Dissertationen zum Thema „Oil as pesticide“

Thesis (Ph.D. (Horticulture)) -- University of Western Sydney, 2002.
"A thesis submitted to the University of Western Sydney for the fulfillment of study for a degree of Doctor of Philosophy in Horticulture" "Principal supervisor: Robert Spooner-Hart, co-supervisor: Andrew Beattie, co-supervisor: Alfie Meats" Bibliography : leaves 231-265.

The results of the 3-year project successfully indicated that petroleum-derived spray oils can be used for effective control of a range of citrus pests including citrus leafminer, Asiatic citrus psyllid, chaff scale, red scale, citrus red mite. The results suggested that it should be possible, through use of horticultural and agricultural mineral oils and enhanced natural enemy activity, to reduce the number of pesticide sprays applied annually in China from 14-16 sprays to significantly fewer sprays in most regions. The results are also valuable as references for the implementation of citrus integrated pest management programs in Australia and other citrus-growing countries. However, despite extensive use of PDSOs in citrus and other crops since the late 1800s, few studies have been undertaken to determine their disruptive effects on orchard ecosystems or to compare their effects with those of synthetic pesticides, and these studies are limited in their sc

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A produção orgânica é um sistema que permite alcançar bons níveis de produtividade, evitando ao mesmo tempo os riscos de contaminação química do agricultor, dos consumidores e do meio ambiente. Pelo fato da planta de jambu ser bastante utilizada como medicamento alternativo e por indústrias de cosméticos, vem aumentando o interesse devido às suas características físico-químicas. No entanto, as pesquisas sobre essa cultura ainda são muito incipientes. Existem poucos trabalhos e uma insuficiente diversidade de análises físico-químicas que possam caracterizar e diferenciar os tipos de cultivo em relação ao jambu. Assim, o objetivo do presente estudo foi analisar o óleo essencial e os compostos antioxidantes em diferentes partes de jambu (folha e inflorescência) cultivado sob adubação orgânica e mineral, além de caracterizar os minerais no solo e nas plantas, nos diferentes tipos de cultivo. O experimento foi conduzido na Fazenda Experimental São Manuel (São Manuel-SP), pertencente à Faculdade de Ciências Agronômicas - UNESP, campus de Botucatu) e na mesma época. O delineamento estatístico foi em blocos casualizados em esquema fatorial (2 x 6), duas fontes de adubação (orgânica e mineral) e seis doses de esterco de curral e uréia, com quatro repetições para todas as análises efetuadas, exceto para as características de potencial antioxidante e espilantol, que foram utilizadas três repetições. Os experimentos realizados apresentaram como tratamentos seis doses de adubação mineral (0, 30, 60, 90, 120, 150 g m-2 de uréia), aplicadas parceladas em duas vezes e seis doses de adubação orgânica (0, 2, 4, 6, 8 e 10 kg m-de esterco de curral), aplicadas no plantio. As características avaliadas foram teores de nutrientes na parte aérea, altura de plantas, massa fresca e seca, composição química do óleo essencial, teor de acido ascórbico; potencial...
The organic production it is a system that will achieve good levels of productivity, while avoiding the risk of chemical contamination of farmers, consumers and the environment. Because the plant jambu be widely used as alternative medicine and cosmetic industries, has been increasing interest due to their physical and chemical characteristics. However, the researches on this crop are still very incipient. There is little work and an insufficient variety of physical and chemical analysis that can characterize and differentiate the types of cultivation on the jambu.The purpose of this study was to analyze the essential oil and the antioxidant compounds in different parts of jambu (leaf and inflorescence) grown under organic and mineral fertilizer, and characterize the minerals in soil and plants in different types of cultivation. The experiment was conducted led in (Experimental Farm São Manuel (São Manuel-SP), belonging to the Faculty of Agricultural Sciences - UNESP, campus of Botucatu) and at the same time. The statistical design was factorial (2 x 6), two sources of fertilizer (organic and mineral) and six doses of the kraal manure and urea, with four replications for all analysis performed, except for the characteristics of potential antioxidant and spilantol, which were used three repetitions. The experiments presented treatments as six doses of conventional fertilization (0, 30, 60, 90, 120, 150 g m-2, urea), applied in two split doses of fertilizer and six non-conventional (0, 2, 4, 6, 8 and 10 kg m-2 of the kraal manure), applied at planting. The characteristics were nutrient content in shoot, plant height, fresh and dry weight, chemical composition of essential oil, ascorbic acid content, antioxidant potential, and presence of pesticides. The results show that the compounds were present in this study were trans-caryophyllene, germacrene D, L-dodecene and espatulenol and... (Complete abstract click electronic access below)

Originaire de l'Inde, le neem (Azadirachta indica Juss.) est un arbre présent dans les zones tropicales sèches et subtropicales d'Asie, d'Amérique et d'Afrique. Au Sénégal, il produit en moyenne 50 kg par an d'un fruit sous forme de drupe ellipsoïdale, qui contient en général une graine, d'un poids moyen de 270 ± 30 à 91 % de matière sèche. La variabilité des caractéristiques des graines (45 à 48 % de coques fibreuses : cellulose 52 à 54 %, hémicelluloses 24 à 28 %, lignine 7 à 9 % ; 52 à 55 % d'amandes : lipides 45 à 58 %, protéines 20 à 23 %j) et des huiles extraites (acides palmitiques : 17 à 19 %, stéarique : 14,5 à 17,5 %, oléique : 42 à 48,5 %, linoléique : 16,5 à 20 % ; stérols totaux : 3 à 5 g/kg) est analysée pour 5 régions du Sénégal. L'extraction de l'azadirachtine, principal principe actif phytosanitaire de la graine, par différents solvants (méthanol, éthanol, eau) révèle une teneur de 2 g par kg de graine, localisée essentiellement dans l'amande (3,9 g/kg). Les conditions d'expression de l'huile de graine de neem sont étudiées en presse mono-vis OMEGA 20 et en extrudeur bi-vis CLEXTRAL BC 21. Dans les meilleures conditions, 65 et 68 % de l'huile sont exprimées, 7 à 10 % de l'azadirachtine sont entraînées avec l'huile, et le tourteau contient 14 % de lipides, 14 % de protéines et près de 2 g/kg d'azadirachtine. Le fractionnement acqueux, sous cisaillement intense des graines, conduit à l'extraction de 55 % des lipides, 50 % des protéines et 80 % de l'azadirachtine, séparés sous forme d'une émulsion stable, de composition : eau 70 %, huile 25 %, protéines 4 %, azadirachtine 6 g/kg, et d'une phase aqueuse. L'étude de la mise en œuvre du procédé d'extraction et de séparation, en extrudeur bi-vis CLEXTRAL BC 21 puis BC 45, permet de produire en continu 0,3 kg d'émulsion stable par kg de graine traitée (20 kg/h) avec un ratio eau/graine de 2 et une température de 60°C. Le tourteau ne contient plus que 0,6 g/kg d'azadirachtine, et l'émulsion stable qui en contient 5 g/kg peut être directement mise en œuvre dans les formulations d'insecticide totalement biosourcés
Originally from India, neem (Azadirachta indica Juss.) is a tree found in the dry tropics and subtropics of Asia, America and Africa. In Senegal, it produces an average of 50 kg per year of a fruit as a drupe ellipsoid, which generally contains a seed, with an average weight of 270 ± 30 to 91% dry matter. The variability of seeds (45 to 48% of capsular cellulose 52-54%, 24-28% hemicellulose, lignin 7-9% 52-55% almonds: 45 to 58% lipids, proteins 20 to 23% j) and extracted oils (palmitic acid: 17 to 19%, stearic: 14.5 to 17.5%, oleic acid: 42 to 48.5%, linoleic: 16.5 to 20% total sterols: 3 5 g / kg) was analyzed for five regions of Senegal. Extraction of azadirachtin, the main active ingredient of the plant seed by different solvents (methanol, ethanol, water) shows a content of 2 g per kg of seed, mainly localized in the kernel (3.9 g / kg ). The expression conditions of neem seed oil were studied in single-screw press OMEGA 20 and twin-screw CLEXTRAL BC 21. Under optimum conditions, 65 and 68% of the oil is expressed, from 7 to 10% of azadirachtin are entrained with the oil and meal contains 14% fat, 14% protein and about 2 g / kg azadirachtin. Watery splitting under intense shear seeds, led to the extraction of 55% lipids, 50% protein and 80% of azadirachtin, separated as a stable emulsion, composition: water 70% oil 25%, 4% protein, 6 g azadirachtin / kg, and an aqueous phase. The study of the implementation of the method of extraction and separation, twin-screw extruder and then CLEXTRAL BC 21 BC 45, produces continuous stable emulsion 0.3 kg per kg of treated seed (20 kg / h) with a ratio water / seed of 2 and a temperature of 60 ° C. The cake contains only 0.6 g / kg of azadirachtin, and stable emulsion which contains 5 g / kg can be directly implemented in the formulations of insecticide biosourced completely

