Made available in DSpace on 2016-06-02T19:29:31Z (GMT). No. of bitstreams: 1 3411.pdf: 2299382 bytes, checksum: 44ff227a0e9cd4657b1aca56caa5179c (MD5) Previous issue date: 2010-12-20 / Universidade Federal de Sao Carlos / The plants release primary and secondary metabolites in the environment that may influence the development of adjacent vegetation, this interference phenomenon is called allelopathy. It is recognized as an important ecological process because it interferes with the structure, distribution, composition and dynamics of plant communities. Studies on allelopathic interactions may be useful in the search for natural phytotoxins are produced by plants or microorganisms to be used as natural herbicides, more specific and less harmful to the environment. According to floristic survey conducted by IBGE, Myrtaceae family is one of the major in the cerrado ecosystem. This study attempted to clarify the following issues: species of Myrtaceae family present in the cerrado (Brazilian savanna) exhibit allelopathic potential? There is a similar allelopathic response within genera? Among the active species, which is most promising for starting a bioprospecting? Some of these species has potential as a herbicide for use in agroforestry or organic production of food? To answer these questions were conducted experiments of seed germination and seedling growth of target species cultivated and weedy, and chemical extraction of active compounds in leaves of Myrcia tomentosa. The leaves of Blepharocalyx salicifolius, Campomanesia pubescens, Eugenia bimarginata, Eugenia klotzschiana, Eugenia myrcianthes, Eugenia punicifolia, Myrcia bella, Myrcia lingua, Myrcia multiflora, Myrcia splendens, Myrcia tomentosa, Psidium australe, Psidium cinereum, Psidium laruotteanum and Psidium rufum were collected , cleaned, crushed and stored in plastic bags until use. In the first stage, were carried out the germination and growth bioassays using aqueous extracts of leaf in a concentration of 10% (w / v). We selected three target species, Lactuca sativa and Solanum lycopersicum, both eudicotyledonous and a monocotyledonous Allium cepa. The extracts were applied to all Myrtaceae species compared with the control (distilled water). In the second phase, bioassays were carried out using aqueous extracts of leaves at concentrations of 5 and 10% (w / v). We selected as target species three weeds Euphorbia heterophylla, Echinochloa crus-galli and Ipomoea grandifolia. The leaf extracts of B. salicifolius, M. multiflora, M. splendens and M. tomentosa were compared to negative control (distilled water) and positive (herbicide Oxyfluorfen). In the third stage were carried out biotests germination, growth, and coleoptile of wheat (Triticum aestivum) to direct chemical extraction of active compounds of M. tomentosa. The extractions were carried out using dried leaves powdered and organic solvents of different polarity, the extracts were fractionated using chromatographic column and purified by HPLC. The isolated and purified compounds were identified in RMN13C and RMN1H, by comparison of spectra. The results showed that aqueous extracts of twelve out of fifteen donor species evaluated showed allelopathic activity and each species showed a distinct behavior regarding the allelopathic activity, no grouping by taxonomic proximity. Evaluating the four species most active on weeds species, was detected the potential and efficiency of the extracts, since these were more toxic to weeds species than the herbicide. The leaf extracts of M. tomentosa stood out for demonstrating high activity even at low concentrations, so was chemical extraction from powdered of leaves of M. tomentosa were isolated two compounds from the ethyl acetate extract: juglanin and avicularin, the difference between ix both is the presence of one hydroxyl attached to carbon 3' in avicularin molecule, this difference has an phytotoxic effect more pronounced in the juglanin. This paper is the first report of the presence of the flavonoids kaempferol (juglanin) and quercetin (avicularin) in species of Myrtaceae of cerrado (Brazilian savanna) and gave foundation for future studies on bioprospecting of the M. tomentosa, which did not find any reports of allelopathic studies, fractionation and identification of chemical compounds. / Os vegetais liberam metabolitos primarios e secundarios no ambiente que podem influenciar no desenvolvimento da vegetacao adjacente, este fenomeno de interferencia e denominado alelopatia. E reconhecida como um processo ecologico importante, pois interfere na estrutura, distribuicao, composicao e dinamica de comunidades vegetais. Estudos sobre interacoes alelopaticas podem ser uteis na busca por fitotoxinas naturais, produzidas por plantas ou microrganismos a serem empregados como herbicidas naturais, mais especificos e menos prejudiciais ao ambiente. De acordo com inventario floristico realizado pelo IBGE a familia Myrtaceae e uma das principais em riqueza e diversidade no ecossistema de cerrado. Assim, este trabalho tentou esclarecer as seguintes questoes: especies da familia Myrtaceae presentes no cerrado apresentam potencial alelopatico? Existe semelhanca na resposta alelopatica dentro dos generos? Dentre as especies ativas, qual a mais promissora para se iniciar uma bioprospeccao? Alguma dessas especies apresenta potencial para utilizacao como herbicida em sistemas agroflorestais ou de producao organica de alimentos? Para responder essas perguntas foram realizados bioensaios de germinacao de diasporos e crescimento de plantulas, de especies alvo cultivadas e infestantes de cultura, e extracao quimica de compostos ativos em folhas de Myrcia tomentosa. As folhas maduras de Blepharocalyx salicifolius, Campomanesia pubescens, Eugenia bimarginata, Eugenia klotzschiana, Eugenia myrcianthes, Eugenia punicifolia, Myrcia bella, Myrcia lingua, Myrcia multiflora, Myrcia splendens, Myrcia tomentosa, Psidium australe, Psidium cinereum, Psidium laruotteanum e Psidium rufum foram coletadas, higienizadas, trituradas e armazenadas em embalagens plasticas ate a utilizacao. Na primeira etapa, os bioensaios de germinacao e crescimento, foram efetuados utilizando-se extratos aquosos de po de folhas em concentracao de 10% (p/v). Como especies receptoras foram selecionadas duas eudicotiledoneas Lactuca sativa e Solanum lycopersicum e, uma monocotiledonea Allium cepa, nas quais foram aplicados os extratos de todas as especies de Myrtaceae comparadas ao controle (agua destilada). Na segunda etapa, os bioensaios foram efetuados utilizando-se extratos aquosos de po de folhas em concentracao de 5 e 10% (p/v). Como especies receptoras foram selecionadas as infestantes de cultura Euphorbia heterophylla, Echinochloa crus-galli e Ipomoea grandifolia, nas quais foram aplicados os extratos de folhas de