Herbicides have become a key component in modern agricultural production. Meanwhile, there is a concern that some herbicides persist past the growing season of the treated crop, and negatively influence the production of the subsequently planted crops. Amongst various herbicides used in western Canada, acetohydroxyacid synthase (AHAS)-inhibiting herbicides warrant special attention given their residual properties and acute plant toxicity at low concentrations in soil. Soil residual AHAS inhibitors have the potential to influence both leguminous host plants and their bacterial symbiotic partners; consequently, the use of an AHAS inhibitor in a given year can negatively influence the inoculation success and grain yield of legumes cropped in the following year. <p>The present thesis project focused on one of the AHAS inhibiting herbicides (flucarbazone) and studied its potential for carryover injury and negative influence on the success of inoculation in field pea. A series of growth chamber and field experiments were conducted to test the following null hypothesis: the presence of residual flucarbazone in soil does not affect nodulation of field pea by inoculum rhizobia. <p>A growth chamber experiment clearly demonstrated the susceptibility of field pea to the presence of flucarbazone in soil where the lowest concentration of flucarbazone amendment (5 ìg kg1) significantly reduced the crop growth. In contrast, a field study failed to reveal any negative effects of flucarbazone use on crop growth and N2 fixation. <p>It was concluded that if the weather and soil conditions favour decomposition of flucarbazone as described in the present study, flucarbazone applied at the recommended field rate will not persist into the following season at high enough concentrations to negatively influence field pea growth, grain yields, and inoculation success. To ensure safety of rotational crops, it is important to strictly adhere to the herbicide application guidelines. Additionally, producers are cautioned to be particularly aware of the environmental and soil conditions that may reduce the rate of herbicide degradation.

El control d'herbicides i altres anàlits orgànics presents en el medi ambient constitueix una pràctica habitual en els laboratoris des de l'establiment de legislacions que limiten la seva concentració. Per aquesta raó, cal el desenvolupament de noves metodologies analítiques per al seguiment de compostos orgànics en el medi. Molt sovint aquests anàlits es troben a nivells traça en aigües i sòls, conjuntament amb un alt contingut de substàncies húmiques i fúlviques. Així, un dels reptes existents és el tractament de la mostra (extracció, concentració i "clean-up" d'aquests anàlits per a una bona quantificació). Aquests processos han de venir complementats per tècniques cromatogràfiques que permetin la mesura final dels anàlits.La investigació que es presenta en aquesta tesi es centra en el desenvolupament d'un mètode per a la determinació de 2,4-D i MCPA i els seus metabòlits fenòlics i d'un altre per a la determinació de cafeïna. El primer dels procediments desenvolupats s'ha aplicat al seguiment dels herbicides i els metabòlits fenòlics en sòls d'un camp de golf, mentre que el segon s'ha emprat per a la determinació de cafeïna en aigües naturals i, posteriorment, en aigües residuals. / The control of herbicides and other organic pollutants present in the environment has become a routine practise in many laboratories since the establishment of legislations that indicates the maximum allowed levels for these compounds. For this reason, it is necessary to develop new analytical methodologies for the monitoring of organic compounds in the environment. These analytes are often found at trace levels in waters and soils, with a high humic and fulvic organic matter content associated. One of the most important challenges in this field is the sample treatment (i.e. extraction, concentration and clean-up of the compounds to obtain a correct quantification). These procedures have to be coupled to chromatographic techniques to allow the determination of the compounds. This study is devoted to the development of a method for the determination of 2,4-D, MCPA and their phenolic metabolites and another method for the determination of caffeine. The first method has been applied for the monitoring of the herbicides and their metabolites in soils from a golf course; the second has been applied to the determination of caffeine in natural and urban wastewaters.