Resumo: A produção orgânica é um sistema que permite alcançar bons níveis de produtividade, evitando ao mesmo tempo os riscos de contaminação química do agricultor, dos consumidores e do meio ambiente. Pelo fato da planta de jambu ser bastante utilizada como medicamento alternativo e por indústrias de cosméticos, vem aumentando o interesse devido às suas características físico-químicas. No entanto, as pesquisas sobre essa cultura ainda são muito incipientes. Existem poucos trabalhos e uma insuficiente diversidade de análises físico-químicas que possam caracterizar e diferenciar os tipos de cultivo em relação ao jambu. Assim, o objetivo do presente estudo foi analisar o óleo essencial e os compostos antioxidantes em diferentes partes de jambu (folha e inflorescência) cultivado sob adubação orgânica e mineral, além de caracterizar os minerais no solo e nas plantas, nos diferentes tipos de cultivo. O experimento foi conduzido na Fazenda Experimental São Manuel (São Manuel-SP), pertencente à Faculdade de Ciências Agronômicas - UNESP, campus de Botucatu) e na mesma época. O delineamento estatístico foi em blocos casualizados em esquema fatorial (2 x 6), duas fontes de adubação (orgânica e mineral) e seis doses de esterco de curral e uréia, com quatro repetições para todas as análises efetuadas, exceto para as características de potencial antioxidante e espilantol, que foram utilizadas três repetições. Os experimentos realizados apresentaram como tratamentos seis doses de adubação mineral (0, 30, 60, 90, 120, 150 g m-2 de uréia), aplicadas parceladas em duas vezes e seis doses de adubação orgânica (0, 2, 4, 6, 8 e 10 kg m-de esterco de curral), aplicadas no plantio. As características avaliadas foram teores de nutrientes na parte aérea, altura de plantas, massa fresca e seca, composição química do óleo essencial, teor de acido ascórbico; potencial... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The organic production it is a system that will achieve good levels of productivity, while avoiding the risk of chemical contamination of farmers, consumers and the environment. Because the plant jambu be widely used as alternative medicine and cosmetic industries, has been increasing interest due to their physical and chemical characteristics. However, the researches on this crop are still very incipient. There is little work and an insufficient variety of physical and chemical analysis that can characterize and differentiate the types of cultivation on the jambu.The purpose of this study was to analyze the essential oil and the antioxidant compounds in different parts of jambu (leaf and inflorescence) grown under organic and mineral fertilizer, and characterize the minerals in soil and plants in different types of cultivation. The experiment was conducted led in (Experimental Farm São Manuel (São Manuel-SP), belonging to the Faculty of Agricultural Sciences - UNESP, campus of Botucatu) and at the same time. The statistical design was factorial (2 x 6), two sources of fertilizer (organic and mineral) and six doses of the kraal manure and urea, with four replications for all analysis performed, except for the characteristics of potential antioxidant and spilantol, which were used three repetitions. The experiments presented treatments as six doses of conventional fertilization (0, 30, 60, 90, 120, 150 g m-2, urea), applied in two split doses of fertilizer and six non-conventional (0, 2, 4, 6, 8 and 10 kg m-2 of the kraal manure), applied at planting. The characteristics were nutrient content in shoot, plant height, fresh and dry weight, chemical composition of essential oil, ascorbic acid content, antioxidant potential, and presence of pesticides. The results show that the compounds were present in this study were trans-caryophyllene, germacrene D, L-dodecene and espatulenol and... (Complete abstract click electronic access below)
Orientador: Giuseppina Pace Pereira Lima
Coorientador: Rumy Goto
Banca: Márcia Ortiz Mayo Marques
Banca: Atila Francisco Mogor
Mestre

