Estimation of standard enthalpy of formation of alkanes in gaseous state by calculating size, structural and electronic parameters in the molecules

A quantitative analysis is made on the correlation ship of thermodynamic property, i.e., standard enthalpy of formation (ΔH fº) with Kier's molecular connectivity index(¹Xv),vander waal's volume (Vw) electrotopological state index (E) and refractotopological state index (R) in gaseous state of alkanes. The regression analysis reveals a significant linear correlation of standard enthalpy of formation (ΔH fº) with ¹Xv, Vw, E and R. The equations obtained by regression analysis may be used to estimate standard enthalpy of formation (ΔH fº) of alkanes in gaseous state.

Development and validation of spectroscopic methods for simultaneous estimation and dissolution of ofloxacin and ornidazole in tablet dosage forms

The aim of this work was to develop and validate simple, accurate and precise spectroscopic methods (multicomponent, dual wavelength and simultaneous equations) for the simultaneous estimation and dissolution testing of ofloxacin and ornidazole tablet dosage forms. The medium of dissolution used was 900 ml of 0.01N HCl, using a paddle apparatus at a stirring rate of 50 rpm. The drug release was evaluated by developed and validated spectroscopic methods. Ofloxacin and ornidazole showed 293.4 and 319.6nm as λmax in 0.01N HCl. The methods were validated to meet requirements for a global regulatory filing. The validation included linearity, precision and accuracy. In addition, recovery studies and dissolution studies of three different tablets were compared and the results obtained show no significant difference among products.

Bayesian methods for estimation, optimization and experimental design

Mathematical models often contain parameters that need to be calibrated from measured data. The emergence of efficient Markov Chain Monte Carlo (MCMC) methods has made the Bayesian approach a standard tool in quantifying the uncertainty in the parameters. With MCMC, the parameter estimation problem can be solved in a fully statistical manner, and the whole distribution of the parameters can be explored, instead of obtaining point estimates and using, e.g., Gaussian approximations. In this thesis, MCMC methods are applied to parameter estimation problems in chemical reaction engineering, population ecology, and climate modeling. Motivated by the climate model experiments, the methods are developed further to make them more suitable for problems where the model is computationally intensive. After the parameters are estimated, one can start to use the model for various tasks. Two such tasks are studied in this thesis: optimal design of experiments, where the task is to design the next measurements so that the parameter uncertainty is minimized, and model-based optimization, where a model-based quantity, such as the product yield in a chemical reaction model, is optimized. In this thesis, novel ways to perform these tasks are developed, based on the output of MCMC parameter estimation. A separate topic is dynamical state estimation, where the task is to estimate the dynamically changing model state, instead of static parameters. For example, in numerical weather prediction, an estimate of the state of the atmosphere must constantly be updated based on the recently obtained measurements. In this thesis, a novel hybrid state estimation method is developed, which combines elements from deterministic and random sampling methods.

