Deep chlorophyll maximum and upper ocean structure interactions: Case of the Guinea Thermal Dome

Deep Chlorophyll Maximum (DCM) modifies the upper ocean heat capture distribution and thus impacts water column temperature and stratification, as well as biogeochemical processes. This energetical role of the DCM is assessed using a 1 m-resolution 1D physical-biogeochemical model of the upper ocean, using climatological forcing conditions of the Guinea Dome (GD). This zone has been chosen among others because a strong and shallow DCM is present all year round. The results show that the DCM warms the seasonal thermocline by +2 degrees C in September/October and causes an increase of heat transfer from below into the mixed layer (ML) by vertical diffusion and entrainment, leading to a ML warming of about 0.3 degrees C in October. In the permanent thermocline, temperature decreases by up to 2 degrees C. The result is a stratification increase of the water column by 0.3 degrees C m(-1) which improves the thermocline realism when compared with observations. At the same time, the heating associated with the DCM is responsible for an increase of nitrate (+300%, 0.024 mu M), chlorophyll (+50%, 0.02 mu g l(-1)) and primary production (+45%: 10 mg C m(-2) day(-1)) in the ML during the entrainment period of October. The considered concentrations are small but this mechanism could be potentially important to give a better explanation of why there is a significant amount of nitrate in the ML. The mechanisms associated with the DCM presence, no matter which temperature or biogeochemical tracers are concerned, are likely to occur in a wide range of tropical or subpolar regions; in these zones a pronounced DCM is present at least episodically at shallow or moderate depths. These results can be generalized to other thermal dome regions where relatively similar physical and biogeochemical structures are encountered. After testing different vertical resolutions (10 m, 5 m, 2.5 m, 1 m and 0.5 m), we show that using at least a 1 to vertical resolution model is mandatory to assess the energetical importance of the DCM.

Concentration of floating biogenic material in convergence zones

Some organisms that live just below the sea surface (the neuston) are known more as a matter of curiosity than as critical players in biogeochemical cycles. The hypothesis of this work is that their existence implies that they receive some food from an upward flux of organic matter. The behaviour of these organisms and of the associated organic matter, hereafter mentioned as floating biogenic material (FBM) is explored using a global physical-biogeochemical coupled model, in which its generation is fixed to 1% of primary production, and decay rate is of the order of I month. The model shows that the distribution of FBM should depart rapidly from that of primary production.. and be more sensitive to circulation patterns than to the distribution of primary production. It is trapped in convergence areas, where it reaches concentrations larger by a factor 10 than in divergences, thus enhancing and inverting the contrast between high and low primary productivity areas. Attention is called on the need to better understand the biogeochemical processes in the first meter of the ocean, as they may impact the distribution of food for fishes, as well as the conditions for air-sea exchange and for the interpretation of sea color.

Daily morphological changes determined by high-energy events on an embayed beach: a qualitative model

This paper examines the daily morphological responses of Sununga Beach, an embayed beach located on the south-eastern Brazilian coast, to storms in the South Atlantic Ocean. The main mechanisms and timing of beach erosion and accretion, the relationship between wave height and direction, and beach volume changes are considered, to establish a qualitative model for short-term embayed beach morphological changes. The methodology consisted of daily topographic surveys during the month of May in 2001, 2002, and 2003, using an RTK-GPS (real-time kinematics global positioning system). Weather and wave model results were used to correlate hydrodynamics and beach morphology. The results indicate that the morphodynamics of Sununga Beach are characterized by a process of beach rotation, which occurred more or less clearly during all three surveys. Unlike what has been commonly described in the literature for longer time intervals and alternations of fair and stormy weather, the beach rotation processes on Sununga Beach occurred under conditions of moderate-to-high wave energy change (wave heights greater than 2 m). An integrated evaluation of the behaviour of the meteorological aspects, together with beach morphology, enabled us to recognize that extra-tropical cyclones were the most important agent in remobilizing the beach planform, whether in beach rotation or in cross-shore erosion. Copyright (C) 2010 John Wiley & Sons, Ltd.