U radu je izvršena karakterizacija sirove (površinske) vode na lokalitetima: akumulaciono jezero, nizvodna deonica do izvorišta namenjenog za vodosnabdevanje, na lokalitetu samog izvo-rišta i na ulazu u poluindustrijsko istraživačko postrojenje. Ustanovljene su sledeće karakteristike sirove vode: eutrofne karakteristike akumulacionog jezera u vremenskom periodu od kraja juna do sredine septembra meseca; fekalna zagađenost deonice od akumulacionog jezera do izvorišta na-menjenog za vodosnabdevanje; veliki raspon temperature u toku godine (4-19ºC); niske vrednosti mutnoće vode u najvećem delu godine uz povremen i kratkotrajan izrazit porast ovog parametra (<1 NTU do >90 NTU); promena sadržaja organskih materija u vodi (izraženih preko potrošnje ka-lijum-permanganata u kiseloj sredini i UV apsorbancije na 254 nm); izražen potencijal za formira-njem nusprodukata dezinfekcije (THM) u toku obilnih padavina. Na poluindustrijskom istraživačkom postrojenju izvršeno je ispitivanje različitih tehnoloških vari-janti pripreme vode za piće iz površinske vode namenjene vodosnabdevanju uz primenu savreme-nih tehnoloških rešenja i adekvatnog tretmana u slučaju ekscesa izazvanih ljudskom aktivnošću. Primenjenim tretmanom vode procesima ozonizacije-koagulacije-flokulacije-sedimentacije-filtra-cije na poluindustrijskom istraživačkom postrojenju zadovoljena je primarna funkcija redukcije opterećenja vode pre odlaska na završno bistrenje procesom filtracije. Ustanovljeni su najvažniji faktori uticaja na mutnoću vode nakon primenjenih procesa: vrsta koagulanta (najbolji efekti po-stignuti primenom Al₂(SO₄)₃ i FeCl₃) i primenjena doza ozona (pozitivan, mikroflokulacioni efekat ozona postignut pri primenjenim dozama ozona od 0,5-1,0 mgO₃/l). Izračunato je da su pri primeni Al₂(SO₄)₃ kao koagulacionog sredstva dvomedijumski filteri namenjeni završnom bistrenju vode imali najduži filtracioni ciklus. Srednje vrednosti količine uklonjene mutnoće su 2,5- 3,5 puta veće u odnosu na ove vrednosti dobijene pri primeni ostalih koagulanata u fazi koagulacije vode. Značaj primenjenog procesa ozonizacije (doze ozona) uočen je i sa aspekta smanjenja sadržaja prekursora formiranja THM.Ispitivanjem efekta predtretmana vode procesom ozonizacije, primenom vodonik-peroksida i ko-mercijalnog preparata koji u svom sastavu sadrži 25% H₂O₂ + 0,05% Ag u ozoniranu vodu u cilju redukcije broja mikroorganizama uočeni su pozitivni efekti na log₁₀ inaktivacije pri dozama ozona >0,5 mgO₃/l (u slučaju sporogenih sulfitoredukujućih klostridija) i viših vrednosti odnosa H₂O₂/O₃ i H₂O₂+Ag/O₃ (u slučaju ukupnog broja aerobnih organotrofnih bakterija). Prednost primene preparata koji u svom sastavu sadrži 25% H₂O₂ + 0,05% Ag u ozoniranu vodu ogleda se u većem kapa-citetu eliminacije mikroorganizama i pri kraćem hidrauličkom vremenu zadržavanja vode. Analizom frekvencije pojavljivanja jedinjenja koje prouzrokuje nepoželjan miris vode (geosmin) nakon primenjenih procesa ozonizacije-koagulacije-flokulacije-sedimentacije-filtracije ustanovljena je najmanja frekvencija pojavljivanja ovog jedinjenja (10% od ukupnog broja analiziranih uzo-raka) u vodi nakon procesa ozonizacije i njegova potpuna redukcija primenom koagulanta FeCl₃ u fazi koagulacije vode.Pri simulaciji ekscesnih situacija na poluindustrijskom istraživačkom postrojenju (doziranjem sintetičkih organskih jedinjenja pesticida i nafte) utvrđeno je da se primenom procesa ozonizacije-koagulacije-flokulacije-sedimentacije-filtracije uz dodatak AUP u fazi koagulacije vode postiže reduk-cija lindana u vodi za 97%, atrazina 99%, ukupnih ugljovodonika 91% i mineralnih ulja 89%.Svi rezultati dobijeni u toku istraživanja na poluindustrijskom istraživačkom postrojenju posmatra-ni sa aspekta optimizacije tehnoloških uslova pripreme vode za piće i varijabilnog kvaliteta površin-ske vode ukazuju na prvom mestu na neophodnost primene procesa ozonizacije vode i pozitivan efekat unapređenih procesa oksidacije u fazi pripreme vode za dalju obradu, kao i na značaj primenjene vrste koagulanta i aktivnog uglja u prahu u fazi koagulacije i flokulacije vode.
The paper presents the characterisation of raw (surface) water at the following sites: accu-mulation lake, downstream section from the water supply well field at the very site of the well field and at the entrance into pilot plant. The following raw water characteristics have been determined: eutrophic properties of accumulation lake within the time frame from the end of June to the middle of September; faeces pollution of the section from the accumulation lake to the water supply well field; a wide range of temperature during the year (4-19ºC); low values of water turbidity during the largest part of the year, with occasional and short-term emphasised growth  of this parameter (<1NTU to >90 NTU); change in the content of natural organic matters in water (expressed through potassium permanganate consumption in acid environment and UV absorption at 254 nm); ex-pressed potential for disinfection by-products (THM) creation during high rainfall levels.Study of different technological options for drinking water preparation from surface water desig-nated to water supply with application of the latest technological solutions and adequate treatment in cases of accidents caused by human activities has been carried out at the pilot plant.The water treatment composed of ozonation-coagulation-flocculation-sedimentation-filtration applied at the pilot plant satisfied the primary function of reduction of water load prior to departure to the final clarification in filtration process. The most significant factors affecting water turbidity after the applied processes have been determined: type of coagulant (the best effects have been ob-tained by application of Al₂(SO₄)₃ and FeCl₃) and the applied ozone dose (positive, micro-floccula-tion effect of ozone has been obtained with the applied ozone doses of 0,5-1,0 mgO₃/l). It has been calculated that two-media filters designated to final water clarification had the longest filtration cy-cle when Al₂(SО₄)₃ was used as coagulation means. Medium values of quantity of the eliminated tur-bidity are 2,5-3,5 times higher in comparison to  these values obtained when others coagulants were used in the water coagulation phase. The significance of the applied ozonization process (ozone dose) has also been found from the aspect of reduction of THM generation precursor contents. Investigation of effects of water pre-treatment with ozonation process and application of hydrogen-peroxide and commercial preparation containing 25% H₂O₂ + 0,05% Ag in ozonized water aiming at reduction of micro-organisms count showed positive effects on log₁₀ inactivation when >0,5 mgO₃/l doses of ozone were used (in case of sulphito-reducing clostridia) and higher values of H₂O₂/O₃ and H₂O₂+Ag/O₃ ratio (in case of total aerobic organotrophic bacteria count). The advantage of appli-cation of the preparation containing 25% H₂O₂ + 0,05% Ag in ozonized water is reflected in higher microorganisms elimination capacity and shorter hydraulic retention time. The analysis of occurrence frequency of compounds causing unpleasant water odour  (geosmin) af-ter the applied ozonation-coagulation-flocculation-sedimentation-filtration processes showed that the lowest occurrence frequency for this compound (10% of the total number of the analysed sam-ples) in water after ozonisation process  and its total reduction after the application of FeCl₃ coagu-lant in water coagulation phase.In simulation of accidents at pilot plant (dosing of synthetic organic compounds of pesticides and oil) it was found that reduction of lindane in water for 97%, atrazine for 99%, total hydrocarbons for 91% and mineral oils for 89% is accomplished with application of the ozonation-coagulation-floccu-lation-sedimentation-filtration processes with addition of AUP in the phase of water coagulation. All the results that have been obtained during the researches at pilot plant have been considered from the aspect of optimisation of technological conditions of drinking water preparation and vari-able surface water quality point primarily to the necessity of application of water ozonization proc-ess and positive effect of the improved oxidation processes in the phase of water preparation for further processing as well as to the significance of the applied type of coagulant and active powder charcoal in water coagulation and flocculation phase.

Les perturbations environnementales d'origine anthropique favorisent l'établissement de populations invasives. La gestion de ces populations est primordiale pour la santé publique (zoonose, famine), l'environnent (perte de biodiversité), et l'économie (dégâts). L'objectif de cette thèse pluridisciplinaire, menée en conditions naturelles, est d'améliorer les connaissances sur les populations invasives de rongeurs dans des paysages agricoles à grande échelle et d'appréhender les mécanismes d'adaptation qui favorisent une réponse positive aux pressions anthropiques. Les résultats montrent que (1) le rat endémique Rattus tiomanicus, dont la présence est associée à la typologie de l'habitat naturel, et le rat introduit Rattus tanezumi-R3, dont la présence est associée aux activités humaines, constituent les populations invasives des plantations de palmier à huile en Indonésie; (2) leur distribution géographique clinale est probablement contemporaine à l'anthropisation des milieux, et suppose une compétition inter-spécifique; (3) ces grandes populations sont spatialement continues avec un flux génique limité par la distance géographique (caractérisées par un patron d'isolement par la distance) et potentiellement influencé par les transports routiers; (4) R. tanezumi-R3 possède une forte résistance physiologique aux raticides AVK, dont l'origine n'est pas associée à une mutation génétique de la molécule cible mais probablement liée aux enzymes du métabolisme. Ces travaux soulignent des stratégies d'adaptations comportementales et physiologiques des populations invasives de rongeurs en milieux agricoles et procurent des bases pour l'élaboration de stratégies de lutte adaptée

