Calculation of Chemical Potentials and Occupancies in Clathrate Hydrates through Monte Carlo Molecular Simulations

The flexibility of the water lattice in clathrate hydrates and guest-guest interactions has been shown in previous studies to significantly affect the values of the thermodynamic properties, such as chemical potentials and free energies. Here we describe methods for computing occupancies, chemical potentials, and free energies that account for the flexibility of water lattice and guest-guest interactions in the hydrate phase. The methods are validated for a wide variety of guest molecules, such as methane, ethane, carbon dioxide, and tetrahydrodfuran by comparing the predicted occupancy values of guest molecules with those obtained from isothermal isobaric semigrand Monte Carlo simulations. The proposed methods extend the van der Waals and Platteuw theory for clathrate hydrates, and the Langmuir constant is calculated based on the structure of the empty hydrate lattice. These methods in combination with development of advanced molecular models for water and guest molecules should lead to a more thermodynamically consistent theory for clathrate hydrates.

Reproductive dynamics of female spotted seatrout (Cynoscion nebulosus) in South Carolina

We describe reproductive dynamics of female spotted seatrout (Cynoscion nebulosus) in South Carolina (SC). Batch fecundity (BF), spawning frequency (SF), relative fecundity (RF), and annual fecundity (AF) for age classes 1−3 were estimated during the spawning seasons of 1998, 1999, and 2000. Based on histological evidence, spawning of spotted seatrout in SC was determined to take place from late April through early September. Size at first maturity was 248 mm total length (TL); 50% and 100% maturity occurred at 268 mm and 301 mm TL, respectively. Batch fecundity estimates from counts of oocytes in final maturation varied significantly among year classes. One-year-old spotted seatrout spawned an average of 145,452 oocytes per batch, whereas fish aged 2 and 3 had a mean BF of 291,123 and 529,976 oocytes, respectively. We determined monthly SF from the inverse of the proportion of ovaries with postovulatory follicles (POF) less than 24 hours old among mature and developing females. Overall, spotted seatrout spawned every 4.4 days, an average of 28 times during the season. A chronology of POF atresia for water temperature >25°C is presented. Length, weight (ovary-free), and age explained 67%, 65%, and 58% of the variability in BF, respectively. Neither RF (number of oocytes/g ovary-free weight) nor oocyte diameter varied significantly with age. However, RF was significantly greater and oocyte diameter was smaller at the end of the spawning season. Annual fecundity estimates were approximately 3.2, 9.5, and 17.6 million oocytes for each age class, respectively. Spotted seatrout ages 1−3 contributed an average of 29%, 39%, and 21% to the overall reproductive effort according to the relative abundance of each age class. Ages 4 and 5 contributed 7% and 4%, respectively, according to predicted AF values.

Development of a QSPR correlation for the parachor of 1,3-dialkyl imidazolium based ionic liquids

Ionic liquids have received significant interest from both academia and industry for a wide range of applications which often requires knowledge of their thermophysical properties. Quantitative structure-property relationship correlations and group contribution methods for thermophysical properties of ionic liquids are a basic necessity for the development of computer aided molecular design approaches for these liquids and subsequently offer the potential for designing an ionic liquid having a desirable set of thermophysical properties. However, the limited availability of experimental thermophysical data and their quality have prevented the development of such tools. Based on previously reported experimental surface tension data, a correlation of the parachors with the molar volume of the ionic liquids has been developed. The predicted parachor values have been shown to be in good agreement with the experimental data. A maximum deviation of

On the nudging terms at open boundaries in regional ocean models

For open boundary conditions (OBCs) in regional models, a nudging term added to radiative and/or advective conditions during the wave or flow propagation outward from the model domain of interest is widely used, to prevent the predicted boundary values from evolving to become quite different from the external data, especially for a long-term integration. However, nudging time scales are basically unknown, leading to many empirical selections. In this paper, a method for objectively estimating nudging time scales during outward propagation is proposed, by using internal model dynamics near the boundary. We tested this method and other several commonly used OBCs for cases of both an idealized model domain and a realistic configuration, and model results demonstrated that the proposed method improves the model solutions. Many similarities are found between the nudging and mixing time scales, in magnitude, spatial and temporal variations, since the nudging mainly replaces the effect of the mixing terms in this study. However, the mixing time scale is not an intrinsic property of the nudging term because in other studies the nudging term might replace terms other than the mixing terms and, thus, should reflect other characteristic time scales.