Cargo Traffic on the Helsinki-Tallinn Route

The twin-city model has found to increase economical activity and well-being. The similar economical, social and cultural background of Finland and Estonia as well as the EU integration give good preconditions to create a twin-city of Helsinki and Tallinn. The relatively long distance between Helsinki and Tallinn is challenging. Therefore, good transport infrastructure and functioning connections are required to form a twin-city of Helsinki and Tallinn. The connections between these cities can be considered also in broader perspective than only from the viewpoint of the twin-city concept. New markets areas have been emerged in Europe due to collapse of planned economy and integration of Europe. Also the transport routes to the markets are changing. The Hel-sinki-Tallinn sea route can be considered as a fast route to the new markets in the Cen-tral and Eastern Europe. The Helsinki-Tallinn sea route is also a potential route to the Western European markets. This study provides an analysis of transport and cargo flows between Finland and Esto-nia for regional and local planners. The main purpose of the study is to clarify the pre-sent situation of the seaborne cargo flows on the Helsinki-Tallinn route and how the cargo flows will develop in the future. The study focuses on the following thematic enti-ties: the Finnish and Estonian seaborne transport system and cargo flows, the structure and volume of the cargo flows on the Helsinki-Tallinn route, the hinterland cargo flows on the Helsinki-Tallinn route and the transport methods used on the Helsinki-Tallinn route. The study was carried out as a desk research, a statistical analysis and an inter-view study during the spring–autumn 2011. The study reveals that during the period 2002–2010 the volume of the seaborne cargo traffic between Finland and Estonia has increased significantly while the trend of the trade volume between Finland and Estonia has remained nearly constant. This indicates that the route via Estonia is increasingly used in the Finnish foreign trade. Because the ports of Helsinki and Tallinn are the main ports in the cargo traffic between Finland and Estonia, the role of the Helsinki-Tallinn route as a sea leg in the hinterland connections of Finland has increased. The growth of the cargo volume on the Helsinki-Tallinn route was estimated to continue on the annual level of 10 % during the next couple of years. In the long run the growth of the cargo volumes depends on the economical and indus-trial development of the former Eastern European countries. If the IMO’s sulphur regu-lations will come in force, the Helsinki-Tallinn route will become one of the main routes also to the Western European markets, besides of the route via Sweden. The study also shows that the fast and reliable connections year round on the Helsinki-Tallinn route have made it possible for service and logistics companies to reconsider their logistics strategies in a new way in the both side of the Gulf of Finland. Anyway, the ropax concept is seen as the only economical profitable solution on the Helsinki-Tallinn route because cargo and passenger traffic are supporting each other. The trucks (vehicle combinations) will remain the main mode of transport on the Helsinki-Tallinn route because general cargo is the main commodity on the route. IMO’s sulphur regula-tions and the changes in the structure of the Finnish industry may create prerequisites for rail road transport in the hinterland connections of Finland. The twin-city model has found to increase economical activity and well-being. The similar economical, social and cultural background of Finland and Estonia as well as the EU integration give good preconditions to create a twin-city of Helsinki and Tallinn. The relatively long distance between Helsinki and Tallinn is challenging. Therefore, good transport infrastructure and functioning connections are required to form a twin-city of Helsinki and Tallinn. The connections between these cities can be considered also in broader perspective than only from the viewpoint of the twin-city concept. New markets areas have been emerged in Europe due to collapse of planned economy and integration of Europe. Also the transport routes to the markets are changing. The Hel-sinki-Tallinn sea route can be considered as a fast route to the new markets in the Cen-tral and Eastern Europe. The Helsinki-Tallinn sea route is also a potential route to the Western European markets. This study provides an analysis of transport and cargo flows between Finland and Esto-nia for regional and local planners. The main purpose of the study is to clarify the pre-sent situation of the seaborne cargo flows on the Helsinki-Tallinn route and how the cargo flows will develop in the future. The study focuses on the following thematic enti-ties: the Finnish and Estonian seaborne transport system and cargo flows, the structure and volume of the cargo flows on the Helsinki-Tallinn route, the hinterland cargo flows on the Helsinki-Tallinn route and the transport methods used on the Helsinki-Tallinn route. The study was carried out as a desk research, a statistical analysis and an inter-view study during the spring–autumn 2011. The study reveals that during the period 2002–2010 the volume of the seaborne cargo traffic between Finland and Estonia has increased significantly while the trend of the trade volume between Finland and Estonia has remained nearly constant. This indicates that the route via Estonia is increasingly used in the Finnish foreign trade. Because the ports of Helsinki and Tallinn are the main ports in the cargo traffic between Finland and Estonia, the role of the Helsinki-Tallinn route as a sea leg in the hinterland connections of Finland has increased. The growth of the cargo volume on the Helsinki-Tallinn route was estimated to continue on the annual level of 10 % during the next couple of years. In the long run the growth of the cargo volumes depends on the economical and indus-trial development of the former Eastern European countries. If the IMO’s sulphur regu-lations will come in force, the Helsinki-Tallinn route will become one of the main routes also to the Western European markets, besides of the route via Sweden. The study also shows that the fast and reliable connections year round on the Helsinki-Tallinn route have made it possible for service and logistics companies to reconsider their logistics strategies in a new way in the both side of the Gulf of Finland. Anyway, the ropax concept is seen as the only economical profitable solution on the Helsinki-Tallinn route because cargo and passenger traffic are supporting each other. The trucks (vehicle combinations) will remain the main mode of transport on the Helsinki-Tallinn route because general cargo is the main commodity on the route. IMO’s sulphur regula-tions and the changes in the structure of the Finnish industry may create prerequisites for rail road transport in the hinterland connections of Finland.