O azeite é o principal ingrediente da dieta mediterrânica devido às suas propriedades antioxidantes, aos benefícios associados à regulação dos níveis de colesterol e à prevenção das doenças cardiovasculares. Em Portugal o azeite assume um papel importante tanto a nível cultural como socioeconómico, sendo que nos últimos anos, a olivicultura tem sofrido grandes modificações, tendo-se assistido à intensificação da produção, sobretudo devido à conversão dos olivais tradicionais em sistemas de produção intensivo e super-intensivo, o que pressupõem uma maior utilização de pesticidas. Contudo, os pesticidas aplicados ao olival podem persistir até à fase de colheita e, consequentemente serem transferidos para o azeite, dado que o processo de transformação é meramente físico/ mecânico. Assim, por forma a garantir a segurança alimentar do consumidor é crucial desenvolver metodologias analíticas capazes de determinar resíduos de pesticidas no azeite. Porém, a análise de pesticidas em amostras vegetais com elevado teor de gordura é uma tarefa extremamente difícil devido à inerente complexidade da matriz. Com a finalidade de ultrapassar as limitações associadas às técnicas de preparação de amostra convencionalmente utilizadas, no presente trabalho desenvolveuse uma metodologia altamente seletiva para a extração e quantificação de cada um dos pesticidas em estudo (dimetoato, terbutilazina e deltametrina), a qual teve por base a utilização de polímeros molecularmente impressos como materiais adsorventes na extração em fase sólida (MISPE). Em concreto, as metodologias MISPE foram implementadas com sucesso para a quantificação destes pesticidas em amostras de azeite dopadas com concentrações iguais aos limites máximos de resíduos de pesticidas, permitindo obter taxas de recuperação de 90 % para o dimetoato, 92 % para a terbutilazina e 90 % para a deltametrina. Deve ainda salientar-se que estas metodologias revelaram-se bastante robustas, precisas, de fácil aplicação, requerem um reduzido manuseamento das amostras e as colunas MISPE podem ser reutilizáveis sem perder a especificidade para os analitos alvo; Abstract: Trace Analysis of Pesticides in Olive Oil: Application of Molecularly Imprinted Polymers Olive oil is the main ingredient of the Mediterranean diet due to its antioxidant properties, benefits associated with the regulation of cholesterol levels and capacity to prevent cardiovascular disease. In Portugal the olive oil plays an important role in country`s culture and socio-economic development. In recent years, olive groves has undergone major changes, namely the intensification of production, mainly due to conversion of traditional olive groves in intensive and super-intensive production systems, which require a greater use of pesticides. Moreover, pesticides applied to olive trees may persist until the harvest stage, and consequently can be transferred to the olive oil, since the transformation process is purely physical/ mechanical. Thus, in order to ensure consumer’s food safety is crucial the development of efficient analytical methodologies to determine pesticide residues in olive oil. However, the analysis of pesticides in samples with high fat content is an extremely difficult task due to the inherent complexity of the matrix. In order to overcome the limitations associated with conventional sample preparation techniques, in this work a highly selective methodology for extraction and quantification of each pesticide under study (dimethoate, terbuthylazine and deltamethrin), based on the use of molecularly imprinted polymers as adsorbent materials in the solid phase extraction (MISPE) has been developed. The MISPE methodologies have been successfully implemented for the quantification of these pesticides in olive oil samples spiked with concentrations equal to the tolerated maximum residue limits, allowing to obtain recovery rates of 90 % for dimethoate, 92 % for terbuthylazine and 90 % for deltamethrin. It should also be noted that these methodologies have proved to be very robust, accurate, easy to use, require a reduced sample handling and, also, MISPE columns can be regenerate and reusable without losing the specificity for target analytes.

For chemigation of nonsoluble pesticides, small oil-pesticides droplets (dmax tend to wash-off from foliage while large droplets tend to stick. Large droplets (dmax are buoyant, tend to rise in the irrigation pipeline and exit at the beginning of the pipeline; thus, uniformity and efficacy are poor. For this research, a new chemigation system was proposed. The system removes water from the irrigation pipeline, injects the oil-pesticide into the water stream, increases dispersion velocity in successively smaller tubing diameters, and finally injects the dispersion back into the irrigation pipeline. The higher velocity flow with high turbulent shear forces breaks the oil-pesticide into desired size droplets. Droplet break-up research was reviewed, and a model developed to predict maximum droplet size and size distribution. A maximum relative error of 40% was observed when dmax predicted by the model was compared against literature data. Equations to predict friction factor in helically coiled pipes and effective viscosity of oil-in-water dispersions were evaluated. The friction factor predicted by the Ito equation was in good agreement with the experimental data. Effective viscosity of soybean oil- and kerosene-in-water dispersions was predicted satisfactorily by the Richardson equation with k₄ = 2.5. Finally, center pivot field experiments were conducted using the new and conventional chemigation systems. For the conventional system, the soybean oil uniformity coefficient along the lateral was 61%, and oil applied over the last tenth of irrigated area was 9% of the initial concentration. For the new system, the uniformity coefficient was 73% and 98% for dmax of 875 mum and 98 mum, respectively; oil applied over the last tenth of the area was 27% and 90% of the initial concentration. Field data were compared with those predicted from a pipeline transport model for nonsoluble pesticides. Agreement between the model and the field data was excellent for both experiments using the new chemigation system. Based on the field results and simulation analyses, droplets < 150 μm should be desirable to keep the discharge uniformity coefficient over 97%, for 0.92 ≤ ρ(d)/ρ(c) ≤ 1.04.

Diploma thesis is focused on study of compounds of terpenic nature in mint plants. Terpenic compounds are volatile hydrocarbons formed by several isoprenoid units with low molecular weight which cause the typical smell of plants. Presence of these compounds cause that plants seem to be fungicidal, bactericidal and insecticidal. Due to these properties, they can be used as botanical pesticides which are not toxic and no resistant organisms occur. Each plant contains relatively low concentrations of these compounds and therefore elicitors must be used for the increasing of terpenes amount. Elicitors activate defensive mechanisms in the plant leading to higher defense abilities and production of secondary metabolites. The identification and quantification of analytes was determined by gas chromatography in connection with mass spectrometry.

Numerosos químicos de origem industrial e natural estão a aumentar a nível global, enquanto os seus efeitos de longo-termo permanecem desconhecidos. A coruja-da-torres é um bom bioindicador de poluição ambiental e as suas penas podem ser utilizadas como ferramentas de biomonitorização minimamente invasivas. A variação intra-individual das concentrações de mercúrio pode ser minimizada através do cálculo de uma média a partir de várias penas do indivíduo, independentemente do tipo de pena. Várias penas do mesmo ninho podem ser combinadas para obter uma melhor estimativa da contaminação no território. Penas de indivíduos atropelados são representativas da contaminação ao nível regional. Menor bioacumulação está relacionada com culturas irrigadas e paisagens agrícolas heterogéneas. O habitat parece mediar a transferências de mercúrio do solo para as presas, e da cadeia trófica até à coruja-das-torres. As penas podem ser particularmente úteis para detetar pesticidas organoclorados em desuso, que geralmente ocorrem em concentrações residuais, embora a contaminação externa deva ser avaliada; Summary: Numerous industrial and natural chemicals are increasing worldwide, while their long-term effects on wildlife and human health remain unknown. Barn owls are good biondicators of environmental pollution and their feathers may be used as minimally invasive monitoring tools. Intra-individual variation in mercury concentrations can be minimized by calculating an average from several feathers from an individual, regardless of feather type. Several feathers from the same nest may be pooled to better represent the average mercury contamination in the territory. Feathers from road-killed barn owls are representative of contamination at a regional level. Lower bioaccumulation in the barn owl is linked with irrigated crops and heterogeneous agricultural landscapes. Habitat seems to mediate the transfer of mercury from the soil to the prey, and along the food web to the barn owl. Feathers may be particularly suitable to detect legacy organochlorine pesticides which generally occur in residual concentrations, but external contamination should be assessed.

