La produzione e l’uso del Metile di Bromuro, un fumigante estesamente usato in agricoltura, sono stati sottoposti a severe restrizioni dovute alla sua azione di depletore dello strato di ozono. Questa tesi è rivolta ad indagare il destino e le caratteristiche ambientali di due tra le più importanti alternative chimiche all’uso del Bromuro di Metile: l’ 1,3-Dicloropropene (1,3-D) e la Cloropicrina (CP). 1,3-D è un fumigante del suolo, con spiccata attività nematocida, consistente di due isomeri (Z), e (E)-1,3-D; nella sua formulazione sono presenti, inoltre, un esteso numero di impurezze clorurate potenzialmente correlate al processo produttivo. In laboratorio, è stato effettuato uno studio per valutare la stabilità idrolitica delle impurezze clorurate e per prevederne, quindi, il destino ambientale. Allo stesso tempo un piano di monitoraggio è stato svolto per valutare il leaching dell’1,3-D, dei suoi metaboliti, e delle impurezze clorurate. La CP è anch’essa un fumigante del suolo, caratterizzato da un importante profilo tossicologico. Questo lavoro ha valutato l’esposizione degli operatori e l’emissione in atmosfera durante e dopo l’applicazione nel suolo, secondo le pratiche agronomiche vigenti. Infine tramite l’applicazione di modelli matematici quali FOCUS PELMO e FOCUS PEARL si è valutato il destino ambientale della CP rispetto alle acque di falda. La simulazione è stata eseguita in 5 scenari europei realistici. / Production and use of methyl bromide, a soil fumigant, are being restricted because of this chemical’s deleterious effects on stratospheric ozone concentrations. This research examines the environmental fate and properties of methyl bromide replacement: 1,3-Dichloropropene (1,3-D), and Chloropicrin (CP). 1,3-D is a broad-spectrum soil fumigant used to control numerous species of soil-borne plant-parasitic nematodes. 1,3-D consists of two isomers, (Z)- and (E)-1,3-D, and has a number of low-level chlorinated compounds that could potentially be part of the manufacturing process. This study has investigated the hydrolytic stability, under biotic and abiotic conditions, of an extensive representative list of 1,3-D potentially related chlorinated compounds. Furthermore, a monitoring programme was carried out to investigate the leaching of all of this compounds. CP is a broad-spectrum fumigant chemical which is extensively used in agriculture and has an important toxicological profile. This study has assessed CP emission in the atmosphere and operator exposure during and after application in soil through injection of the test substances with routine agronomical application. Finally the environmental fate of CP and its metabolite dichloronitromethane in groundwater were investigated through the use of simulation model FOCUS PELMO and FOCUS PEARL using fully justified input parameters in five realistic scenarios.

No description available.

Icicles are a ubiquitous and picturesque feature of cold winter weather. Their familiar form emerges from a subtle interplay between the solidification dynamics of ice and the gravity-driven flow of the thin water film flowing over their evolving surface. The latent heat released by freezing is advected by the water film and ultimately carried away by the surrounding sub-zero air, which is also flowing. Like many processes far from equilibrium, icicle growth can exhibit nonlinear pattern formation. While scaling theory predicts that icicles converge to `platonic', self-similar shapes, natural icicles often exhibit regular ripple patterns about their circumference, which are due to a morphological instability. This thesis presents a comprehensive experimental study of icicles that sheds new light on the dynamics of their growth and the origin of their form. A table-top apparatus was designed and built for the controlled growth of icicles, under different conditions of temperature, water supply rate, ambient air motion, and water purity. Image analysis and Fourier methods were used to examine their morphology. Contrary to theoretical expectations, ripples do not appear on icicles made from pure water. Instead, ripples grow and travel on icicles made from salt solutions, even at very low concentrations. The addition of non-ionic surfactant or dissolved gases does not produce ripples, unless ionic impurities are also present. The ripple wavelength is independent of time and growth conditions. The ripple amplification rate and traveling velocity vary weakly with the ionic concentration, as do the tip and radial growth speeds of the icicle. While the tip and radial growth also depend on the ambient temperature and input mass flux, the ripple dynamics is not correlated with extrinsic conditions. If the ambient temperature or input mass flux is sufficiently low, the tip growth only advances for a short period of time before it ceases. After cessation, the shape of the icicle deviates increasingly from self-similarity. The most self-similar icicles are made from pure water with the surrounding air gently stirred, whereas icicles made from impure water in still air tend to grow multiple tips.