B. salicifolius, M. multiflora, M. splendens e M. tomentosa, comparadas ao controle negativo (agua destilada) e ao positivo (herbicida Oxifluorfem). Na terceira etapa, foram efetuados biotestes de germinacao, crescimento e de coleoptilo de trigo para direcionar a extracao quimica de compostos ativos de M. tomentosa. Para tanto as extracoes foram feitas empregando-se o po de folhas e os solventes organicos de diferentes polaridades. Os extratos foram fracionados em coluna cromatografica e purificados em CLAE. Os compostos isolados e purificados foram identificados em RMN13C e RMN1H, por comparacao de espectros. Os resultados mostraram que extratos aquosos de doze das quinze especies doadoras avaliadas apresentaram atividade alelopatica e cada especie demonstrou comportamento distinto em relacao a atividade alelopatica, nao houve agrupamento por proximidade taxonomica. Avaliando as quatro especies mais ativas sobre especies invasoras, constatou-se o potencial e a eficiencia dos extratos, uma vez que estes foram mais fitotoxicos as especies invasoras que o herbicida. O extrato foliar de M. tomentosa destacou-se por demonstrar elevada atividade mesmo em baixa concentracao, assim foi realizada a extracao quimica do po folhas desta especie. Foram isolados dois compostos do extrato acetato de etila: juglanina e avicularina, o que as diferencia e a hidroxila ligada ao carbono 3 na molecula de avicularina, esta diferenca produziu efeito fitotoxico mais acentuado da molecula de vii juglanina. O presente trabalho relatou pela primeira vez a presenca dos flavonoides kaempferol (juglanina) e quercetina (avicularina) em uma especie de Myrtaceae do cerrado e deu embasamento para futuros estudos relativos a bioprospeccao da especie Myrcia tomentosa, da qual nao se encontrou nenhum relato de estudos alelopaticos, fracionamento e identificacao de compostos quimicos.

Made available in DSpace on 2014-07-29T16:24:16Z (GMT). No. of bitstreams: 1 Dissertacao Kassia Aparecida Garcia Barbosa.pdf: 931610 bytes, checksum: 10046fdd236ad9643625e61fc8a6a851 (MD5) Previous issue date: 2010-11-29 / This study evaluated the effect of herbicides on the population density of H. glycines in soybean cultivars, (one resistant and three susceptible) in natural infestation conditions. Experiments were done in Campo Alegre de Goiás and Gameleira de Goiás, agricultural year 2006/07, using randomized blocks, with three repetitions. The treatments were arranged in a factorial design 4 x 4 + 1, with four cultivars (BRSGO Ipameri, BRSGO Luziânia, BRSGO Jataí BRS Silvânia RR), four forms of weed control (hand weeding, chlorimuron-ethyl + lactofen, chlorimuron-ethyl and haloxyfop-methyl), and additional treatment represented by the combination of transgenic cultivar BRS Silvânia RR and herbicide glyphosate. In agricultural year 2009/2010, another test was conducted in Gameleira de Goiás, with four repetitions, in a factorial design 2 x 4 + 2, involving two cultivars (BRSGO Chapadões and BRSGO 8360), four forms of weed control (hand weeding, lactofen, chlorimuron-ethyl; haloxifop-r), and two additional treatments represented by the combination of transgenic cultivar BRS Valiosa RR with control manual weed and chemical control via herbicide glyphosate. In the agricultural year 2006/07, in Campo Alegre de Goiás, eighty days after planting, there was less formation of viable cysts in cultivar BRS Silvânia RR associated with the application of clorimuron + lactofen, compared to manual control. In Gameleira de Goias, it was found, forty days after planting, increase in the number of viable cysts using herbicides, compared with manual control, in cultivar susceptible BRSGO Luziânia, BRSGO Ipameri, resistant to H. glycines, the number of viable cysts was lower when applied herbicides clorimuron+lactofen or haloxyfop, compared the application of clorimuron. The herbicides had no effect on the number of females in susceptible and resistant cultivars in the year 2009/10. In cultivar susceptible BRSGO 8360, the herbicide haloxifop led to a smaller number of females, in comparison with clorimuron, 45 days after sowing. The herbicide lactofen, in the cultivar BRSGO Chapadões (resistant) was associated with increase in the number of viable cysts 45 days after sowing. This herbicide affects negatively the biomass of leaves, fresh green beans and dry bean in the cultivars BRSGO Chapadões and BRSGO 8360. / O trabalho objetivou avaliar o efeito de herbicidas sobre a densidade populacional de H. glycines em cultivares de soja (uma resistente e três suscetíveis), em condições naturais de infestação. Experimentos foram conduzidos em Campo Alegre de Goiás e Gameleira de Goiás, safra 2006/07, utilizando delineamento de blocos casualizados, com três repetições. Os tratamentos foram arranjados em esquema fatorial 4x4+1, sendo: quatro cultivares (BRSGO Ipameri, BRSGO Luziânia, BRSGO Jataí, BRS Silvânia RR); quatro formas de controle de plantas daninhas (arranquio manual, chlorimuron-etil+lactofen, chlorimuron-etil e haloxyfop-metil); e o tratamento adicional representado pela combinação da cultivar transgênica BRS Silvânia RR e o herbicida glifosato. Na safra 2009/10, outro ensaio foi conduzido em Gameleira de Goiás, com quatro repetições, em esquema fatorial 2x4+2, envolvendo duas cultivares (BRSGO Chapadões e BRSGO 8360) quatro formas de controle de plantas daninhas (arranquio manual, lactofen, chlorimuron-etil e haloxifop-r), e os dois tratamentos adicionais que consistiram das combinações entre a cultivar BRS Valiosa RR com o controle manual das plantas daninhas e com o controle químico via herbicida glifosato. Na safra 2006/07, em Campo Alegre de Goiás, aos oitenta dias após o plantio, observou-se menor formação de cistos viáveis na cultivar BRS Silvânia RR, associado à aplicação de clorimuron + lactofen, em comparação ao controle manual. Em Gameleira de Goiás, verificou-se, aos quarenta dias após o plantio, aumento do número de cistos viáveis com o uso de herbicidas, em comparação com o controle manual, na cultivar suscetível BRSGO Luziânia, já na cultivar BRSGO Ipameri, resistente a H. glycines, o número de cistos viáveis foi menor quando se aplicou os herbicidas clorimuron+lactofen ou haloxifop, em comparação à aplicação de clorimuron. Na safra 2009/10, os herbicidas não influenciaram o comportamento das cultivares (resistente ou suscetíveis) quanto ao número de fêmeas. Na cultivar suscetível BRSGO Luziânia, o herbicida haloxifop possibilitou a formação de menor número de fêmeas, em comparação com clorimuron, aos 45 dias após o plantio. O herbicida lactofen, em BRSGO Chapadões, resistente, esteve associado com o aumento na formação de cistos viáveis, aos 45 dias após o plantio. Este herbicida afetou negativamente a produção de biomassa de planta seca, vagem fresca e vagem seca nas cultivares BRSGO Chapadões e BRSGO 8360.