The research topic has as its main objective the modeling of the flow of contaminant (mineral oil) following a road accident involving a heavy transport vehicle carrying 24 tons of CHEMOL pesticide, produced by the company Chemia S.p.A. of Sant’Agostino (FE). The target area is the ex-cave Olmi, currently used as a flood retention basin in the town of Calderara di Reno (BO), N-E of Bologna's Marconi airport, which is the final destination of the vehicle. Within this context, the thesis work concerned first of all the georeferencing and the study of an environmental report performed on the target area useful in the study of the hydrogeology of the soil and its stratigraphy. Subsequently, it was necessary to use the HSSM software to model the flow of contaminant in the soil. After this initial study, the Fault Tree (FTA) was built, the final event of which is the achievement of the target area, within a given time limit, a concentration higher than the limit given by the legislation. The failure rate of each basic event, which leads to the realization of the final event, was evaluated using values ​​derived from technical reports, with the exception of the event consisting in exceeding the concentration limit value in the target area. For the latter event, a Monte Carlo simulation was used, combining the values ​​of hydraulic conductivity and initial concentration of contaminant, which were the values ​​most affected by uncertainty. Finally, these values ​​were entered into the aforementioned HSSM software to evaluate the results. The probability of failure of this basic event was obtained by having the software compile a number of times equal to that of the possible combinations. The final calculation of the result, deriving from the constructed tree, was carried out using Boolean algebra, a method typically used in this probabilistic risk calculation technique. Below are elements relating to the techniques available for the removal of the pollutant.

The results of the 3-year project successfully indicated that petroleum-derived spray oils can be used for effective control of a range of citrus pests including citrus leafminer, Asiatic citrus psyllid, chaff scale, red scale, citrus red mite. The results suggested that it should be possible, through use of horticultural and agricultural mineral oils and enhanced natural enemy activity, to reduce the number of pesticide sprays applied annually in China from 14-16 sprays to significantly fewer sprays in most regions. The results are also valuable as references for the implementation of citrus integrated pest management programs in Australia and other citrus-growing countries. However, despite extensive use of PDSOs in citrus and other crops since the late 1800s, few studies have been undertaken to determine their disruptive effects on orchard ecosystems or to compare their effects with those of synthetic pesticides, and these studies are limited in their sc
Doctor of Philosophy (PhD)

Arbuscular mycorrhizal fungi (AMF) play a crucial role in improving the growth of a vast majority of plants. Past researchers have discovered that agricultural practices have a significant negative effect on the diversity of AMF. Arbuscular mycorrhizal fungi are reported to enhance plant nutrient uptake, stress tolerance, and soil aggregate formation which are key aspects of productive low-input farming. The objective of this study was to investigate the effects of four pesticides on the ability of AMF to colonize the roots of okra plants (Abelmoschus esculentus). The pesticides being tested include two synthetic chemicals (glyphosate and carbaryl) and two organic chemicals (neem oil and citrus oil). The tested parameters included crop yield, plant biomass, leaf matter CNP, and the percentage of mycorrhizal colonization in roots. The results of this study show that the organic chemicals had no significant effect on AMF colonization while the synthetic chemicals did have somewhat of a negative effect on colonization.

A citricultura, introduzida no Brasil na época da colonização e explorada comercialmente a partir dos anos 30 do século passado, é um setor de grande importância para o agronegócio brasileiro. Atualmente, o Brasil detém 50% da produção mundial de laranja e cerca de 85% de toda exportação mundial, representando uma captação de divisas de cerca de 2,5 bilhões de dólares por ano, devido principalmente à exportação do suco de laranja. Apesar do suco ser o principal produto de exportação da citricultura, vários subprodutos com valor comercial são obtidos durante seu processo de produção, tais como os óleos essenciais cítricos. Esses subprodutos localizam-se na casca da fruta e são obtidos durante o processo de extração do suco de laranja por prensagem a frio. Devido ao uso intensivo de pesticidas na citricultura e que muitas vezes se acumula na casca da fruta é comum à obtenção de óleos essenciais com resíduos de pesticidas, o que reduz seu preço de mercado internacional e limita sua inserção em mercados exigentes como o Europeu, Japonês e Americano, por exemplo. Este trabalho propõe o desenvolvimento de metodologias eletroanalíticas para a determinação de alguns pesticidas amplamente utilizados na citricultura brasileira e que têm sido encontrados nos óleos essenciais produzidos pelas indústrias de processamento. Inicialmente, foram realizados testes para avaliação da eletroatividade de três pesticidas (piridafention, cihexatina e bromopropilato) amplamente utilizados no Brasil, mas que são proibidos na maioria dos países importadores, sendo, portanto, de importância estratégica. Utilizando-se a técnica de voltametria cíclica verificou-se que o piridafention apresenta resposta sobre o eletrodo compósito de grafite-poliuretana (GPU), a cihexatina apresentou eletroatividade sobre o eletrodo de filme de bismuto e o bromopropilato não foi eletroativo nas superfícies eletródicas testadas. Varreduras realizadas com voltametria cíclica mostraram que o piridafention apresenta um pico de redução em -0,80 V (vs. EECS) sobre eletrodo compósito de GPU em meio ácido (tampão Britton-Robinson 0,1 mol L-1) com características de processo irreversível. Em seguida, desenvolveu-se uma metodologia eletroanalítica, utilizando a técnica de voltametria de onda quadrada (SWV), com a otimização do pH da solução (1,0) e demais parâmetros da SWV como a frequência (80 s-1), amplitude do pulso (50 mV) e incremento de varredura (ΔEi = 5 mV). Curvas analíticas foram obtidas no intervalo de 1,46 a 17,1 µmol L-1, apresentando boa linearidade, com coeficiente de determinação (r2) de 0,998. Os limites de detecção (LD) e de quantificação (LQ) obtidos foram de 0,27 µmol L-1 e 0,92 µmol L-1, respectivamente. A precisão da metodologia desenvolvida foi avaliada por meio da repetibilidade e a reprodutibilidade e a exatidão determinada pelo erro relativo. Os testes de recuperação realizados pelo método de adição de padrão forneceram valores de 98%. A metodologia eletroanalítica desenvolvida para determinação do piridafention foi aplicada em amostras de óleo essencial de laranja, contaminadas com três níveis de concentração 1,5, 2,9 e 5,9 µmol L-1. Foram avaliados quatro procedimentos de extração líquido-líquido, utilizando água Milli-Q como extrator: i) agitação manual da mistura (10 mL de óleo e 10 mL de água) por 4 minutos com repetição do procedimento por 3 vezes; ii) agitação magnética da mistura (5 mL de óleo e 50 mL de água) por 20 minutos em uma única etapa, à temperatura ambiente; iii) agitação magnética da mistura (5 mL de óleo e 50 mL de água) por 20 minutos em uma única etapa, à temperatura de 45°C; iv) agitação da mistura em mesa orbital com tempo de agitação variando de 5 até 180 minutos. Os melhores resultados foram obtidos com o procedimento utilizando a agitação por mesa orbital (iv), sendo recomendado, portanto, para extração do piridafention em amostras de óleo essencial de laranja. No caso da cihexatina, os testes realizados visando à determinação de uma metodologia eletroanalítica mostraram uma baixa reprodutibilidade do eletrodo filme de bismuto inviabilizando a sua aplicação na eletroanálise da cihexatina. Entretanto, devido à importância da cihexatina e do bromopropilato recomenda-se a realização de mais estudos eletroquímicos com o objetivo de se estabelecer novos métodos de análise.
The citrus production introduced in Brazil during the colonization period and commercially exploited since 1930, is very important for the Brazilian agribusiness. Currently, Brazil is responsible for 50% of the total world citrus production and for about 85% of the citrus world exportation trade, representing an income of about 2.5 billion dollars for the country yearly. The orange juice is the major product of the citrus industry, but other commercially valuable byproducts can be obtained during the manufacturing process, such as the citrus essential oils. These byproduct, located at the orange fruit exocarp, are extracted during the juice production process by cold pressing. Due to the use of pesticides in the citrus production, these agrochemicals can be occasionally presented in extracted essential oil products as unwished residues, which significantly reduce their values in the international market and restrict their insertion in exigent markets as the European, Japanese and North American, for instance. This study aim to develop electroanalytical methodologies for the determination of some pesticides widely employed in the Brazilian citrus production and that has been found in the essential oils produced by the processing industries. Preliminar tests were conducted to evaluate the electroactivity of three pesticides (pyridaphention, cyhexatin and bromopropylate) widely applied in Brazil, but not regulated for use in most of the importing countries. Using the cyclic voltammetry technique, these experiments showed that pyridaphenthion presented a good electrochemical response on the graphite-polyurethane composite electrode (GPU), cyhexatin showed electroactivity on thin bismuth film electrode and bromopropylate was not electroactive on the tested electodes. Studies conducted using cyclic voltammetry showed that pyridaphenthion presents a reduction peak in -0.8 V (vs. ESCE) on GPU in acidic medium (Britton - Robinson buffer 0.1 mol L- 1(BR)) with features of an irreversible process. The electroanalytical methodology for pyridaphenthion analysis was developed using square wave voltammetry (SWV) with optimization of pH (1.0) and the SWV scanning parameters, as pulse frequency (80 s-1), amplitude (50 mV), and increment (ΔEi = 5 mV). An analytical curve was obtained for concentrations ranging from 1.46 a 17.1 µmol L-1, showing good linearity expressed in the determination coefficient (r2) of 0.998. The detection limit (LOD) and quantification limit (LOQ) obtained were 0.27 µmol L-1 and 0.92 µmol L-1, respectively. The precision was evaluated by means its repeatability and reproductibility, while accuracy was assessed by means relative error. Recovery experiments conducted using the standard addition method provided a concentration recovering level of 98%. The electroanalytical methodology developed for pyridaphenthion was applied in citrus essential oil samples spiked with three concentration levels 1.5, 2.9 and 5.9 µmol L-1. Four liquid-liquid extraction procedures were evaluated using only Milli-Q purified water as extracting agent: i) manual stirring of the mixture (10 mL of essential oil and 10 mL of water) during 4 minutes, repeating the procedure three times; ii) magnetic stirring of the mixture (5 mL of essential oil and 50 mL of water) during 20 minutes, in a single step, at room temperature; iii) magnetic stirring of the mixture (5 mL of essential oil and 50 mL of water) during 20 minutes, in a single step, at 45o C; iv) orbital shaking of the mixture (5 mL of essential oil and 50 mL of water) for different period of times varying from 5 to 180 minutes. The best results were obtained with the procedure using the orbital shaking table (iv), which is, therefore, recommended for extraction of pyridaphention residues in citrus essential oils samples. For the cyhexatin, studies carried out aiming to determine an electroanalytical methodology, showed low reproducibility of the bismuth film, preventing its application in the electroanalysis of cyhexatin. However, due to the importance of these pesticides in citrus essential oils production it is recommended additional studies regarding the electrochemistry and electroanalysis of these chemicals.