Calibration and validation of hydrodynamic, salt and heat transport models for Ria de Aveiro lagoon (Portugal)

Ria deAveiro is a very complex shallow water coastal lagoon located on the northwest of Portugal. Important issues would be left unanswered without a good understanding of hydrodynamic and transport processes occurring in the lagoon. Calibration and validation of hydrodynamic, salt and heat transport models for Ria de Aveiro lagoon are presented. The calibration of the hydrodynamic model was performed adjusting the bottom friction coefficient, through the comparison between measured and predicted time series of sea surface elevation for 22 stations. Harmonic analysis was performed in order to evaluate the model's accuracy. To validate the hydrodynamic model measured and predicted SSE values were compared for 11 stations, as well as main flow direction velocities for 10 stations. The salt and heat transport models were calibrated comparing measured and predicted time series of salinity and water temperature for 7 stations, and the RMS of the difference between the series was determined. These models were validated comparing the model results with an independent field data set. The hydrodynamic and the salt and heat transport models for Ria de Aveiro were successfully calibrated and validated. They reproduce accurately the barotropic flows and can therefore adequately represent the salt and heat transport and the heat transfer processes occurring in Ria deAveiro.

Drift from the use of handheld knapsack pesticide sprayers in Boyacá (Colombian Andes)

Offsite pesticide losses in tropical mountainous regions have been little studied. One example is measuring pesticide drift soil deposition, which can support pesticide risk assessment for surface water, soil, bystanders, off target plants and fauna. This is considered a serious gap, given the evidence of pesticide-related poisoning in those regions. Empirical data of drift deposition of a pesticide surrogate, Uranine tracer, within one of the highest potato producing regions in Colombia, characterized by small plots and mountain orography, is presented. High drift values encountered in our study reflect the actual spray conditions using handled knapsack sprayers. Comparison between measured and predicted drift values using three existing empirical equations showed important underestimation. However, after their optimization based on measured drift information, the equations showed a strong predictive power for this study area and the study conditions. The most suitable curve to assess mean relative drift was the IMAG calculator after optimization.

Calculating Flash Point Numbers from Molecular Structure: An Improved Method for Predicting the Flash Points of Acyclic Alkanes

We report a novel method for calculating flash points of acyclic alkanes from flash point numbers, N(FP), which can be calculated from experimental or calculated boiling point numbers (Y(BP)) with the equation N(FP) = 1.020Y(BP) - 1.083 Flash points (FP) are then determined from the relationship FP(K) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901 For it data set of 102 linear and branched alkanes, the correlation of literature and predicted flash points has R(2) = 0.985 and an average absolute deviation of 3.38 K. N(FP) values can also be estimated directly from molecular structure to produce an even closer correspondence of literature and predicted FP values. Furthermore, N(FP) values provide a new method to evaluate the reliability of literature flash point data.

Insights into the Molecular Requirements for the Anti-obesity Activity of a Series of CB1 Ligands

Two-dimensional and 3D quantitative structure-activity relationships studies were performed on a series of diarylpyridines that acts as cannabinoid receptor ligands by means of hologram quantitative structure-activity relationships and comparative molecular field analysis methods. The quantitative structure-activity relationships models were built using a data set of 52 CB1 ligands that can be used as anti-obesity agents. Significant correlation coefficients (hologram quantitative structure-activity relationships: r 2 = 0.91, q 2 = 0.78; comparative molecular field analysis: r 2 = 0.98, q 2 = 0.77) were obtained, indicating the potential of these 2D and 3D models for untested compounds. The models were then used to predict the potency of an external test set, and the predicted (calculated) values are in good agreement with the experimental results. The final quantitative structure-activity relationships models, along with the information obtained from 2D contribution maps and 3D contour maps, obtained in this study are useful tools for the design of novel CB1 ligands with improved anti-obesity potency.