Herbicides have become a key component in modern agricultural production. Meanwhile, there is a concern that some herbicides persist past the growing season of the treated crop, and negatively influence the production of the subsequently planted crops. Amongst various herbicides used in western Canada, acetohydroxyacid synthase (AHAS)-inhibiting herbicides warrant special attention given their residual properties and acute plant toxicity at low concentrations in soil. Soil residual AHAS inhibitors have the potential to influence both leguminous host plants and their bacterial symbiotic partners; consequently, the use of an AHAS inhibitor in a given year can negatively influence the inoculation success and grain yield of legumes cropped in the following year. <p>The present thesis project focused on one of the AHAS inhibiting herbicides (flucarbazone) and studied its potential for carryover injury and negative influence on the success of inoculation in field pea. A series of growth chamber and field experiments were conducted to test the following null hypothesis: the presence of residual flucarbazone in soil does not affect nodulation of field pea by inoculum rhizobia. <p>A growth chamber experiment clearly demonstrated the susceptibility of field pea to the presence of flucarbazone in soil where the lowest concentration of flucarbazone amendment (5 ìg kg1) significantly reduced the crop growth. In contrast, a field study failed to reveal any negative effects of flucarbazone use on crop growth and N2 fixation. <p>It was concluded that if the weather and soil conditions favour decomposition of flucarbazone as described in the present study, flucarbazone applied at the recommended field rate will not persist into the following season at high enough concentrations to negatively influence field pea growth, grain yields, and inoculation success. To ensure safety of rotational crops, it is important to strictly adhere to the herbicide application guidelines. Additionally, producers are cautioned to be particularly aware of the environmental and soil conditions that may reduce the rate of herbicide degradation.

From the Proceedings of the 1977 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - April 15-16, 1977, Las Vegas, Nevada / Hydrologic information is needed to understand and control water pollution from semiarid rangelands. However, the hydrologic systems under any given conditions must be understood and the effects of various land uses predicted. Based on the concept of partial area response, a runoff tracer study was conducted on two small watersheds. The watersheds were partitioned into four geomorphic subzones or hydrologic response units. Each of the four zones on both watersheds was treated with about 1 kg/ha of an individual water soluble herbicide. Runoff volumes and sources estimated using the tracers were consistent with results from simulation studies. Also, the principle of corresponding runoff and pollutant discharge rates was used to develop two methods of runoff hydrograph estimation from each of the geomorphic subzones. Method 1 matched the mean total concentration and total runoff volume. Method 2 matched the instantaneous total concentration and the instantaneous runoff rate from the entire watershed. Results from the two methods suggested that, although they may be equivalent with respect to runoff volume, Method 2 may be more consistent with respect to peak discharge.

Les objectifs de développement de systèmes de culture durables imposent aux acteurs du développement rural une conception (ou reconception) et une évaluation de ces systèmes. Le prototypage peut être une méthodologie efficace de conception. Cependant, cette méthode conduit souvent les chercheurs à être seuls concepteurs alors que parallèlement l'appropriation des innovations dépend fortement de l'implication des autres acteurs dans les différentes étapes de conception et d'évaluation des nouveaux systèmes. En réponse, des approches participatives sont de plus en plus fréquentes pour pallier à cette difficulté d'appropriation tandis qu'une évaluation multicritère apporte une réponse aux objectifs d'évaluation de la durabilité des systèmes. La méthode développée dans cette thèse -nommée DISCS pour 're-Design and assessment of Innovative