This study examined the exposure of the Eastern Screech-owl (Otus asio) to contaminants in apple orchards of southern Quebec. Using a worstcase scenario approach, secondary exposure to three organophosphorus insecticides, (phosmet, azinphosmethyl and phosalone), two anticoagulant rodenticides, (chlorophacinone and diphacinone), and residues of previously applied organochlorines, particularly DDT and metabolites, was assessed. Exposure to PCBs and trace metals was also considered. Small mammal species preyed upon by Screech-owls were captured in orchards for residue analysis on a continual basis for persistent compounds or after insecticide and rodenticide applications. Beginning in the winter of 2000, 98 nest boxes were constructed and installed in woods inhabited by Screech-owls, adjacent to orchards. These boxes were then repeatedly inspected for pellets and prey remains. Estimated exposure of Screech-owls 0-60 hr post-application was 0.641 mg/kg for phosmet and azinphosmethyl and 0.401 mg/kg for phosalone. Exposure to phosmet at this level may warrant concern. The acute poison zinc phosphide is now the primary means of small mammal control in the study area and the possibility of exposure to anticoagulant rodenticides is diminishing. Observed DDE residues were most elevated in the short-tailed shrew (Blarina brevicauda) and ranged from <1.00 to 26.29 ug/g (wet wt) in whole-body pools. A Screech-owl egg found in a nest box between two orchards may have been thinned by as much as 19.8%, of concern because thinning maintained at 15.0 - 20.0% has been linked to population decline. Only background levels of PCBs and trace metals were detected. Finally, over 950 Screech-owl case files were also obtained from one Canadian and seven United States wildlife rehabilitation facilities and analyzed for evidence that pesticide exposure was an underlying or contributing cause of admissions.

L’utilisation croissante de pesticides dans l'agriculture peut entraîner de graves risques pour la santé humaine. En effet, des résidus de pesticides peuvent être retrouvés à l’état de trace dans de nombreux produits de grande consommation. Leur identification et leur analyse quantitative à l’état de trace dans des échantillons complexes, tel que les huiles végétales, constituent un défi analytique majeur. Malgré le potentiel élevé de méthodes analytiques comme la chromatographie en phase liquide couplée à la spectrométrie de masse (LC-MS/MS), l’introduction d’une étape d’extraction et de purification des extraits avant l’analyse chromatographique s’avère nécessaire. Afin d'augmenter la sélectivité de cette étape de traitement de l'échantillon, la synthèse des supports à empreintes moléculaires générant un mécanisme de reconnaissance moléculaire a été envisagé. Cette étude se concentre sur une famille de pesticides, les organophosphorés (OP), qui présentent des disparités structurales importantes et une gamme de polarité assez large (log P compris entre 0,7 et 4,7). Deux approches ont été envisagées pour la synthèse de ces supports imprimés. La première approche consiste à réaliser une polymérisation par voie radicalaire en utilisant des monomères organiques dans des solvants organiques peu polaires pour obtenir des polymères à empreintes moléculaires (MIP). La seconde approche consiste à produire les supports par voie sol-gel via l’hydrolyse puis la condensation d'organosilanes dans un milieu polaire pour produire des silices imprimées (MIS). Pour les deux approches, différentes conditions de synthèse ont été criblées en utilisant différentes molécules empreintes, monomères et solvants. La sélectivité des polymères imprimés résultants a d'abord été évaluée en étudiant les profils de rétention des OP en milieu pur. Les interactions non-spécifiques ont été évaluées en étudiant parallèlement la rétention des OP sur des supports non-imprimés (NIP/NIS) qui ont été synthétisés dans les mêmes conditions que les MIP/MIS mais sans introduire la molécule empreinte. Il est apparu que les supports MIP/MIS présentaient une complémentarité en termes d'extraction sélective des OP visés : les OP les plus polaires ont été extraits sélectivement par le MIS alors que les OP modérément polaires ont été extraits sélectivement par le MIP. La capacité de ces supports a été évaluée et se révèle adaptée à l'analyse des OP à l’état de traces dans des huiles végétales. Après avoir vérifié la répétabilité de la procédure d'extraction et des synthèses, les performances de ces supports ont été étudiées dans des milieux réels
The increasing use of pesticides in agriculture causes serious health risks to humans. These pesticides may possibly be found in vegetable oils used as cosmetic ingredients. Their identification and reliable quantitative analysis at trace levels constitute a challenge for the safe use of such oils despite the high potential of analytical methods such as liquid chromatography coupled to mass spectrometry (LC-MS/MS). Their determination at low concentration levels in complex oil samples requires an extraction and a purification step. In order to increase the selectivity of the sample treatment step, the synthesis of imprinted sorbents can be considered. This study focusses on a group of pesticides, the organophosphorus (OPs) that present some structural disparity and belong to a wide range of polarity (log P values between 0.7 and 4.7). To produce imprinted sorbents, a first approach of synthesis consists in the radical polymerization of organic monomers in moderately polar organic solvents to obtain molecularly imprinted polymers (MIPs). The second one, the Sol-Gel approach, consists in the hydrolysis and then condensation of organosilanes in a polar medium to produce molecularly imprinted silicas (MIS). For both approaches, different conditions of synthesis were screened using different template molecules, monomers and solvents. The selectivity of the resulting imprinting polymers was first evaluated by studying the extraction profiles of OPs in pure media on MIP and MIS. The non-specific interactions were estimated by studying in parallel the retention of OPs on non-imprinted polymers synthesized in the same conditions as imprinted sorbents but in the absence of the template molecule. Both sorbents MIP/MIS present a complementarity in terms of selective extraction of the target OPs: polar OPs were extracted selectively using the MIS while moderately polar OPs were selectively extracted by the MIP. The capacity of these supports was evaluated and was consistent with the analysis of OPs at trace levels in real oil samples. After studying the repeatability of the extraction procedure and of the reliability of the syntheses, the performances of these supports were studied in real media. For this, MIP/MIS were applied to the selective extraction of OPs from different vegetable oils (almond, olive and sunflower oil) and similar results were obtained for the three different oils. Their potential in terms of ability to remove matrix interfering compounds were higher than those of the conventional method based on the use of C18 silica. The estimated limits of quantifications were lower than the Maximum Residue Levels (MRLs) established by EU Regulation 396/2005 for these compounds in oils