Made available in DSpace on 2017-07-10T19:23:36Z (GMT). No. of bitstreams: 1 Denilson.pdf: 4098476 bytes, checksum: 61dc064a679354a8ec986c07c33444c3 (MD5) Previous issue date: 2013-07-05 / Large amounts of herbicides are used in agriculture to control weeds that pose risks to crops, resulting in increased production cost of farms. Also, if not applied properly, its use can cause resistance of spontaneous plants and result in residues in the environment, in the soil, the water or in toxicity to the crops. The objective of this research was to evaluate the residue of the 2,4-D herbicide in soil and its correlation with yield, as well as physical and chemical properties of the soil. The experiment was conducted on a farm in the city of Nova Santa Rosa, in the state of Paraná in the years 2011 and 2012. The main crops grown in the area are corn and soybeans, in rotation. Soil samples were collected to determine their physical and chemical properties and for analysis of residual 2,4-D before implementation (RI) and after application (RF) of the 2,4-D herbicide. Initially, the glyphosate herbicide was applied in a single dose (2.5 L ha-1) and then the 2,4-D herbicide was applied at two doses (1,0 and 1,5 L ha-1) with boom sprayer and, after 5 days of application, soil samples were collected for analysis of RF. After extracting the 2,4-D from the soil, high performance liquid chromatography (HPLC) was carried out to detect the active ingredient. In order to map the spontaneous plants, before and after spraying the herbicide the method of systematic sampling was used. The soybean yield for both years were also analyzed, and finally, spatial correlation of the parameters evaluated was performed. The results of RI of 2,4-D in the soil in both years, demonstrating that this is a herbicide that can remain retained in the soil over time and, depending on the soil characteristics, the preparation of the area and climatic conditions, this time can be longer. In 2011, the maximum detection of the active ingredient was 609 μg kg-1 and in 2012 was 652 μg kg-1. The RI of 2,4-D in the soil showed negative spatial correlation for chemical attributes K, organic matter and pH and for physical density, macroporosity, microporosity, total porosity and soil moisture it showed positive spatial correlation with sand and the chemical attributes Cu, Mg, Mn, P and Zn in the first year assessed. In 2012 the spatial correlation was positive with clay. The spontaneous plants type horseweed (Conyza bonariensis), did not present spatial correlation among the parameters evaluated in 2011, however, showed a positive correlation with the micropores of the soil in 2012. As residual 2,4-D in the soil and many attributes analyzed presented spatial correlation, spatial correlation among the variables analyzed proved to be an important tool to understand the influence of a parameter over the other. Both doses satisfactorily controlled the incidence of spontaneous plants. The 2,4-D showed some points with detection and other with no detection of the active ingredient in the soil, a fact that demonstrates the importance of assessing the spatial correlation of soil properties (chemical and physical) with residual herbicide in the soil, determining the influence of one attribute over the other. / Grandes quantidades de herbicidas são utilizadas na agricultura para controlar plantas espontâneas que oferecem riscos às plantações, acarretando aumento do custo de produção das propriedades agrícolas. Além disso, se não forem aplicados corretamente podem ocasionar a resistência das plantas espontâneas e resultar em residual no ambiente, quer seja no solo, na água ou na toxidez para as culturas. O objetivo desta pesquisa foi avaliar o residual do herbicida 2,4-D no solo e a sua correlação com a produtividade e os atributos químicos e físicos do solo. O experimento foi desenvolvido em uma propriedade agrícola, do município de Nova Santa Rosa/Paraná nos anos de 2011 e 2012. As principais culturas cultivadas na área são o milho e a soja em sistema de rotação. Foram realizadas amostragens de solo para determinação dos seus atributos químicos e físicos e para análise do residual de 2,4-D antes da aplicação (RI) e após a aplicação (RF) do herbicida 2,4-D. Inicialmente, foi aplicado o herbicida glifosato em dosagem única (2,5 L ha-1) e, em seguida, aplicou-se o herbicida 2,4-D em duas doses (1,0 e 1,5 L ha-1) com pulverizador de arrasto e, após 5 dias da aplicação, amostras de solo foram coletadas para análise do RF de 2,4-D. Após a extração do 2,4-D do solo foi efetuada a determinação por meio de cromatografia líquida de alto desempenho (HPLC) para detecção do ingrediente ativo. Para o mapeamento das plantas espontâneas, antes e após a pulverização do herbicida foi utilizado o método da amostragem sistemática. Também foi avaliada a produtividade da soja para ambos os anos e, por fim, foi efetuada a correlação espacial dos parâmetros avaliados. Os resultados do RI de 2,4-D no solo em ambos os anos, demonstram que este é um herbicida que pode permanecer retido no solo com o passar do tempo e, dependendo das características do solo, do preparo da área e das condições climáticas será maior ou menor. Em 2011, o valor máximo de detecção do ingrediente ativo foi de 609 μg kg-1 e em 2012 foi de 652 μg kg-1. O RI de 2,4-D no solo apresentou correlação espacial negativa para os atributos químicos K, matéria orgânica e pH e para os atributos físicos densidade do solo, macroporosidade, microporosidade, porosidade total e umidade do solo e correlação espacial positiva com a areia e com os atributos químicos Cu, Mg, Mn, P e Zn no primeiro ano avaliado. Já em 2012, a correlação espacial foi positiva com a argila. As plantas espontâneas do tipo buva (Conyza bonariensis) não apresentaram correlação espacial com os parâmetros avaliados em 2011, porém apresentaram correlação positiva com os microporos do solo em 2012. Como residual de 2,4-D no solo e muitos atributos analisados apresentaram dependência espacial, a correlação espacial entre as variáveis analisadas mostrou-se uma ferramenta importante para se conhecer a interferência de um parâmetro sobre o outro. Ambas as doses controlaram de modo satisfatório a incidência de plantas espontâneas. O 2,4-D apresentou alguns pontos com detecção e outros sem detecção do ingrediente ativo no solo, fator que demonstra a importância de avaliar a correlação espacial dos atributos do solo (químicos e físicos) com o residual do herbicida no solo, determinando a influência de um atributo sobre outro.