Sustainable Cropping Systems' - met en œuvre un processus de reconception des systèmes de culture par une approche participative tout en développant des outils d'évaluation multicritère spécifiques à chaque catégorie d'acteurs impliqués. La méthode DISCS s'inscrit tout de même dans la lignée de la méthodologie du prototypage mais se différencie par une démarche itérative à trois échelles d'étude (parcelle expérimentale, exploitation agricole et territoire) afin de s'assurer que les innovations et les critères d'évaluation répondent bien aux attentes des acteurs. A chaque étape du processus de reconception une évaluation est réalisée à l'aide d'un jeu d'indicateurs et ce aux trois échelles d'étude. DISCS a été testée sur le système de culture agrumicole en Guadeloupe (Antilles Françaises) dans un but de réduire l'utilisation des pesticides. Cinq prototypes de gestion de l'enherbement ont été conçus collectivement puis testés sur une station expérimentale selon les principes d'une approche systémique et évalués à l'aide d'indicateurs. Nous montrons dans ce travail que des systèmes de culture innovants peuvent être les produits d'une co-conception entre les producteurs et les chercheurs. DISCS permet aussi de définir explicitement le rôle de tous les différents acteurs impliqués dans le processus de reconception du système de culture. DISCS est particulièrement adaptée à la reconception des systèmes de culture pérenne notamment grâce à son processus d'amélioration pas à pas et itératif. Les outils d'évaluation multicritère développés, et notamment les indicateurs, permettent quant à eux de fournir des outils d'aide à la décision directement utilisables par les acteurs assurant ainsi un lien étroit entre la recherche et le développement. Dans cette thèse, nous présentons les premières étapes de reconception du système agrumicole guadeloupéen basée sur la méthode DISCS, à savoir du diagnostic initial pour identifier les objectifs d'amélioration du système en collaboration avec les acteurs, jusqu'à l'évaluation multicritère des prototypes de gestion de l'enherbement basée sur un jeu d'indicateurs approprié. Notre travail nous permet aujourd'hui de recommander des techniques de gestion de l'enherbement en jeunes vergers d'agrumes répondant aux contraintes actuelles de développement de systèmes de culture durable.

La guerre du Viêt Nam mit la forêt au cœur des enjeux militaires. Nées des controverses sur les conséquences environnementales des épandages d'herbicides, des hypothèses ont émergé sur les impacts de cette pratique : différentiels selon les unités paysagères, aggravés par les perturbations anthropiques antérieures et postérieures à la guerre. Relevant de la biogéographie, l'analyse géohistorique confronte des sources souvent divergentes et privilégie les princeps pour reconstituer, à des dates clés, les paysages d'une province au cœur du conflit. L'état actuel de partition en trois unités - plaine, collines et montagnes - révèle le lien entre perturbation et accessibilité. Circa 1954, les pratiques précoloniales et coloniales avaient déjà perturbé les écosystèmes, de manière croissante des montagnes vers la plaine. Les impacts d'une guerre dirigée contre le milieu furent directs et indirects. Après-guerre, ils furent aggravés par les pratiques civiles, qui bloquèrent la reconquête spontanée et provoquèrent déboisements et déforestations ; la pression s'accrut dans les collines et les montagnes, plus affectées par la guerre. Depuis circa 1990, les décisions politiques ont placé officiellement la forêt entre protection et développement mais elles se heurtent aux nécessités du développement économique. La reconquête, dirigée, accélérée par la plantation d'espèces à croissance rapide, est engagée dans des sylvosystèmes perturbés et épargnés par la guerre. Aujourd'hui, dans les trois unités paysagères, les zones défoliées ne sont pas identifiables : cicatrisation, poursuite du recul des forêts surtout ont fait leur œuvre. Restent visibles les géofaciès de cratères et les anciennes bases militaires américaines. La conjugaison des perturbations empêche l'identification du strict impact actuel de la guerre et relativise celui-ci ; plus affaiblis sont les sylvosystèmes de la plaine qui, moins touchés, subissent une forte pression séculaire.