Kernel-Based Ranking. Methods for Learning and Performance Estimation

Machine learning provides tools for automated construction of predictive models in data intensive areas of engineering and science. The family of regularized kernel methods have in the recent years become one of the mainstream approaches to machine learning, due to a number of advantages the methods share. The approach provides theoretically well-founded solutions to the problems of under- and overfitting, allows learning from structured data, and has been empirically demonstrated to yield high predictive performance on a wide range of application domains. Historically, the problems of classification and regression have gained the majority of attention in the field. In this thesis we focus on another type of learning problem, that of learning to rank. In learning to rank, the aim is from a set of past observations to learn a ranking function that can order new objects according to how well they match some underlying criterion of goodness. As an important special case of the setting, we can recover the bipartite ranking problem, corresponding to maximizing the area under the ROC curve (AUC) in binary classification. Ranking applications appear in a large variety of settings, examples encountered in this thesis include document retrieval in web search, recommender systems, information extraction and automated parsing of natural language. We consider the pairwise approach to learning to rank, where ranking models are learned by minimizing the expected probability of ranking any two randomly drawn test examples incorrectly. The development of computationally efficient kernel methods, based on this approach, has in the past proven to be challenging. Moreover, it is not clear what techniques for estimating the predictive performance of learned models are the most reliable in the ranking setting, and how the techniques can be implemented efficiently. The contributions of this thesis are as follows. First, we develop RankRLS, a computationally efficient kernel method for learning to rank, that is based on minimizing a regularized pairwise least-squares loss. In addition to training methods, we introduce a variety of algorithms for tasks such as model selection, multi-output learning, and cross-validation, based on computational shortcuts from matrix algebra. Second, we improve the fastest known training method for the linear version of the RankSVM algorithm, which is one of the most well established methods for learning to rank. Third, we study the combination of the empirical kernel map and reduced set approximation, which allows the large-scale training of kernel machines using linear solvers, and propose computationally efficient solutions to cross-validation when using the approach. Next, we explore the problem of reliable cross-validation when using AUC as a performance criterion, through an extensive simulation study. We demonstrate that the proposed leave-pair-out cross-validation approach leads to more reliable performance estimation than commonly used alternative approaches. Finally, we present a case study on applying machine learning to information extraction from biomedical literature, which combines several of the approaches considered in the thesis. The thesis is divided into two parts. Part I provides the background for the research work and summarizes the most central results, Part II consists of the five original research articles that are the main contribution of this thesis.

ESTIMATION OF CORK PRODUCTION USINGAERIAL IMAGERY1

ABSTRACT Inventory and prediction of cork harvest over time and space is important to forest managers who must plan and organize harvest logistics (transport, storage, etc.). Common field inventory methods including the stem density, diameter and height structure are costly and generally point (plot) based. Furthermore, the irregular horizontal structure of cork oak stands makes it difficult, if not impossible, to interpolate between points. We propose a new method to estimate cork production using digital multispectral aerial imagery. We study the spectral response of individual trees in visible and near infrared spectra and then correlate that response with cork production prior to harvest. We use ground measurements of individual trees production to evaluate the model’s predictive capacity. We propose 14 candidate variables to predict cork production based on crown size in combination with different NDVI index derivates. We use Akaike Information Criteria to choose the best among them. The best model is composed of combinations of different NDVI derivates that include red, green, and blue channels. The proposed model is 15% more accurate than a model that includes only a crown projection without any spectral information.