Representation of the Weddell Sea deep water masses in the ocean component of the NCAR-CCSM model

We examine Weddell Sea deep water mass distributions with respect to the results from three different model runs using the oceanic component of the National Center for Atmospheric Research Community Climate System Model (NCAR-CCSM). One run is inter-annually forced by corrected NCAR/NCEP fluxes, while the other two are forced with the annual cycle obtained from the same climatology. One of the latter runs includes an interactive sea-ice model. Optimum Multiparameter analysis is applied to separate the deep water masses in the Greenwich Meridian section (into the Weddell Sea only) to measure the degree of realism obtained in the simulations. First, we describe the distribution of the simulated deep water masses using observed water type indices. Since the observed indices do not provide an acceptable representation of the Weddell Sea deep water masses as expected, they are specifically adjusted for each simulation. Differences among the water masses` representations in the three simulations are quantified through their root-mean-square differences. Results point out the need for better representation (and inclusion) of ice-related processes in order to improve the oceanic characteristics and variability of dense Southern Ocean water masses in the outputs of the NCAR-CCSM model, and probably in other ocean and climate models.

Connections between the Sznajd model with general confidence rules and graph theory

The Sznajd model is a sociophysics model that is used to model opinion propagation and consensus formation in societies. Its main feature is that its rules favor bigger groups of agreeing people. In a previous work, we generalized the bounded confidence rule in order to model biases and prejudices in discrete opinion models. In that work, we applied this modification to the Sznajd model and presented some preliminary results. The present work extends what we did in that paper. We present results linking many of the properties of the mean-field fixed points, with only a few qualitative aspects of the confidence rule (the biases and prejudices modeled), finding an interesting connection with graph theory problems. More precisely, we link the existence of fixed points with the notion of strongly connected graphs and the stability of fixed points with the problem of finding the maximal independent sets of a graph. We state these results and present comparisons between the mean field and simulations in Barabasi-Albert networks, followed by the main mathematical ideas and appendices with the rigorous proofs of our claims and some graph theory concepts, together with examples. We also show that there is no qualitative difference in the mean-field results if we require that a group of size q > 2, instead of a pair, of agreeing agents be formed before they attempt to convince other sites (for the mean field, this would coincide with the q-voter model).

Hydration and anomalous solubility of the Bell-Lavis model as solvent

We address the investigation of the solvation properties of the minimal orientational model for water originally proposed by [Bell and Lavis, J. Phys. A 3, 568 (1970)]. The model presents two liquid phases separated by a critical line. The difference between the two phases is the presence of structure in the liquid of lower density, described through the orientational order of particles. We have considered the effect of a small concentration of inert solute on the solvent thermodynamic phases. Solute stabilizes the structure of solvent by the organization of solvent particles around solute particles at low temperatures. Thus, even at very high densities, the solution presents clusters of structured water particles surrounding solute inert particles, in a region in which pure solvent would be free of structure. Solute intercalates with solvent, a feature which has been suggested by experimental and atomistic simulation data. Examination of solute solubility has yielded a minimum in that property, which may be associated with the minimum found for noble gases. We have obtained a line of minimum solubility (TmS) across the phase diagram, accompanying the line of maximum density. This coincidence is easily explained for noninteracting solute and it is in agreement with earlier results in the literature. We give a simple argument which suggests that interacting solute would dislocate TmS to higher temperatures.

Stickiness in a bouncer model: A slowing mechanism for Fermi acceleration

Some phase space transport properties for a conservative bouncer model are studied. The dynamics of the model is described by using a two-dimensional measure preserving mapping for the variables' velocity and time. The system is characterized by a control parameter epsilon and experiences a transition from integrable (epsilon = 0) to nonintegrable (epsilon not equal 0). For small values of epsilon, the phase space shows a mixed structure where periodic islands, chaotic seas, and invariant tori coexist. As the parameter epsilon increases and reaches a critical value epsilon(c), all invariant tori are destroyed and the chaotic sea spreads over the phase space, leading the particle to diffuse in velocity and experience Fermi acceleration (unlimited energy growth). During the dynamics the particle can be temporarily trapped near periodic and stable regions. We use the finite time Lyapunov exponent to visualize this effect. The survival probability was used to obtain some of the transport properties in the phase space. For large epsilon, the survival probability decays exponentially when it turns into a slower decay as the control parameter epsilon is reduced. The slower decay is related to trapping dynamics, slowing the Fermi Acceleration, i.e., unbounded growth of the velocity.