La industria textil valenciana y española está sufriendo una de las mayores crisis de su historia. La pérdida de empleo industrial se sucede mes tras mes y las perspectivas son cada vez menos halagüeñas. Como en otras circunstancias adversas, la innovación y el desarrollo de nuevos productos podría ser una solución a estos problemas. Entre los productos que presentas mayores perspectivas en la actualidad, pero sobre todo un futuro cercano, están los textiles diseñados para la agricultura, los llamados Agro-textiles. Estos productos pueden y deben de ser utilizados allí donde la pérdida de suelo sea alta como es el caso de los campos de cultivo. Pero también tienen presentes y futuras aplicaciones en la agricultura con el fin de reducir el uso de herbicidas, mejorar las condiciones térmicas e hídricas de los suelos y reducir la pérdida de nutrientes, semillas, suelo y agua. Estas aplicaciones en la agricultura deben de conocerse y aplicarse para la obtención de mayores rentabilidades en los cultivos. Durante cuatro años se ha estado realizando un trabajo de campo previo para la obtención de datos relevantes que nos sirvan para efectuar un cálculo de la viabilidad de su utilización. La tesis que se presenta versa sobre el uso de Agrogeotextiles haciendo mención a la necesidad en algunos caso de su utilización, pero introduciendo como novedad la variable sostenibilidad La Tesis Doctoral se divide en dos grandes bloques; el primero de ellos trata de corroborar la importancia de la utilización de los agrotextiles como aportación a la sostenibilidad medioambiental en difentes campos de actuación.En el segundo bloque sirve para traducir la obtención de resultados económicos en un estudio de viabilidad o no del agrotextil estudiando determinadas variables y a posteriori se corrobora el mismo mediante un estudio de modelización de la eficiencia, nunca antes utilizado en este campo. / Giménez Morera, A. (2010). Utilización de Agrotextiles. Análisis de viabilidad y modelización de la eficacia [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/8509 / Palancia

<p>Ispitana je kinetika i mehanizam fotokatalitičke&nbsp;razgradnje herbicida kvinmeraka i klomazona u prisustvu&nbsp;UV/TiO₂&nbsp; Degussa P25, odnosno piklorama i&nbsp; klopiralida&nbsp;<br />primenom UV/TiO₂&nbsp; Wackherr pri različitim&nbsp;eksperimentalnim uslovima. Praćena je i kinetika&nbsp;razgradnje odabranih herbicida direktnom fotolizom uz&nbsp;primenu sunčevog, UV i vidljivog zračenja, kao i u&nbsp;odsustvu svetlosti. Pored toga, upoređena je efikasnost&nbsp;<br />UV/TiO₂&nbsp; Degussa P25, odnosno UV/TiO₂&nbsp; Wackherr sa&nbsp;vidljivim zračenjem, kao i direktnom fotolizom u&nbsp;prisustvu pomenutih izvora svetlosti.&nbsp; U cilju procene&nbsp;<br />citotoksičnosti klomazona i klopiralida, kao i sme&scaron;e&nbsp;klomazona i klopiralida i njihovih intermedijera nastalih&nbsp;tokom fotokatalitičke razgradnje ispitan je&nbsp; in vitro&nbsp; rast&nbsp;<br />ćelijskih linija&nbsp; MRC-5 i H-4-II-E.&nbsp; Nakon ispitivanja&nbsp;fotokatalitičke razgradnje odabranih herbicida u dvaput&nbsp;destilovanoj vodi, praćena je njihova razgradnja i u&nbsp;prirodnim vodama. Takođe, ispitan je uticaj dodatka&nbsp;hidrogenkarbonata i huminske kiseline na efikasnost&nbsp;razgradnje odabranih herbicida. Fotokatalitička razgradnja&nbsp;klomazona, piklorama i mekopropa je ispitivana i u&nbsp;prisustvu UV/TiO₂&nbsp; nanocevi. Aktivnost katalizatora TiO_2&nbsp;Wackherr&nbsp; i TiO₂&nbsp; nanocevi je upoređena sa TiO₂&nbsp; Degussa&nbsp;P25.</p> / <p>The kinetics and mechanism of photocatalytic degradation&nbsp;of the herbicides quinmerac and clomazone in the&nbsp;presence of UV/TiO₂&nbsp; Degussa P25, and of picloram and&nbsp;clopyralid using UV/TiO₂&nbsp; Wackherr under different&nbsp;experimental conditions were studied. The kinetics of&nbsp;degradation of selected herbicides by direct photolysis&nbsp;using sunlight, UV and visible radiation, and in the&nbsp;absence of light were followed. In addition, the&nbsp;efficiencies of UV/TiO₂&nbsp; Degussa P25 and UV/TiO_2&nbsp;Wackherr &nbsp;were compared with visible radiation and direct&nbsp;photolysis in the presence of the above mentioned light&nbsp;sources. In order to evaluate the cytotoxicity of clomazone&nbsp;<br />and clopyralid alone and in their mixture with&nbsp;intermediates formed during the photocatalytic&nbsp;degradation, in vitro growth of cell lines, MRC-5 and H-4-II-E was followed. After examining&nbsp; the photocatalytic&nbsp;degradation of selected herbicides in double distilled&nbsp;water, their decomposition in natural waters was also&nbsp;followed. Also, the influence of hydrogencarbonate and&nbsp;humic acid addition on the efficiency of degradation of&nbsp;selected herbicides was studied. Photocatalytic&nbsp;degradations of clomazone, picloram and mecoprop were&nbsp;investigated in the presence of UV/TiO_2&nbsp;nanotubes. Activities of the catalysts TiO₂&nbsp; Wackherr and TiO_2&nbsp;nanotubes were compared to TiO₂ Degussa P25.</p>