Icicles are a ubiquitous and picturesque feature of cold winter weather. Their familiar form emerges from a subtle interplay between the solidification dynamics of ice and the gravity-driven flow of the thin water film flowing over their evolving surface. The latent heat released by freezing is advected by the water film and ultimately carried away by the surrounding sub-zero air, which is also flowing. Like many processes far from equilibrium, icicle growth can exhibit nonlinear pattern formation. While scaling theory predicts that icicles converge to `platonic', self-similar shapes, natural icicles often exhibit regular ripple patterns about their circumference, which are due to a morphological instability. This thesis presents a comprehensive experimental study of icicles that sheds new light on the dynamics of their growth and the origin of their form. A table-top apparatus was designed and built for the controlled growth of icicles, under different conditions of temperature, water supply rate, ambient air motion, and water purity. Image analysis and Fourier methods were used to examine their morphology. Contrary to theoretical expectations, ripples do not appear on icicles made from pure water. Instead, ripples grow and travel on icicles made from salt solutions, even at very low concentrations. The addition of non-ionic surfactant or dissolved gases does not produce ripples, unless ionic impurities are also present. The ripple wavelength is independent of time and growth conditions. The ripple amplification rate and traveling velocity vary weakly with the ionic concentration, as do the tip and radial growth speeds of the icicle. While the tip and radial growth also depend on the ambient temperature and input mass flux, the ripple dynamics is not correlated with extrinsic conditions. If the ambient temperature or input mass flux is sufficiently low, the tip growth only advances for a short period of time before it ceases. After cessation, the shape of the icicle deviates increasingly from self-similarity. The most self-similar icicles are made from pure water with the surrounding air gently stirred, whereas icicles made from impure water in still air tend to grow multiple tips.

La plupart des modules photovolta¨ıques produits sont `a base de silicium.L’efficacit´e de ces modules d´epend fortement de la qualit´e cristalline du siliciumutilis´ee ainsi que de la quantit´e d’impuret´es pr´esente dans le lingotd’origine d’o`u sont issus les modules. Les lingots de silicium sont obtenus aucours d’un proc´ed´e de solidification, durant lequel les impuret´es sont extraitespar ph´enom`ene de s´egr´egation. Le processus de s´egr´egation est influenc´e parl’´ecoulement dans le liquide durant l’´etape de solidification. L’utilisation d’unchamp magn´etique externe permet le contrˆole de l’´ecoulement dans le bainliquide. Dans cette ´etude, l’effet d’un ´ecoulement forc´e sur le processus des´egr´egation est ´etudi´e. Pour cela un dispositif exp´erimental (VB2) et unmod`ele num´erique ont ´et´e d´evelopp´es dans le but de comprendre le rˆole del’´ecoulement sur la forme de l’interface et sur la s´egr´egation des impuret´es. / The photovoltaic modules are generally produced using silicon wafers. Theirelectrical efficiency is related to the crystal quality, which is influenced bythe presence of pollutants in the ingots from which the wafers are cut. Siliconingots are obtained as a result of solidification processes, which implygrowing a crystal from melt. During this solidification process, impurities areseparated from the silicon. The segregation process is greatly influenced bythe melt velocity during the solidification process. The control of the meltflow during the crystallization process can be achieved using external magneticfields. This thesis presents the results of the study on the influence ofthe forced convection induced by a travelling magnetic field (TMF) duringthe solidification process, using both an experimental set-up (VB2) and anumerical model.