Dans le cadre de la protection de l'environnement, l'eau et l'atmosphère sont deux milieux particulièrement surveillés. La réglementation impose la détection et le dosage d'une liste de produits mais les besoins analytiques sont considérables. Les méthodes biotechnologiques présentent l'avantage d'indiquer l'impact du produit sur la matière vivante. Ces méthodes sont mises en œuvre au laboratoire ou sur site. La détection d'une toxicité globale ou ciblée, <i>in situ</i> et en temps réel, est privilégiée. Les biocapteurs sont des outils répondant à cette attente. Au cours de l'étude, deux biocapteurs, l'un ampérométrique, l'autre fluorimétrique sont conçus. Tous deux intègrent le même biorécepteur, <i>Chlorella vulgaris</i>. Une nouvelle méthode d'immobilisation des micro-algues est mise au point. Elle permet d'obtenir des lots de membranes reproductibles, fonctionnelles 7 jours, donnant une réponse <i>in vivo</i> à valeur statistique, réutilisables et conservables. Des essais conduits sur des thylakoïdes extraits des cellules végétales ne donnent pas d'aussi bons résultats. L'association des membranes algales avec les deux types de transducteur montre que <i>Chlorella vulgaris</i> est sensible à des produits divers : herbicides, métaux, solvants. Les limites de détection pour des herbicides sont particulièrement basses, inférieures aux normes. Pour plusieurs produits testés, des courbes d'étalonnage sont données. Les deux types de biocapteur fonctionnent en milieu aqueux, en mode batch et en mode flux. Le biocapteur de fluorescence algale à fibres optiques possède des qualités de reproductibilité et de maniabilité plus intéressantes que le biocapteur ampérométrique. Le biocapteur de fluorescence est testé sur des lixiviats de bois, solutions naturelles complexes ; le biocapteur ampérométrique est adapté à l'utilisation en phase gazeuse, il détecte alors le méthanol vapeur et le perchloroéthylène en aérosol. Une autre partie de l'étude consiste à caractériser l'impact des toxiques sur <i>Chlorella vulgaris</i>. L'analyse est conduite en microscopie électronique à balayage et en microscopie optique couplée à l'analyse d'images. Ces deux méthodes originales restent à perfectionner. Les résultats de nos essais préliminaires semblent encourageants pour la détection du produit toxique et l'accès à son mécanisme d'action.

Made available in DSpace on 2015-03-26T13:40:04Z (GMT). No. of bitstreams: 1 texto completo.pdf: 721867 bytes, checksum: 85d9a5894fb1c5c90727aacafdb3de95 (MD5) Previous issue date: 2014-07-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The sweet sorghum can become an important alternative for ethanol production in the sugar cane offseason. For this, adjustments will be necessary in the arrangement of sorghum plants in the field, to use all the available infrastructure and logistics in ethanol plants that use sugar cane as raw material. Besides adjusting the spacing of sweet sorghum cultivation machinery harvesters sugar cane, another factor to be researched refers to weed management. Sorghum is characterized by its slow initial growth which makes it very susceptible to weed competition in the early stage of growth. This fact is compounded by low efficiency of herbicides registered for weed control grasses. In the search for solutions to these problems, this research evaluated the effects of plant arrangements associated with application of herbicides on weed dynamics, sweet sorghum growth and yield. The experiment was conducted under field conditions and evaluated three plant arrangements with spacings of 0.25 m, 0.45 m 0,45 - 0,45 - 0,90 m, keeping the population of 120,000 plants per hectare in all spacings, which were either not associated with herbicide application. At 7, 14 and 28 days after herbicide application visual intoxication plants, weed control and data collection for phytosociological studies of weed community were evaluated. The fresh weight, plant height, stem diameter, mass of broth and °Brix of the sorghum stock were evaluated at harvest, 120 days after sowing. It also assessed chemical characteristics of the broth as the concentrations of sucrose, glucose and fructose, by high performance liquid chromatography efficiency. For phytosociological studies, weed populations were analyzed by calculations of density, frequency and abundance relative importance value (IVI) and similarity index (SI). We conclude that the reduction in sweet sorghum spacing increases the fresh culture weight and the application of the herbicide mixture may be an option in the management of weeds in sorghum, mainly