of PAHs, on the other hand, is a technique applied to soil and groundwater which has been removed from the site via excavation (soil) or pumping (water). Hazardous contaminants are converted in controlled bioreactors into harmless compounds in an efficient manner. 1.4 Bioavailability of PAH in the subsurface Frequently, PAH contamination in the environment is occurs as contaminants that are sorbed onto soilparticles rather than in phase (NAPL, non aqueous phase liquids). It is known that the biodegradation rate of most PAHs sorbed onto soil is far lower than rates measured in solution cultures of microorganisms with pure solid pollutants (Alexander and Scow, 1989; Hamaker, 1972). It is generally believed that only that fraction of PAHs dissolved in the solution can be metabolized by microorganisms in soil. The amount of contaminant that can be readily taken up and degraded by microorganisms is defined as bioavailability (Bosma et al., 1997; Maier, 2000). Two phenomena have been suggested to cause the low bioavailability of PAHs in soil (Danielsson, 2000). The first one is strong adsorption of the contaminants to the soil constituents which then leads to very slow release rates of contaminants to the aqueous phase. Sorption is often well correlated with soil organic matter content (Means, 1980) and significantly reduces biodegradation (Manilal and Alexander, 1991). The second phenomenon is slow mass transfer of pollutants, such as pore diffusion in the soil aggregates or diffusion in the organic matter in the soil. The complex set of these physical, chemical and biological processes is schematically illustrated in Figure 1. As shown in Figure 1, biodegradation processes are taking place in the soil solution while diffusion processes occur in the narrow pores in and between soil aggregates (Danielsson, 2000). Seemingly contradictory studies can be found in the literature that indicate the rate and final extent of metabolism may be either lower or higher for sorbed PAHs by soil than those for pure PAHs (Van Loosdrecht et al., 1990). These contrasting results demonstrate that the bioavailability of organic contaminants sorbed onto soil is far from being well understood. Besides bioavailability, there are several other factors influencing the rate and extent of biodegradation of PAHs in soil including microbial population characteristics, physical and chemical properties of PAHs and environmental factors (temperature, moisture, pH, degree of contamination). Figure 1: Schematic diagram showing possible rate-limiting processes during bioremediation of hydrophobic organic contaminants in a contaminated soil-water system (not to scale) (Danielsson, 2000). 1.5 Increasing the bioavailability of PAH in soil Attempts to improve the biodegradation of PAHs in soil by increasing their bioavailability include the use of surfactants , solvents or solubility enhancers.. However, introduction of synthetic surfactant may result in the addition of one more pollutant. (Wang and Brusseau, 1993).A study conducted by Mulder et al. showed that the introduction of hydropropyl-ß-cyclodextrin (HPCD), a well-known PAH solubility enhancer, significantly increased the solubilization of PAHs although it did not improve the biodegradation rate of PAHs (Mulder et al., 1998), indicating that further research is required in order to develop a feasible and efficient remediation method. Enhancing the extent of PAHs mass transfer from the soil phase to the liquid might prove an efficient and environmentally low-risk alternative way of addressing the problem of slow PAH biodegradation in soil.