This study is presented in nine chapters as follows: Chapter one reviews the reported literature on the NMR of natural diamond. The NMR signal of diamond consists on a single line at 39 ppm from TMS and two hyperfine lines due to 13C interactions. The reported relaxation times, measured in natural diamond, synthetic diamonds and 13C enriched diamonds, are discussed. The second chapter introduces the apparatus used, which included a Bruker Avance NMR spectrometer, a Bruker ESP380E pulsed EPR spectrometer and a high powersband DNP system. The availability of this excellently equiped laboratory presented a unique opportunity to perform this investigation. Chapter three outlines the experimental techniques used as well as the manner in which the acquired data was processed. The fourth chapter presents an overview of the most common defects found in diamond. Proposed models of these defects are presented and the resulting EPR spectra displayed. The methods developed to determine the paramagnetic impurity concentration from the EPR line width and the spin-spin relaxation times are presented in the fifth chapter. The line width gives the total paramagnetic impurity concentration to about 10 ppm. The spin-spin relaxation time allows the determination of Pl and P2 paramagnetic impurity concentrations individually, to much lower levels from measurements on the central and hyperfine lines. This information was used in the explanation of the relaxation behaviour for the various diamonds investigated. The temperature dependence of the paramagnetic electron relaxation times is reported in the sixth chapter. The results obtained are consistent with the findings in prior work that Pl impurities are typical Jahn Teller centres. Two diamonds, however, display trends that depart from this theory. These diamonds contain N3 defect centres, which appear to be responsible for this behaviour. It was found in these experiments that, bar thermal expansion effects, the spin-spin relaxation time is essentially independent of temperature. The seventh chapter deals with the solid state and thermal mixing effects. The relevant theory, results obtained and a discussion of these results, are presented. The effect of impurity concentration, defect types, microwave power, the exposure time and the offset from resonance on the polarisation rates and the 13C polarisation are investigated in depth. Finally the effect of applying the DNP treatment on the central and hyperfine lines is discussed. The pulsed DNP process is presented in the eighth chapter. The relevant theory, the effects of matching of the Hartmann-Hahn condition, impurity concentrations and types, on the polarisation rate and signal enhancement of JJC nuclei is given. A comparison to the continuous wave techniques is then made. The ninth chapter summarises the achievements and recommendations for further work. / Physics / D. Phil. (Physics)

The quality of food wheat is annually evaluated with all deliveries of agricultural primary production in the chosen farming enterprise. During the years 2008 - 2012 particular characteristics with files of 42 - 222 samples were determined, except for the year of 2009 when only one supply was technologically incorporated to food wheat. Countrywide observation of the quality of food wheat is executed in Agricultural research institute Kroměříž, Ltd and in Agrotest fyto, Ltd. It is co-financed by Ministry of Agriculture within a functional task which follows the project of Ministry of Agriculture number QG50041 Factors of quality and safety with food grains (2005-2010). Harvest samples, obtained from producers in time span 2008-2012, were represented by files of 500-1035 samples. Characteristics which influence the quality of the grains as well as criteria and methods of the evaluation of food wheat were described. Their applications in Agrotest fyto, Ltd and under operating conditions in ZZN Pelhřimov a.s. were given. Average values of observed parameters were calculated from the results of each testing in the laboratory of the detached post Záhoří and consequently compared with countrywide norm and the norm of South Bohemia. The quality of food wheat grains in years 2008-2012 showed a large-scale variability in particular parameters both at countrywide level and in South Bohemia as well as in chosen farming enterprise. Final quality was considerably influenced by course of weather annually.