aimed at controlling grasses. However, doses above 960 g ha-1 s-metolachlor and atrazine mixture may compromise the growth and productivity of sweet sorghum. The Cyperus esculentus and Oxalis latifolia species shown to be more tolerant to herbicides, considering that showed higher IVI values, independent of treatment assessed. / O sorgo sacarino pode se tornar importante alternativa para produção de etanol na entressafra da cana-de-açúcar. Para isso, serão necessários ajustes no arranjo das plantas de sorgo no campo, para utilização de toda a infraestrutura e logística disponíveis nas usinas de etanol que utilizam a cana-de-açúcar como matéria prima. Além do ajuste do espaçamento de cultivo do sorgo sacarino às máquinas colhedoras de cana-de-açúçar, outro fator a ser pesquisado refere-se ao manejo de plantas daninhas. O sorgo se caracteriza por possuir crescimento inicial lento o que o torna muito susceptível à interferência das plantas daninhas na fase inicial de crescimento. Este fato é agravado devido à baixa eficiência dos herbicidas registrados para controle de plantas daninhas gramíneas. Na busca de soluções para esses problemas, nessa pesquisa foram avaliados os efeitos de arranjos de plantas associado a aplicação de herbicidas sobre a dinâmica das plantas daninhas, crescimento e produtividade do sorgo sacarino. O experimento foi realizado em condições de campo, sendo avaliados três arranjos de plantas com espaçamentos de 0,25 m, 0,45 m e 0,45-0,45-0,90 m, mantendo-se a população de 120.000 plantas por hectare em todos os espaçamentos, os quais foram ou não associados a aplicação de herbicidas. Aos 7, 14 e 28 dias após a aplicação dos herbicidas foram avaliadas a intoxicação visual das plantas, o controle das plantas daninhas e coleta de dados para os estudos fitossociológicos da comunidade infestante. A matéria fresca, altura de plantas, diâmetro de colmo, massa de caldo e °Brix do caldo do sorgo foram avaliados no momento da colheita, 120 dias após semeio. Também avaliou-se as características química do caldo quanto as concentrações de sacarose, glicose e frutose, por cromatografia líquida de alta eficiência. Para os estudos fitossociológicos, as populações de plantas daninhas foram analisadas por meio de cálculos de densidade, frequência e abundância relativa, índice de valor de importância (IVI) e índice de similaridade (IS). Conclui-se que, a redução no espaçamento entre linhas do sorgo sacarino aumenta a massa fresca da cultura e a aplicação da mistura de herbicidas pode ser opção no manejo de plantas daninhas no sorgo sacarino, principalmente, objetivando o controle de gramíneas. No entanto, doses acima de 960 g ha-1 de s-metolachlor em mistura com atrazine podem comprometer o crescimento e produtividade do sorgo sacarino. As espécies Cyperus esculentus e Oxalis latifolia demonstram ser mais tolerantes aos herbicidas aplicados, tendo em vista que apresentaram maiores valores IVI, independente do tratamento avaliado.

É grande a preocupação quanto à presença de poluentes persistentes (POP) no ambiente aquático, devido ao potencial destes micropoluentes em afetar organismos aquáticos e a saúde humana. Dentre os POP estão os herbicidas atrazina (ATZ) e amicarbazona (AMZ), empregados no controle de ervas daninhas no cultivo de cana-de-açúcar, responsável por grande parte do consumo de herbicidas no país. O conhecimento do destino desses compostos no meio ambiente é essencial para avaliar seus potenciais impactos, embora não haja na literatura estudos detalhados relacionados a esse tema. No presente trabalho, através da combinação de resultados de experimentos realizados em simulador solar empregando matéria orgânica natural isolada, dados da literatura e simulações matemáticas, foi investigado o destino ambiental fotoquímico da AMZ, considerando as características de corpos d\'águas brasileiros. Analogamente e para fins de comparação, simulou-se o destino ambiental fotoquímico da ATZ com base em informações da literatura. Os resultados das simulações indicaram que a matéria orgânica dissolvida e a profundidade da coluna d\'água são as variáveis que mais influenciam na persistência dos dois herbicidas. O tempo de meiavida pode chegar a aproximadamente 2 meses e 1 ano, para AMZ e ATZ, respectivamente. Assim como é importante o entendimento do destino ambiental dos POP, também é essencial a investigação de processos avançados de oxidação desses poluentes, muitos dos quais são fotoirradiados. Procurando contribuir nesse sentido, neste trabalho estudou-se a fotólise da ATZ sob radiação UV em 254 nm, considerando