Estimation of the potential evapotranspiration by a simplified penman method

The numerous methods for calculating the potential or reference evapotranspiration (ETo or ETP) almost always do for a 24-hour period, including values of climatic parameters throughout the nocturnal period (daily averages). These results have a nil effect on transpiration, constituting the main evaporative demand process in cases of localized irrigation. The aim of the current manuscript was to come up with a model rather simplified for the calculation of diurnal daily ETo. It deals with an alternative approach based on the theoretical background of the Penman method without having to consider values of aerodynamic conductance of latent and sensible heat fluxes, as well as data of wind speed and relative humidity of the air. The comparison between the diurnal values of ETo measured in weighing lysimeters with elevated precision and estimated by either the Penman-Monteith method or the Simplified-Penman approach in study also points out a fairly consistent agreement among the potential demand calculation criteria. The Simplified-Penman approach was a feasible alternative to estimate ETo under the local meteorological conditions of two field trials. With the availability of the input data required, such a method could be employed in other climatic regions for scheduling irrigation.

Estimation of transpiration of the 'Valencia' orange young plant using thermal dissipation probe method

Most studies on measures of transpiration of plants, especially woody fruit, relies on methods of heat supply in the trunk. This study aimed to calibrate the Thermal Dissipation Probe Method (TDP) to estimate the transpiration, study the effects of natural thermal gradients and determine the relation between outside diameter and area of xylem in 'Valencia' orange young plants. TDP were installed in 40 orange plants of 15 months old, planted in boxes of 500 L, in a greenhouse. It was tested the correction of the natural thermal differences (DTN) for the estimation based on two unheated probes. The area of the conductive section was related to the outside diameter of the stem by means of polynomial regression. The equation for estimation of sap flow was calibrated having as standard lysimeter measures of a representative plant. The angular coefficient of the equation for estimating sap flow was adjusted by minimizing the absolute deviation between the sap flow and daily transpiration measured by lysimeter. Based on these results, it was concluded that the method of TDP, adjusting the original calibration and correction of the DTN, was effective in transpiration assessment.

Estimation of evaporation in the Banabuiú dam, in the state of Ceará, Brazil, by different combined methods, derived from the Penman equation

The state of Ceará, Brazil, has 75% of its area covered by Brazilian semiarid, with its peculiar features. In this state, the dams are constituted in water structure of strategic importance, ensuring, both in time and space, the development and supply of water to population. However, construction of reservoirs results in various impacts that should be carefully observed when deciding on their implementation. One of the impacts identified as negative is the increased evaporation, which constitutes a major component of water balance in reservoirs, especially in arid regions. Several methods for estimating evaporation have been proposed over time, many of them deriving from the Penman equation. This study evaluated six different methods for estimating evaporation in order to determine the most suitable for use in hydrological models for water balance in reservoirs in the state of Ceará. The tested methods were proposed by Penman, Kohler-Nordenson-Fox, Priestley-Taylor, deBruim-Keijman, Brutsaert-Stricker and deBruim. The methods presented good performance when tested for water balance during the dry season, and the Priestley-Taylor was the most appropriate, since the data from de simulated water balance with evaporation estimated by this method were the closest of the water balance data observed from measures of reservoir level and the elevation-volume curve provided by the Company of Management of Water Resources of the state of Ceará - COGERH.