Quantum critical scaling at a Bose-glass/superfluid transition: Theory and experiment for a model quantum magnet

In this paper we investigate the quantum phase transition from magnetic Bose Glass to magnetic Bose-Einstein condensation induced by amagnetic field in NiCl2 center dot 4SC(NH2)(2) (dichloro-tetrakis-thiourea-nickel, or DTN), doped with Br (Br-DTN) or site diluted. Quantum Monte Carlo simulations for the quantum phase transition of the model Hamiltonian for Br-DTN, as well as for site-diluted DTN, are consistent with conventional scaling at the quantum critical point and with a critical exponent z verifying the prediction z = d; moreover the correlation length exponent is found to be nu = 0.75(10), and the order parameter exponent to be beta = 0.95(10). We investigate the low-temperature thermodynamics at the quantum critical field of Br-DTN both numerically and experimentally, and extract the power-law behavior of the magnetization and of the specific heat. Our results for the exponents of the power laws, as well as previous results for the scaling of the critical temperature to magnetic ordering with the applied field, are incompatible with the conventional crossover-scaling Ansatz proposed by Fisher et al. [Phys. Rev. B 40, 546 (1989)]. However they can all be reconciled within a phenomenological Ansatz in the presence of a dangerously irrelevant operator.

Effects of catalyst load in Pt and Pb-based catalysts using formic acid oxidation as a model

In this paper, we discuss the effects of catalyst load with respect to carbon powder for several Pt and Pb-based catalysts, using formic acid as a model molecule. The discussion is based on electrochemical tests, a complete morphological investigation and theoretical calculations. We show that the Pt and Pb-based catalysts presented activity in formic acid oxidation at very low catalyst loads (e.g., 0.5% in respect to the carbon content). Physical characterisations demonstrate that the electrodes are composed of separated phases of Pt and lead distributed in Pt nanometric-sized islands that are heterogeneously dispersed on the carbon support and Pb ultra-small particles homogeneously distributed throughout the entire carbon surface, as demonstrated by the microscopy studies. At high catalyst loads, very large clusters of Pb(x)O(y) could be observed. Electrochemical tests indicated an increase in the apparent resistance of the system (by a factor of 19.7 Omega) when the catalyst load was increased. The effect of lead in the materials was also studied by theoretical calculations (OFT). The main conclusion is that the presence of Pb atoms in the catalyst can improve the adsorption of formic acid in the catalytic system compared with a pure Pt-based catalyst. (C) 2011 Elsevier B.V. All rights reserved.

New insights on reaction pathway selectivity promoted by crown ether phase-transfer catalysis: Model ab initio calculations of nucleophilic fluorination

Crown ethers have the ability of solubilizing inorganic salts in apolar solvents and to promote chemical reactions by phase-transfer catalysis. However, details on how crown ethers catalyze ionic S(N)2 reactions and control selectivity are not well understood. In this work, we have used high level theoretical calculations to shed light on the details of phase-transfer catalysis mechanism of KF reaction with alkyl halides promoted by 18-crown-6. A complete analysis of the of the model reaction between KF(18-crown-6) and ethyl bromide reveals that the calculations can accurately predict the product ratio and the overall kinetics. Our results point out the importance of the K* ion and of the crown ether ring in determining product selectivity. While the K* ion favors the S(N)2 over the E2 anti pathway, the crown ether ring favors the S(N)2 over E2 syn route. The combination effects lead to a predicted 94% for the S(N)2 pathway in excellent agreement with the experimental value of 92%. A detailed analysis of the overall mechanism of the reaction under phase-transfer conditions also reveals that the KBr product generated in the nucleophilic fluorination acts as an inhibitor of the 18-crown-6 catalyst and it is responsible for the observed slow reaction rate. (C) 2012 Elsevier B.V. All rights reserved.