<p>Kao &scaron;to je poznato, RS-2-(4-hlor-o-toliloksi)propionska kiselina (MCPP),&nbsp;(4-hlor-2-metilfenoksi)sirćetna kiselina (MCPA) i 3,6-dihlorpiridin-2-karboksilna kiselina &nbsp;(klopiralid) su herbicidi sa veoma &scaron;irokim spektrom dejstva, a pored toga su rastvorljivi u&nbsp;vodi, te&scaron;ko biorazgradljivi i prema literaturnim podacima su, nažalost, veoma često prisutni&nbsp;herbicidi u pijaćoj vodi. Proces heterogene fotokatalize uz primenu TiO₂i UV zračenja se&nbsp;pokazao kao veoma pogodan način za njihovo uklanjanje iz vode. Međutim, zbog velikog&nbsp;energetskog procepa od 3,2 eV (anataze-oblik), odnosno, 3,0 eV (rutil-oblik), veoma mali&nbsp;udeo bliskih UV zraka iz sunčeve svetlosti (oko 3&minus;4%) biva iskori&scaron;ćen u toku&nbsp;fotokatalitičkog procesa, &scaron;to ukazuje na to da je TiO_2&nbsp;praktično neaktivan u prisustvu&nbsp;sunčeve svetlosti. Na osnovu literaturnih podataka je zapaženo da postoji mogućnost&nbsp;fotorazgradnje pojedinih supstrata u prisustvu TiO_2&nbsp;primenom vidljive svetlosti. Na&nbsp;primeru MCPP je ispitana aktivnost TiO_2&nbsp;Degussa P25 kao fotokatalizatora u prisustvu&nbsp;vidljive svetlosti. Na osnovu refleksionih spektara je utvrđeno da MCPP adsorbovan na&nbsp;TiO_2&nbsp;Degussa P25 apsorbuje vidljivi deo spektra (&lambda; &ge;400 nm). Nastali prelazni kompleks&nbsp;je potvrđen FTIR merenjima. Efikasnost TiO2Degussa P25 primenom vidljive svetlosti je&nbsp;upoređena sa sunčevim i UV zračenjem, kao i direktnom fotolizom u prisustvu pomenutih&nbsp;izvora zračenja. Brzina fotokatalitičke razgradnje MCPP primenom vidljive svetlosti iznosi&nbsp;0,86 &mu;mol dm^&minus;3min^&minus;1, &scaron;to je oko 4 puta brže u poređenju sa direktnom fotolizom. Nadalje&nbsp;je ustanovljena optimalna masena koncentracija katalizatora od oko 8 mg cm^&minus;3, koja je&nbsp;znatno vi&scaron;a u poređenju sa primenom UV zračenja. Razlog je najverovatnije različit&nbsp;mehanizam fotorazgradnje koji se odvija primenom vidljivog i UV zračenja. Naime,&nbsp;prisustvo 2-metil-2-propanola (poznatog hvatača&nbsp;^&bull;OH-radikala) praktično ne utiče na&nbsp;brzinu fotokatalitičke razgradnje MCPP p rimenom vidljive svetlosti, &scaron;to ukazuje da se&nbsp;mehanizam razgradnje MCPP primenom &nbsp;vidljive svetlosti ne odvija posredstvom&nbsp;^&bull;OH-radikala, za razliku od onog uz primenu UV zračenja.</p><p>S obzirom da se katalizator TiO_2&nbsp;Degussa P25 uz primenu vidljive svetlosti nije&nbsp;<br />pokazao kao naročito efikasan kada je u pitanju razgradnja sva tri herbicida i imajući u&nbsp;vidu da se u poslednje vreme iz razloga praktične primene sve vi&scaron;e pribegava procesu dopovanja TiO_2&nbsp;različitim tipovima metala (alkalnih, zemnoalkalnih, prelaznih i dr.) i nemetala (halogenida, halkogenida i dr.), u okviru ove doktorske disertacije je ispitana aktivnost N-TiO₂(sintetisanih mokrim i suvim putem) i TiO_2&nbsp;(rutil) dopovanog sa različitim količinama Fe³⁺-jona (0,13&minus;1,48 at.%) pri razgradnji herbicida MCPP i MCPA primenom vidljive svetlosti. Pored toga je ispitana efikasnost TiO_2&nbsp;(anataze) takođe dopovanog sa različitim količinama Fe³⁺-jona (0,71&minus;1,80 at.%) na primeru MCPP.&nbsp;</p><p>Poredeći N-TiO_2&nbsp;(sintetisan mokrim putem) i N-TiO_2&nbsp;(sintetisani suvim putem), primećeno&nbsp;je da je u drugom slučaju efikasnost katalizatora veća oko 2 puta. Isto tako je zapažena u&nbsp;slučaju MCPP ne&scaron;to veća fotokatalitička aktivnost N-TiO_2&nbsp;(sintetisani suvim putem) u&nbsp;poređenju sa TiO_2&nbsp;(anataze). Kada je u pitanju MCPA aktivnost sva tri katalizatora je&nbsp;veoma slična. Pored toga je zapažena veća efikasnost N-TiO_2&nbsp;(sintetisan mokrim putem) u&nbsp;poređenju sa TiO_2&nbsp;Degussa P25 (oko 1,5 puta) i oko 5 puta u odnosu na direktnu fotolizu,&nbsp;dok su N-TiO_2&nbsp;(sintetisani suvim putem) oko 3 puta efikasniji u poređenju sa TiO_2&nbsp;Degussa P25 i oko 10 puta u &nbsp;poređenju sa direktnom fotolizom. Brzina solarne razgradnje&nbsp;je preko 100 puta manja nego primenom vidljivog i UV zračenja, &scaron;to je posledica različitih&nbsp;intenziteta pomenutih izvora ozračivanja i različitih uslova pri kojima je vr&scaron;ena razgradnja. &nbsp;Ustanovljena je optimalna masena koncentracija N-TiO_2&nbsp;(sintetisan mokrim putem) od&nbsp;4 mg cm^&minus;3.</p><p>Prilikom razgradnje MCPP i MCPA je nađeno da je brzina veća kada se kao&nbsp;katalizator &nbsp;koristi TiO_2&nbsp;(rutil) u poređenju sa Fe-TiO_2&nbsp;i da sa povećanjem količine Fe³⁺-jona fotokatalitička aktivnost uglavnom opada. Kada je kao fotokatalizator kori&scaron;ćen TiO_{2 &nbsp;}<br />(anataze) dopovan različitim količinama Fe³⁺-jona (od 0,71 do 1,80 at.