Soil penetration resistance in a rhodic eutrudox affected by machinery traffic and soil water content

Soil compaction caused by machinery traffic reduces crop yields. This study aimed to evaluate the effects of intensive traffic, and the soil water content, on the soil penetration resistance (PR) of a Rhodic Eutrudox (Distroferric Red Latosol, Brazilian Classification), managed under no-tillage (NT). The experiment consisted of six treatments: NT with recent chiseling, NT without additional compaction, and NT with additional compaction by 4, 8, 10 and 20 passes of a harvester with a weight of 100 kN (70 kN on the front axle). Undisturbed soil samples were collected at 5.5-10.5 cm and 13.5-18.5 cm depth to quantify the soil bulk density (BD). The PR was assessed in four periods, using an impact penetrometer, inserted in the soil to a depth of 46 cm. The effect of traffic intensities on the PR was small when this variable was assessed with the soil in the plastic consistency. Differences in PR among treatments increased as the soil water content decreased. The increase in the values of PR and BD was higher in the first passes, but the increase in the number of traffics resulted in deeper soil compaction. The machinery traffic effects on PR are better characterized in the friable soil consistency.

Construction and calibration of TDR probes for volumetric water content estimation in a Distroferric Red Latosol

The determination of volumetric water content of soils is an important factor in irrigation management. Among the indirect methods for estimating, the time-domain reflectometry (TDR) technique has received a significant attention. Like any other technique, it has advantages and disadvantages, but its greatest disadvantage is the need of calibration and high cost of acquisition. The main goal of this study was to establish a calibration model for the TDR equipment, Trase System Model 6050X1, to estimate the volumetric water content in a Distroferric Red Latosol. The calibration was carried out in a laboratory with disturbed soil samples under study, packed in PVC columns of a volume of 0.0078m³. The TDR probes were handcrafted with three rods and 0.20m long. They were vertically installed in soil columns, with a total of five probes per column and sixteen columns. The weightings were carried out in a digital scale, while daily readings of dielectric constant were obtained in TDR equipment. The linear model θν = 0.0103 Ka + 0.1900 to estimate the studied volumetric water content showed an excellent coefficient of determination (0.93), enabling the use of probes in indirect estimation of soil moisture.

Changes in water availability in the soil due to tractor traffic

Frequent traffic of tractors in agricultural soils, promotes soil compaction and affects the flow and water availability. The aim of this research was to study the effect of compaction induced by tractor traffic on water availability in the soil under different traffic intensities on the same path (0, 1, 3, 6 and 10 passages), to two tractors with 3.3 and 2.6 ton of weights, over three different surface conditions. The study was conducted in an Andisol, representative soil of the study area. It was determined the behavior of the water retention curve, obtaining the gravitational water, available water and hygroscopic water, to 10 and 30 cm of depth. The hygroscopic water is the most prevalent with values ​​of up to 80% of the total water present in the soil. The water retention curves showed increases in the values ​​of field capacity and wilting point and behaviors "flattened" indicating a high sensitivity to the applied treatments, representative of compacted soils, which give the surfaces studied characteristics do not suitable for normal crop development.

Estimation of alluvial recharge in the semiarid

In areas where there is irrigated agriculture, the recuperation of water reserves in alluvial aquifers may occur preferentially due to precipitation. Recharging can be evaluated from variation information of water depth measured in piezometers or observation wells. Thus, the aim of this research is to study the recharge in the alluvial aquifer formed by the Mimoso temporary stream in the semiarid region of Pernambuco (PE), Brazil, using the method of the fluctuation of the water level. This system is typical on the Brazilian Northeast semiarid region, using groundwater for domestic supply and for irrigation on small scale agriculture. Monthly potentiometric levels and rainfall data were used. The selected period for the study, from January 2002 to October 2009, involved extreme events of flooding and droughts as well as regular years, providing a better understanding of the behavior of the alluvial recharge. It was found that the system responds significantly to precipitation events. It was also observed that even with different soil textures in the study area, recharge factors were not significantly different. The study provided a better understanding of the behavior of aquifer recharge and its relationship with the soil and the rainfall events in the region.