Microstructure evolution modeling of square-diamond pass hot bar rolling of AISI 4135 steel

In this study, kinetics of the static (SRX) and metadynamic recrystallization (MDRX) of AISI4135 steel was investigated using hot torsion tests. Continuous torsion tests were carried out to determine the critical strain for dynamic recrystallization (DRX). The times for 50% recrystallization of SRX and MDRX were determined, respectively, by means of interrupted torsion tests. Furthermore, austenite grain size (AGS) evolution due to recrystallization (RX) was measured by optical microscopy. With the help of the evolution model established, the AGS for hot bar rolling of AISI4135 steel was predicted numerically. The predicted AGS values were compared with the results using the other model available in the literature and experimental results to verify its validity. Then, numerical predictions depending on various process parameters such as interpass time, temperature, and roll speed were made to investigate the effect of these parameters on AGS distributions for square-diamond pass rolling. Such numerical results were found to be beneficial in understanding the effect of processing conditions on the microstructure evolution better and control the rolling processes more accurately.

Strategies for improving the thermal performance and comfort levels of a kindergarten in the mountains of Nepal

Located on the Annapurna trekking trail in Nepal, Siurung is a remote mountain village where outside influences are almost non-existent. The thermal comfort levels of a recently-constructed kindergarten are well below international standards because of the climate and poor building envelope. A TRNSYS model of the kindergarten has been used to predict the current occupant comfort levels and subsequently determine the most effective way to alter the traditional construction methods to improve comfort levels. Improvements investigated were: reduced air infiltration, roof and wall insulation (separately and together), installation of a smokeless stove and a combination of all strategies.The model predicted that in the current building the PMV ranges from -1.94 in October to - 0.99 in July. It also predicted that the current PPD (%) ranges from 100 in January to 26 in July. With the combination of strategies, the predicted PMV values were all improved to between -1.08 and +0.34, and the PPD values of all months except January were reduced to below 10%. When improving the comfort levels of an existing school, reducing air infiltration, adding roof insulation and installing a smokeless stove are the most effective strategies. When constructing a new school, however, reducing air infiltration and adding insulation to the walls and roof are the most effective and feasible strategies. If a smokeless stove can be afforded and transported to the site, it is recommended that one be installed as it provides a more significant improvement than any other single strategy.

Application of species distribution models to explain and predict the distribution, abundance and assemblage structure of nearshore temperate reef fishes

 Aim: The purpose of this study was to create predictive species distribution models (SDMs) for temperate reef-associated fish species densities and fish assemblage diversity and richness to aid in marine conservation and spatial planning. Location: California, USA. Methods: Using generalized additive models, we associated fish species densities and assemblage characteristics with seafloor structure, giant kelp biomass and wave climate and used these associations to predict the distribution and assemblage structure across the study area. We tested the accuracy of these predicted extrapolations using an independent data set. The SDMs were also used to estimate larger scale abundances to compare with other estimates of species abundance (uniform density extrapolation over rocky reef and density extrapolations taking into account variations in geomorphic structure). Results: The SDMs successfully modelled the species-habitat relationships of seven rocky reef-associated fish species and showed that species' densities differed in their relationships with environmental variables. The predictive accuracy of the SDMs ranged from 0.26 to 0.60 (Pearson's r correlation between observed and predicted density values). The SDMs created for the fish assemblage-level variables had higher prediction accuracies with Pearson's r values of 0.61 for diversity and 0.71 for richness. The comparisons of the different methods for extrapolating species densities over a single marine protected area varied greatly in their abundance estimates with the uniform extrapolation (density values extrapolated evenly over the rocky reef) always estimating much greater abundances. The other two methods, which took into account variation in the geomorphic structure of the reef, provided much lower abundance estimates. Main conclusions: Species distribution models that combine geomorphic, oceanographic and biogenic habitat variables can reliably predict spatial patterns of species density and assemblage attributes of temperate reef fishes at spatial scales of 50 m. Thus, SDMs show great promise for informing spatial and ecosystem-based approaches to conservation and fisheries management. © 2015 John Wiley