%), razgradnja&nbsp;<br />MCPP je u svim slučajevima znatno sporija u odnosu na TiO_2&nbsp;(anataze).</p><p>S obzirom da su prema literaturnim podacima kinetika i mehanizam fotokatalitičke&nbsp;<br />razgradnje klopiralida nepoznati, ispitana je njegova stabilnost pri različitim&nbsp;eksperimentalnim uslovima. Tokom ispitivanja uticaja pH kako u prisustvu, tako i u&nbsp;odsustvu dnevne svetlosti u intervalu pH od 1,0&minus;9,0, nađeno je da ni u jednom slučaju ne&nbsp;dolazi do razgradnje supstrata u periodu od sedam meseci koliko je proces praćen. Takođe&nbsp;je ispitana kinetika fotokatalitičke razgradnje klopiralida primenom UV i vidljivog&nbsp;zračenja u prisustvu TiO_2&nbsp;Degussa P25, kao i direktna fotoliza primenom oba izvora&nbsp;zračenja. Nađeno je da je brzina fotokatalitičke razgradnje primenom UV zračenja veća&nbsp;oko 5 puta u odnosu na direktnu fotolizu. Za praćenje toka fotokatalitičke razgradnje&nbsp;klopiralida je izabrana pH-vrednost od 3,2. Nadalje je zapaženo da se u ispitivanom opsegu početnih koncentracija supstrata (0,5&ndash;3,0 mmol dm^&minus;3) kinetika fotokatalitičke razgradnje klopiralida može opisati pseudo-prvim redom. Pri ispitivanju uticaja masene koncentracije katalizatora (0,5&ndash;8 mg cm^&minus;3) na brzinu razgradnje klopiralida, ustanovljena je optimalna masena koncentracija primenjenog fotokatalizatora od oko 4 mg cm^&minus;3. Izračunata ukupna &nbsp;prividna energija aktivacije iznosi 7,74 kJ mol^&minus;1. Pored toga, prisustvo kiseonika ubrzava reakciju 2 puta, dok dodatak elektron-akceptora kao &scaron;to su (NH₄)₂S₂O₈, H₂O_2&nbsp;i KBrO_3&nbsp;pokazuje značajan i različit efekat na kinetiku fotokatalitičke razgradnje klopiralida. Pri ispitivanju uticaja etanola, kao hvatača slobodnih radikala, nađeno je da se heterogena fotokataliza odvija uglavnom preko ^&bull;OH-radikala.</p><p>Na osnovu LC&ndash;MS/MS (ESI+) merenja ustanovljeno je prisustvo nekoliko&nbsp;intermedijera: 3,6-dihlor-piridin-2-ol, 3,6-dihlor hidroksipiridin-2-karboksilna kiselina i&nbsp;3,3&#39;,6,6&#39;-tetrahlor-2,4&#39;-bipiridin-2&#39;-karboksilna kiselina. Na osnovu identifikovanih&nbsp;intermedijera, kao i kinetičkih rezultata, predložen je mogućput mehanizma fotokatalitičke&nbsp;razgradnje klopiralida.</p><p>Prilikom ispitivanja uticaja strukture molekula na brzinu razgradnje, konstatovano&nbsp;<br />je da u slučaju klopiralida praktično ne dolazi do fotokatalitičke razgradnje u prisustvu&nbsp;TiO_2&nbsp;(anataze) i N-TiO_2&nbsp;(sintetisani suvim putem) uz primenu vidljive svetlosti, kao i u&nbsp;slučaju TiO_2&nbsp;Degussa P25. Pored toga, primenom TiO_2&nbsp;(rutil) i Fe-TiO_2&nbsp;kao&nbsp;fotokatalizatora, sa povećanjem količine Fe³⁺-jona od 0,13 do 1,27 at.% raste brzina&nbsp;razgradnje klopiralida, ukazujući da strukturne osobine supstrata utiču na brzinu njihove&nbsp;razgradnje.</p> / <p>It is well known that RS-2-(4-chloro-o-tolyloxy)propionic acid (MCPP), (4-chloro-2- methyl-phenoxy)acetic acid (MCPA) and 3,6-dichloropyridine-2-carboxylic &nbsp;acid&nbsp;(clopyralid) are herbicides of wide activity spectrum. They are soluble in water, hardly&nbsp;biodegradable and, unfortunately, often present in drinking water.</p><p>Heterogeneous photocatalysis by application of TiO_2&nbsp;and UV radiation proved to&nbsp;be very suitable for their removal from water. However, due toits large energy gap, i.e.&nbsp;3.2 &nbsp;eV (anatase-form) and 3.0 eV (rutile-form), a very small fraction of sunlight in the near&nbsp;UV range (about 3&ndash;4%) is used during photocatalytic process, which is an indication of&nbsp;TiO_2&nbsp;inactivity in the presence of this light source. Some literature data report on the&nbsp;possibility of photodegradation of certain substrates by visible light in the presence of&nbsp;TiO₂. MCPP served as substrate for testing TiO_2&nbsp;Degussa P25 &nbsp;photocatalytic activity in the&nbsp;presence of visible light. On the basis of reflection spectra it was established that MCPP&nbsp;adsorbed on TiO_2&nbsp;Degussa P25 was absorbing visible spectrum radiation (&lambda; &ge;400 nm).&nbsp;The existence of thus formed &nbsp;charge-transfer complex was confirmed with FTIR analysis.&nbsp;The efficiency of &nbsp;TiO_2&nbsp;Degussa P25 with application of visible light was compared to&nbsp;sunlight and UV radiation, as well to directphotolysis in the presence of these light&nbsp;sources. The rate of MCPP photocatalytic degradation by means of visible light is&nbsp;0.86 &mu;mol dm^{&minus;3&nbsp;}min^&minus;1, which is about 4 times faster than direct photolysis. In addition, the&nbsp;optimal &nbsp;catalyst concentration of about 8 mg cm^&minus;3, much higher than using UV radiation,&nbsp;<br />was established. The reason is, probably, a different mechanism of &nbsp;hotodegradation &nbsp;in the&nbsp;presence of visible and UV irradiation. Namely, the presence of 2-methyl-2-propanol&nbsp;(well-known&nbsp;^&bull;OH radical scavenger) has practicallyno effect on the rate of &nbsp;MCPP&nbsp;photocatalytic degradation using visible light, which points that this degradation&nbsp;mechanism does not involve&nbsp;^&bull;OH radicals, in contrast to that established &nbsp;for UV radiation.