Made available in DSpace on 2014-10-09T12:51:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:28Z (GMT). No. of bitstreams: 1 11295.pdf: 3731608 bytes, checksum: 642672d3ddbbe81953275dd174a58822 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/09049-5

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Made available in DSpace on 2014-10-09T12:51:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:28Z (GMT). No. of bitstreams: 1 11295.pdf: 3731608 bytes, checksum: 642672d3ddbbe81953275dd174a58822 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho, os cristais de TlBr foram crescidos pelo método de Bridgman, a partir de materiais purificados pela técnica de fusão zonal. A eficiência da purificação e avaliação da superfície cristalina em relação ao desempenho como detectores de radiação foi observada. Bons resultados foram obtidos com os aprimoramentos realizados nos processos de purificação, crescimento de cristais e na fabricação dos detectores. A resposta à radiação foi verificada excitando os detectores com fontes de raios gama: 241Am (59 keV), 133Ba (80 e 355 keV), 57Co (122 keV), 22Na (511 keV) e 137Cs (662 keV) à temperatura ambiente. Os valores de resolução em energia mais satisfatórios encontrados nesse trabalho foram a partir de detectores mais puros. Os melhores valores de resolução em energia obtidos foram de 10keV (16%), 12keV (15%), 12keV (10%), 28 keV (8%), 31keV (6%) e 36keV (5%) para as energias de 59, 80, 122, 355, 511 e 662 keV, respectivamente. Também foi realizado um estudo da resposta à detecção a uma temperatura de -20ºC e da estabilidade desses detectores. Nos detectores desenvolvidos não houve diferença significativa na resolução tanto em temperatura ambiente quanto na reduzida. Em relação à estabilidade foi observada uma degradação das características espectrométricas sob operação contínua do detector a temperatura ambiente e esta instabilidade variou para cada detector. Ambas características também foram observadas por outros autores. A viabilidade de utilização do cristal de TlBr como fotodetector para acoplamento em cintiladores também foi estudada neste trabalho. TlBr é um material promissor para ser utilizado como fotodetector devido a sua adequada eficiência quântica na região de 350 a aproximadamente 500 nm. Como uma aplicação para este trabalho foram iniciados estudos para fabricação de sondas cirúrgicas utilizando cristais de TlBr como o meio detector. / Neste trabalho, os cristais de TlBr foram crescidos pelo método de Bridgman, a partir de materiais purificados pela técnica de fusão zonal. A eficiência da purificação e avaliação da superfície cristalina em relação ao desempenho como detectores de radiação foi observada. Bons resultados foram obtidos com os aprimoramentos realizados nos processos de purificação, crescimento de cristais e na fabricação dos detectores. A resposta à radiação foi verificada excitando os detectores com fontes de raios gama: 241Am (59 keV), 133Ba (80 e 355 keV), 57Co (122 keV), 22Na (511 keV) e 137Cs (662 keV) à temperatura ambiente. Os valores de resolução em energia mais satisfatórios encontrados nesse trabalho foram a partir de detectores mais puros. Os melhores valores de resolução em energia obtidos foram de 10keV (16%), 12keV (15%), 12keV (10%), 28 keV (8%), 31keV (6%) e 36keV (5%) para as energias de 59, 80, 122, 355, 511 e 662 keV, respectivamente. Também foi realizado um estudo da resposta à detecção a uma temperatura de -20ºC e da estabilidade desses detectores. Nos detectores desenvolvidos não houve diferença significativa na resolução tanto em temperatura ambiente quanto na reduzida. Em relação à estabilidade foi observada uma degradação das características espectrométricas sob operação contínua do detector a temperatura ambiente e esta instabilidade variou para cada detector. Ambas características também foram observadas por outros autores. A viabilidade de utilização do cristal de TlBr como fotodetector para acoplamento em cintiladores também foi estudada neste trabalho. TlBr é um material promissor para ser utilizado como fotodetector devido a sua adequada eficiência quântica na região de 350 a aproximadamente 500 nm. Como uma aplicação para este trabalho foram iniciados estudos para fabricação de sondas cirúrgicas utilizando cristais de TlBr como o meio detector. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/09049-5