Interaction of chitosan and mucin in a biomembrane model environment

Chitosans have been widely exploited in biological applications, including drug delivery and tissue engineering, especially owing to their mucoadhesive properties, but the molecular-level mechanisms for the chitosan action are not known in detail. It is believed that chitosan could affect the mucus by interacting with the proteins mucins, in a process mediated by the cell membrane. In this study we used Langmuir monolayers of dimyristoylphosphatidic acid (DMPA) as simplified membrane models to investigate the interplay between the activity of mucins and chitosan. Surface pressure and surface potential measurements were performed with DMPA monolayers onto which chitosan and/or mucin was adsorbed. We found that the expanding effect from mucin was considerably reduced when chitosan was injected after mucin had been adsorbed on the DMPA monolayer. The results were consistent with the formation of complexes between mucin and chitosan, thus highlighting the importance of electrostatic interactions. Furthermore, chitosan could remove mucin that was co-deposited along with DMPA in Langmuir-Blodgett (LB) films, which could be ascribed to molecular-level interactions between chitosan and mucin inferred from the FTIR spectra of the LB films. In conclusion, the results with Langmuir and LB films suggest that electrostatic interactions are crucial for the mucoadhesive mechanism, which is affected by the complexation between chitosan and mucin. (C) 2012 Elsevier Inc. All rights reserved.

Surface-enhanced Raman spectroscopy studies of organophosphorous model molecules and pesticides

This work reports the analytical application of surface-enhanced Raman spectroscopy (SERS) in the trace analysis of organophosphorous pesticides (trichlorfon and glyphosate) and model organophosphorous compounds (dimethyl methylphosphonate and o-ethyl methylphosphonothioate) bearing different functional groups. SERS measurements were carried out using Ag nanocubes with an edge square dimension of ca. 100 nm as substrates. Density functional theory (DFT) with the B3LYP functional was used for the optimization of ground state geometries and simulation of Raman spectra of the organophosphorous compounds and their silver complexes. Adsorption geometries and marker bands were identified for each of the investigated compound. Results indicate the usefulness of SERS methodology for the sensitive analyses of organophosphorous compounds through the use of vibrational spectroscopy.

Supersymmetric extension of the quantum spherical model

In this work, we present a supersymmetric extension of the quantum spherical model, both in components and also in the superspace formalisms. We find the solution for short- and long-range interactions through the imaginary time formalism path integral approach. The existence of critical points (classical and quantum) is analyzed and the corresponding critical dimensions are determined.

Thermodynamics of Ising model with infinite-range interactions by generalized canonical ensemble

In this work we present the idea of how generalized ensembles can be used to simplify the operational study of non-additive physical systems. As alternative of the usual methods of direct integration or mean-field theory, we show how the solution of the Ising model with infinite-range interactions is obtained by using a generalized canonical ensemble. We describe how the thermodynamical properties of this model in the presence of an external magnetic field are founded by simple parametric equations. Without impairing the usual interpretation, we obtain an identical critical behaviour as observed in traditional approaches.

Alzheimer random walk model: Two previously overlooked diffusion regimes

A non-Markovian one-dimensional random walk model is studied with emphasis on the phase-diagram, showing all the diffusion regimes, along with the exactly determined critical lines. The model, known as the Alzheimer walk, is endowed with memory-controlled diffusion, responsible for the model's long-range correlations, and is characterized by a rich variety of diffusive regimes. The importance of this model is that superdiffusion arises due not to memory per se, but rather also due to loss of memory. The recently reported numerically and analytically estimated values for the Hurst exponent are hereby reviewed. We report the finding of two, previously overlooked, phases, namely, evanescent log-periodic diffusion and log-periodic diffusion with escape, both with Hurst exponent H = 1/2. In the former, the log-periodicity gets damped, whereas in the latter the first moment diverges. These phases further enrich the already intricate phase diagram. The results are discussed in the context of phase transitions, aging phenomena, and symmetry breaking.