</p><p>Since the catalyst TiO_2&nbsp;Degussa P25 with application of visible light was not very&nbsp;<br />efficient in degradation of all three herbicidesand in view that nowadays is very &nbsp;popular&nbsp;doping process of TiO₂ with different types of metals (alkali, alkaline-earth, transition, etc.)&nbsp;and non-metals (halogen, chalcogen, etc.), in the scope of this Ph.D. &nbsp;thesis activities of N-TiO_2&nbsp;(synthesized by wet and dry procedure) and TiO_2&nbsp;(rutile) doped with various amounts&nbsp;of Fe^3+&nbsp;(0.13&ndash;1.48 at.%) in degradation processes of &nbsp;herbicides MCPP and MCPA using&nbsp;visible light were studied. In addition, the efficiency of TiO_2&nbsp;(anatase) doped with various&nbsp;amounts of Fe^3+&nbsp;(0.71&ndash;1.80 at.%) was also tested for MCPP degradation. When comparing&nbsp;N-TiO_2&nbsp;(synthesized by wet procedure) and N-TiO₂ (dry procedure), it was observed that&nbsp;in the latter case the catalyst efficiency was about two times higher. In this case for MCPP&nbsp;was also observed somewhat higher photocatalytic activity of N-TiO₂ (synthesized by dry&nbsp;procedure) in comparison with TiO₂. When activities of all three catalysts towards MCPA&nbsp;are compared, the results are very alike. In addition, higher efficiency of N-TiO_{2 &nbsp;}(wet&nbsp;procedure) comparing to TiO_2&nbsp;Degussa P25 (about 1.5 times) and about 5 times in&nbsp;comparison to direct photolysis were recorded, while N-TiO₂ (dry procedure) was about 3&nbsp;times more efficient than TiO_2&nbsp;Degussa P25 and about 10 times in comparison with direct&nbsp;photolysis. The rate of solar degradation is about 100 times lower than by application of&nbsp;UV and visible radiation, as a consequence of various intensities of the mentioned light&nbsp;sources and different conditions of photodegradation. An optimal concentration of N-TiO₂&nbsp;(wet procedure) of 4 mg cm^&minus;3<br />&nbsp;was established.</p><p>During degradation of MCPP and MCPA it was observed that the rate is higher if&nbsp;TiO₂(rutile) was applied comparing to Fe-TiO_2&nbsp;and with increasing amount of Fe^3+&nbsp;photocatalytic activity mostly decreases. When TiO₂ (anatase) doped with various amounts&nbsp;of Fe^3+&nbsp;(0.71 to 1.80 at.%) was applied for MCPP degradation, the process was much&nbsp;slower than with undoped catalyst.</p><p>Since we have not found relevant literature data on kinetics and mechanism of&nbsp;photocatalytic degradation of clopyralid, its stability in different experimental conditions&nbsp;was tested. In investigating of influences of pH (1.0&ndash;9.0) both in presence and in absence&nbsp;of daylight, in no cases decomposition was observed during seven months experiments.&nbsp;Also, the kinetics of photocatalytic degradation of clopyralid using UV and visible&nbsp;irradiation in the presence of TiO_2&nbsp;Degussa P25 and in direct photolysis by application of&nbsp;both irradiation sources was studied. It was found that the &nbsp;rate of photocatalytic&nbsp;decomposition using UV radiation was 5 times higher comparing to direct photolysis. For&nbsp;clopyralid photocatalytic monitoring a pH value of &nbsp;3.2 was chosen. In addition, in the investigated concentration range (0.5&ndash;3.0 mmol &nbsp;dm^&minus;3) the photocatalytic degradation kinetics of clopyralid in the first stage of the reaction follows approximately a pseudo-first kinetic order. In investigation of influence of catalyst concentration (0.5&ndash;8 mg cm^&minus;3) on the rate of clopyralid degradation the highest reaction rate was observed at 4 mg cm^{&minus;3&nbsp;}of catalyst concentration The apparent activation energy of the reaction being 7.74 kJ mol^&minus;1. The absence of molecular oxygen resulted in a significant decrease (about 2 times) in the rate of clopyralid photodegradation. The effect of the presence of (NH₄)₂S₂O₈, H₂O_2&nbsp;and KBrO₃, acting as electron acceptors along with molecular oxygen affects clopyralid photocatalytic degradation considerably and indifferent ways. By studying the effect of ethanol as a hydroxyl radical scavenger it was shown that the heterogeneous catalysis takes place mainly via ^&bull;OH radicals.</p><p>LC&minus;MS/MS (ESI+) monitoring of the process showed that several pyridine-containing intermediates are formed: 3,6-dichloropyridin-2-ol, 3,6-dichloro&nbsp;hydroxypyridine-2-carboxylic acid and 3,3&#39;,6,6&#39;-tetrachloro-2,4&#39;-bipyridine-2-carboxylic&nbsp;acid. Based on the identified intermediates and overall kinetic results, a probable&nbsp;photocatalytic degradation mechanism was proposed.&nbsp;</p><p>Finally, in the case of clopyralid it was established that practically no degradation&nbsp;<br />occurs in the presence of TiO_2&nbsp;(anatase) and N-TiO₂ (dry procedure) with visible light &nbsp;and&nbsp;also with TiO_2&nbsp;Degussa P25. Besides of that, by using TiO_2&nbsp;(rutile) and Fe-TiO_2&nbsp;as&nbsp;photocatalysts it was noted that increasing the concentration of Fe^3+&nbsp;from 0.13 to 1.27 at.%&nbsp;comes to increasing photodegradation rate of clopyralid. Results indicate that differences&nbsp;in molecular structure of chosen compound, influence obtained photocatalytic activity to a&nbsp;great extent.</p>