Обґрунтована доцільність застосування функціональної залежності «структура – активність» при утилізації непридатних пестицидних препаратів реагентними методами. Показано, що її використання дає змогу заздалегідь прогнозувати можливість цільового отримання додатків до вуглеводневих матеріалів різного функціонального призначення
The expediency of the use of the functional dependence «structure – activity» at the utilization of obsolete pesticides by reagent methods has been substantiated. It has been shown that its use allows in advance to predict the possibility of the objective obtaining of additives to hydrocarbon materials of various functional purposes

Le phytomanagement compte parmi les méthodes innovantes de gestion des sites et sols pollués en raison de son adéquation avec le développement durable. Pour répondre à la double exigence de performances environnementales et économiques, les phytotechnologies sont désormais combinées à la valorisation de la biomasse produite sur sols pollués. Parmi les filières éco-innovantes et non-alimentaires de valorisation de cette biomasse, la culture de plantes à parfums, aromatiques et médicinales (PPAM) pour la production d’huiles essentielles (HE), substances biosourcées à haute valeur ajoutée, a été proposée dans le cadre du projet PhytEO, financé par l’ADEME. Ainsi, ma contribution à ce projet a permis d‘évaluer la pertinence d’un mode de gestion reposant sur la culture de la sauge sclarée et de la coriandre, en présence ou non d’un amendement mycorhizien, en s’appuyant sur des démonstrateurs in situ à l’échelle de l’hectare, parcelles historiquement polluées ou non par les éléments traces (ET). La coriandre ainsi que la sauge sclarée ont toutes deux montré une bonne capacité à s’installer, à se développer et à produire une quantité importante de biomasse sur des sols présentant une forte pollution historique par les ET. Bien que l’ajout d’un amendement biologique à base de champignons mycorhiziens à arbuscules ait permis d’augmenter de façon significative les taux de mycorhization des racines de coriandre et de sauge sclarée, aucun gain n’a été observé ni au niveau de la croissance de ces deux PPAM, ni au niveau de la quantité et de la qualité des HE. Un effet positif en termes d’immobilisation des ET dans le sol, en particulier du Pb, et une réduction des transferts des ET (Cd et Pb) dans les parties aériennes a toutefois été montré chez la sauge sclarée. D’autre part, les HE distillées à partir de la biomasse de sauge sclarée (inflorescences) ou de coriandre (parties aériennes ou graines) cultivées sur sols pollués présentent une qualité très satisfaisante, caractérisée par leur non contamination en ET ou en résidus de pesticides (traces). Leurs compositions chimiques, non altérées par la pollution en ET et l’inoculation mycorhizienne, affichent divers principes actifs dont le linalol, l’acétate de linalyle, le germacrène, l’α-pinène, le γ-terpinène, le 2-décénal, le décanal et le 2-dodécénal. Ainsi, plusieurs propriétés biologiques potentiellement valorisables dans des domaines à vocation non-alimentaire, tels que la protection des cultures (effets fongistatiques, anti-germinatifs et herbicides) ou la santé humaine (effets anti-inflammatoires et antioxydants) ont été mises en évidence. En revanche, en dépit de son fort pouvoir complexant des HE, la β-cyclodextrine n’a montré aucun effet positif sur les propriétés biologiques testées. Par ailleurs, la végétalisation du sol pollué par la sauge sclarée permet une modulation de la structure des communautés bactériennes et fongiques, telluriques et racinaires. Enfin, l’ensemble des résultats de cette étude et de l’analyse technico-économique de la filière PPAM-HE soulignent le haut potentiel de la sauge sclarée dans une démarche de phytomanagement de sols pollués par les ET
To cope with the soil trace element (TE) pollution, phytomanagement was brought forward as an eco-friendly and feasible approach. To meet the dual requirements of environmental and economic performances, phytotechnologies are now combined with the valorisarion of biomass produced on polluted soils. Among the eco-innovative channels intended for the non-food valorisation of the produced biomass, the cultivation of aromatic and medicinal plants producing essential oils (EO), high-added value biosourced products, has been suggested within the framework of PhytEO project, funded by ADEME. Thus, this thesis contributed to evaluate the relevance of a management approach based on clary sage and coriander cultivation, combined or not with a mycorrhizal inoculum, on in situ experimental plots polluted or not with TE. Both clary sage and coriander have shown a good ability to settle in, to grow and to produce high amounts of biomass, despite the presence of high TE concentrations in the soil. The addition of an amendment based on arbuscular mycorrhizal fungi enhanced the mycorrhizal colonisation rates of both coriander and clary sage roots. However, no significant improvement was observed in terms of plants’ growth, EO amounts and quality. Moreover, mycorrhizal inoculation allowed TE immobilisation in soils, in particular Pb, and reduced TE (Cd and Pb) transfers in aerial parts of clary sage. Besides, the EO distilled from clary sage inflorescences and coriander (aerial parts orseeds) grown on TE polluted soils, displayed a highly satisfactory quality, regarding the absence of contamination by TE or pesticide residues (trace amounts). Their chemical compositions were not altered by both TE pollution and mycorrhizal inoculation and were characterized by several active principles, such as linalool, linalyl acetate, germacrene, α-pinene, γ-terpinene, 2-decenal, decanal and 2-dodecenal. Furthermore, several biological properties with potential applications in non-food fields such as crop protection (antifungal, antigerminative and herbicidal) or human healthcare (antioxidant and anti-inflammatory) have been brought forward. However, despite its ability to form inclusion complexes with EO components, β-cyclodextrin has shown no significant improvement of the tested EO biological activities. On another note, the soil revegetation with clary sage displayed a clear shaping of the bacterial and fungal communities, in both the rhizospheric soil and the roots of the aromatic plant species. Altogether, our results combined with the techno-economic feasibility assessment of the channel “aromatic and medicinal plants/EO” have emphasised clary sage as a good candidate for the phytomanagement of TE-polluted soils