os efeitos da taxa específica de emissão de fótons e da concentração inicial do herbicida. Procurou-se investigar detalhadamente o papel de espécies reativas de oxigênio (ROS) neste processo, resultados até então não discutidos na literatura. Além disso, os resultados obtidos para ATZ foram comparados aos disponíveis na literatura para AMZ. A degradação dos dois herbicidas diminui com o aumento da concentração inicial dos herbicidas, seguindo decaimento de pseudo primeira-ordem e aumentando com a taxa de emissão de fótons. Os resultados sugerem a formação de produtos persistentes e as ROS foram apontadas como atores importantes durante a degradação fotolítica dos herbicidas. / The presence of Persistent Organic Pollutants (POP) in aquatic environment is a subject of great concern, especially due to their capacity to affect not only aquatic organisms but also the human health. Herbicides as atrazine (ATZ) and amicarbazone (AMZ) are also classified as POP and are widely applied to control weeds on sugarcane cultivations, which are responsible for the increased consumption of herbicides in Brazil. The knowledge regarding the fate of these compounds once released into the environment represents an important issue and is also a type of information usually lacking in the available literature. Through the use of results obtained in experiments performed with a solar simulator, literature data, and mathematical simulations, the photochemical destination of AMZ in the environment was studied considering the characteristics of Brazilian surface water bodies. For purposes of comparison, the environmental destination of ATZ was also simulated. The results indicate that the dissolved organic matter and the depth of the water column are the most influential variables in the environmental persistence of these pesticides. Their half-life may extend up to 2 months to a year, for AMZ and ATZ, respectively. Besides the environmental fate, this investigation also aims to shine a light on the degradation of these contaminants in irradiated advanced oxidation processes. Accordingly, ATZ photolysis through the use of UV radiation (254 nm) was studied, whilst taking into consideration both the herbicide initial concentration and the specific photon emission rate. Another important contribution of this study is the investigation of the role of reactive oxygen species (ROS) in photolytic processes, a subject not usually discussed in the literature. In addition, a crossed-reference analysis between the results obtained for ATZ and those available in the literature for AMZ is presented. The degradation of both herbicides diminishes with the increase in their initial concentration and follows a pseudo first-order decay, increasing with the photon emission rate. Moreover, the results indicate that the formation of persistent degradation products does occur and that ROS play a crucial role in photolytic herbicide degradation.

Processos de fotodegradação de compostos orgânicos tóxicos têm sido bastante estudados. Este trabalho trata da aplicação do processo foto-Fenton para a degradação de atrazina em água (composto modelo). O efeito das concentrações dos seguintes compostos foi avaliado: peróxido de hidrogênio (2 a 6 mmol L-1) e ferrioxalato de potássio (0,2 a 1 mmol L-1). Os experimentos foram realizados em um reator com lâmpada UV - 8W (254nm). O processo de fotodegradação foi monitorado por medidas de espectrofotometria de absorção molecular automatizada por injeção seqüencial (SIA) para determinação de peróxido de hidrogênio e por cromatografia a líquido de alta eficiência (CLAE) para determinação de atrazina e metabólitos. Os experimentos demonstram que o processo de foto-Fenton é viável para o tratamento de atrazina em água. / Photo-degradation processes of toxic organic compounds have been widely studied. This work describes the application of the photo-Fenton process for degradation of atrazine in water. Atrazine was used as a model compound. The effects of the concentration of the following substances were evaluated: hydrogen peroxide (1 to 6 mmol L-1) and potassium ferrioxalate (0.2 to 1 mmol L-1). The experiments were accomplished in a reactor with an 8W UV lamp at 254 nm. The photo-degradation was monitored by molecular absorption spectrophotometry automated by sequential injection analysis (SIA) for determination of hydrogen peroxide and by high performance liquid chromatography (HPLC) for determínation of atrazine and its metabolites. Experimental results demonstrated that the photo-Fenton process is feasíble for the treatment of atrazine.