Made available in DSpace on 2017-07-10T18:13:14Z (GMT). No. of bitstreams: 1 Denise N de Bastos.pdf: 584150 bytes, checksum: 5ec6369c1a7266f038b37ea1a2b8ccdd (MD5) Previous issue date: 2013-06-26 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The objective of this study was to avaluate the toxicity to Daphnia magna cultivated on a large scale and post-larvae of jundia (Rhamdia quelen) to Glyphosate herbicide and the reference substances. Were used daphnia with age between 2 and 26 hours of life, from large scale cultured arrays. There were performed six sensitivity assays that were composed of seven treatments and three replica, at concentrations of 0; 0.1; 0.3; 0.5; 0.7; 0.9 and 1.2 mg.L-1 of potassium dichromate, with 24 hours duration. The acute toxicity assays, with copper sulfate at concentrations of 0; 0.01; 0.025; 0.05; 0.075 and 0.10 mg.L-1, and to the glyphosate concentrations of 0; 11; 21; 31; 41 and 51 µg.L-1, with three and two replica respectively, and 48 hours duration. However the post-larvae of jundia were exposed to concentrations of 0; 0.5; 1.0; 1.5; 2.0 and 2.5 mg.L-1 of glyphosate, per 96 hours. Each replica was composed of a bottle with 10 individuals. The chronic toxicity test, the daphnia were exposed to concentrations of 0, 2, 4, 6, 8 and 10 µg.L-1 of glyphosate, with 10 replica, being a daphnia per replica, evaluating the survival and fecundity in 21 days. For acute toxicity assays, was calculated mortality using the Median Effective Concentration (EC50) in each test. The mean EC50 for D. magna with potassium dichromate was 0.57 mg.L-1. The value of acute toxicity for copper sulphate was reached at a concentration of 0.034 mg.L-1. And for the glyphosate the EC50 of 32 µg.L-1 is toxic for the species. The chronic assay showed high rate of mortality, possibly the result of unfavourable conditions for the large scale cultivation of arrays, hurt his endurance. For the R. quelen the EC50 was achieved at 0.9 mg. L-1. The results showed that organisms of the species D. magna cultivated on a large scale can be used in acute toxicity tests, but not in chronic toxicity testing, for the assessment of water quality. / O objetivo deste trabalho foi avaliar a toxicidade de Daphnia magna cultivada em larga escala e pós-larvas do jundiá (Rhamdia quelen) ao herbicida Glifosato e a substâncias de referência. Foram utilizadas dáfnias com idade de 2 a 26 horas de vida, provenientes de matrizes cultivadas em larga escala. Foram realizados seis ensaios de sensibilidade que foram compostos por sete tratamentos e três réplicas, nas concentrações de 0; 0,1; 0,3; 0,5; 0,7; 0,9 e 1,2 mg.L-1 de dicromato de potássio, com duração de 24 horas. E os testes de toxicidade aguda, com sulfato de cobre nas concentrações de 0; 0,01; 0,025; 0,05; 0,075 e 0,10 mg.L-1, e para o glifosato as concentrações de 0; 11; 21; 31; 41 e 51 µg.L-1, com três e duas réplicas respectivamente, e duração de 48 horas. Já as pós-larvas de jundiá foram expostas às concentrações de 0; 0,5; 1,0; 1,5; 2,0 e 2,5 mg.L-1 de glifosato, por 96 horas. Cada réplica era composta de um frasco com 10 indivíduos. No teste de toxicidade crônica, as dáfnias foram expostas as concentrações de 0, 2, 4, 6, 8 e 10 µg.L-1 de glifosato, com 10 réplicas, sendo uma dáfnia por réplica, avaliando a sobrevivência e fecundidade em 21 dias. Para os experimentos de toxicidade aguda foi calculada mortalidade através da Concentração Efetiva Mediana (CE50) em cada teste. A média da CE50 para a D. magna com dicromato de potássio foi de 0,57 mg.L-1. O valor de toxicidade aguda para o sulfato de cobre foi alcançado na concentração de 0,034 mg.L-1. Já para o glifosato a CE50 de 32 µg.L-1 é toxica para a espécie. No teste crônico, a alta taxa de mortalidade possivelmente é resultado das condições desfavoráveis no cultivo das matrizes em larga escala, o que prejudicou sua resistência. Para o R. quelen a CE50 alcançada foi em 0,9 mg.L-1. Os resultados demostraram que organismos da espécie D. magna cultivadas em larga escala podem ser utilizados em testes de toxicidade aguda, mas não em testes de toxicidade crônica, para a avaliação da qualidade da água.