Genetic aspects of productive and reproductive traits in a Murrah buffalo herd in São Paulo, Brazil

This study investigated genetic trends of some productive and reproductive traits in a herd of Murrah buffalo raised in São Paulo, Brazil. Variance components for milk production (Mr), length of lactation (LL), calving interval (CI) and age of first calving (AFC) were estimated by che restricted maximum likelihood method, using an animal model. Estimated heritability values were 0.38; 0.01; 0.10 and 0.20 for MP, LL, CI and AFC, respectively. Estimated repeatability values were 0.50, 0.13 and 0.20 for MP, LL and CI, respectively. Means of predicted breeding values for cows, dams and sires according to calving year and the genetic correlations were presented.

Avaliação genética de touros da raça Gir para produção de leite no dia do controle e em 305 dias de lactação

Dados de 32.779 controles mensais, de 3.605 lactações em 305 dias (PL305), de 2.082 vacas Gir, filhas de 281 touros, com partos ocorridos de 1987 a 1999 em 11 rebanhos, foram usados com o objetivo de verificar a viabilidade de utilização da produção de leite no dia do controle (PLDC) em avaliações genéticas de touros da raça Gir. Foram realizadas análises univariadas das PLDC1 a PLDC10 e da PL305 pelo método de máxima verossimilhança restrita, sob modelo animal, incluindo as três primeiras lactações como medidas repetidas de um mesmo animal, diferenciados conforme o grupo contemporâneo de rebanho-ano-estação, de acordo com a idade da vaca ao parto e, do intervalo parto-primeiro controle na PLDC1. As médias observadas e os respectivos desvios-padrão (kg) para PLDC1 a PLDC10 e PL305 foram: 11,97±4,64; 11,93±4,68; 10,98±4,40; 10,18±4,12; 9,66±3,88; 9,20±3,69; 8,63±3,51; 8,08±3,33; 7,59±3,27; 7,22±3,15 e 2.746,17±1.299,90. As estimativas de herdabilidade para as PLDC1 a PLDC10 foram de 0,26; 0,19; 0,18; 0,20; 0,15; 0,13; 0,14; 0,10; 0,11 e 0,10, respectivamente; para a PL305 foi de 0,18. As correlações de ordem dos valores genéticos preditos de 281 touros, obtidos entre as PLDC e a PL305, foram altas, oscilando de 0,85 a 0,94. O percentual de coincidência de touros que seriam selecionados pelos valores genéticos preditos das PLDC2 a PLDC5 foram acima de 80%, a partir de 5% dos melhores classificados pela PL305. em algumas PLDC o nível de coincidência de classificação dos touros com a PL305 foi muito baixo.

Predição de valores genéticos para a produção de leite no dia do controle e para a produção acumulada até 305 dias

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise genética de escores de avaliação visual de bovinos com modelos bayesianos de limiar e linear

O objetivo deste trabalho foi comparar as estimativas de parâmetros genéticos obtidas em análises bayesianas uni-característica e bi-característica, em modelo animal linear e de limiar, considerando-se as características categóricas morfológicas de bovinos da raça Nelore. Os dados de musculosidade, estrutura física e conformação foram obtidos entre 2000 e 2005, em 3.864 animais de 13 fazendas participantes do Programa Nelore Brasil. Foram realizadas análises bayesianas uni e bi-características, em modelos de limiar e linear. de modo geral, os modelos de limiar e linear foram eficientes na estimação dos parâmetros genéticos para escores visuais em análises bayesianas uni-características. Nas análises bi-características, observou-se que: com utilização de dados contínuos e categóricos, o modelo de limiar proporcionou estimativas de correlação genética de maior magnitude do que aquelas do modelo linear; e com o uso de dados categóricos, as estimativas de herdabilidade foram semelhantes. A vantagem do modelo linear foi o menor tempo gasto no processamento das análises. Na avaliação genética de animais para escores visuais, o uso do modelo de limiar ou linear não influenciou a classificação dos animais, quanto aos valores genéticos preditos, o que indica que ambos os modelos podem ser utilizados em programas de melhoramento genético.