Дисертація на здобуття наукового ступеню доктора технічних наук за спеціальністю 05.18.06 − технологія жирів, ефірних масел і парфумерно-косметичних продуктів – Національний технічний університет "Харківський політехнічний інститут" Міністерства освіти і науки України, Харків, 2018 р. Дисертаційну роботу присвячено науковому обґрунтуванню застосування системного комплексного підходу щодо створення сучасних схем технохімічного контролю сировини і готової продукції олійножирових виробництв з використанням виключно інструментальних методів аналізу: газорідинної хроматографії, високоефективної рідинної хроматографії, газової хромато-масспектроскопії, зонального капілярного електрофорезу та ін. На основі узагальнення теоретичних і експериментальних даних розроблено схему забруднення олійного насіння, соняшникової олії та олієжировмісних продуктів природними та антропогенними екотоксикантами: пестицидами, поліхлорованими біфенілами, поліароматичними вуглеводнями, фталатами, сторонніми домішками органічного і неорганічного походження, харчовими добавками. Удосконалено стандартизований метод визначення воскоподібних речовин. Експериментально досліджено розподіл пестицидів різних класів у насінні соняшнику і продуктах його переробки. Розроблено науково обґрунтовані способи визначення пестицидів, в т.ч. за умови їх сумісної присутності. Гармонізовано з міжнародними вимогами спосіб визначення поліароматичних вуглеводнів (ПАВ) і встановлено, що вміст бенз(а)пірену є технологічним маркером по відношенню до суми ПАВ. Розроблено пріоритетний спосіб визначення фталатів, що мігрують з ПЕТ-упаковки у рослинні олії та жировмісні продукти. Теоретично та експериментально обгрунтовано необхідність застосування методів визначення жирнокислотного, ацилгліцерольного (в т.ч. індивідуального) та складу стеролової фракції для ідентифікації олій та жирів, зокрема для виявлення сторонніх домішок мінерального (мінеральних олив) та органічного (нехарчового курячого жиру) походження, тобто для цілей фальсифікації. Створено наукове та методологічне підґрунтя щодо створення національного стандарту щодо контролювання вмісту консервантів у жировмісних продуктах. Розроблено практичні рекомендації щодо удосконалення схем технохімконтролю сировини і готової продукції у виробництві соняшникової олії, в т.ч. фасованої в полімерну тару, маргаринової продукції, майонезу та салатних соусів, купажованих олій.
Thesis for the Doctor's of Engineering by specialty 05.18.06 − technology of fats, essential oils and perfumery and cosmetic products. − National Technical University "Kharkiv Polytechnic Institute" of the Ministry of Education and Science of Ukraine, Kharkiv, 2018. The thesis is devoted to the scientific substantiation of the application of the system complex approach to the creation of modern schemes of techno-chemical control of raw materials and finished products of fat-and-oil production with the use of exclusively instrumental methods of analysis: gas-liquid chromatography, high-performance liquid chromatography, gas chromatography, zonal capillary electrophoresis, etc. It has been developed the scheme on the basis of theoretical and experimental data generalization of oilseed, sunflower oil and oily products contamination by natural and anthropogenic ecotoxicants, namely pesticides, polychlorinated biphenyls, polyaromatic hydrocarbons, phthalates, foreign impurities of organic and inorganic origin, and food additives. The standardized method of determining wax-like substances has been improved. The distribution of pesticides of various classes in sunflower seed and products of its processing has been experimentally investigated. Scientifically grounded methods of pesticide determination have been developed including their simultaneous presence. A priority method for determination of migrating phthalates from PET packaging in vegetable oils and fat-containing products has been developed. The necessity of using methods for determining the fatty acid, acylglycerol (including individual) and composition of the sterol fraction for the identification of oils and fats, in particular for the foreign impurities detection of mineral (mineral oils) and organic (nonfood chicken fat) origin, i.e. for goals of falsification, has been grounded scientifically and theoretically. A scientific and methodological basis for establishing a national standard for controlling the content of preservatives in fatty products has been created. Practical recommendations for improving the schemes of technochemical control of raw materials and finished products in the sunflower oil production, including packed in plastic containers, margarine products, mayonnaise, salad dressings and blended oils have been developed.

Дисертація на здобуття наукового ступеню доктора технічних наук за спеціальністю 05.18.06 − технологія жирів, ефірних масел і парфумерно-косметичних продуктів – Національний технічний університет "Харківський політехнічний інститут" Міністерства освіти і науки України, Харків, 2018 р. Дисертаційну роботу присвячено науковому обґрунтуванню застосування системного комплексного підходу щодо створення сучасних схем технохімічного контролю сировини і готової продукції олійножирових виробництв з використанням виключно інструментальних методів аналізу: газорідинної хроматографії, високоефективної рідинної хроматографії, газової хромато-масспектроскопії, зонального капілярного електрофорезу та ін. На основі узагальнення теоретичних і експериментальних даних розроблено схему забруднення олійного насіння, соняшникової олії та олієжировмісних продуктів природними та антропогенними екотоксикантами: пестицидами, поліхлорованими біфенілами, поліароматичними вуглеводнями, фталатами, сторонніми домішками органічного і неорганічного походження, харчовими добавками. Удосконалено стандартизований метод визначення воскоподібних речовин. Експериментально досліджено розподіл пестицидів різних класів у насінні соняшнику і продуктах його переробки. Розроблено науково обґрунтовані способи визначення пестицидів, в т.ч. за умови їх сумісної присутності. Гармонізовано з міжнародними вимогами спосіб визначення поліароматичних вуглеводнів (ПАВ) і встановлено, що вміст бенз(а)пірену є технологічним маркером по відношенню до суми ПАВ. Розроблено пріоритетний спосіб визначення фталатів, що мігрують з ПЕТ-упаковки у рослинні олії та жировмісні продукти. Теоретично та експериментально обгрунтовано необхідність застосування методів визначення жирнокислотного, ацилгліцерольного (в т.ч. індивідуального) та складу стеролової фракції для ідентифікації олій та жирів, зокрема для виявлення сторонніх домішок мінерального (мінеральних олив) та органічного (нехарчового курячого жиру) походження, тобто для цілей фальсифікації. Створено наукове та методологічне підґрунтя щодо створення національного стандарту щодо контролювання вмісту консервантів у жировмісних продуктах. Розроблено практичні рекомендації щодо удосконалення схем технохімконтролю сировини і готової продукції у виробництві соняшникової олії, в т.ч. фасованої в полімерну тару, маргаринової продукції, майонезу та салатних соусів, купажованих олій.
Thesis for the Doctor's of Engineering by specialty 05.18.06 − technology of fats, essential oils and perfumery and cosmetic products. − National Technical University "Kharkiv Polytechnic Institute" of the Ministry of Education and Science of Ukraine, Kharkiv, 2018. The thesis is devoted to the scientific substantiation of the application of the system complex approach to the creation of modern schemes of techno-chemical control of raw materials and finished products of fat-and-oil production with the use of exclusively instrumental methods of analysis: gas-liquid chromatography, high-performance liquid chromatography, gas chromatography, zonal capillary electrophoresis, etc. It has been developed the scheme on the basis of theoretical and experimental data generalization of oilseed, sunflower oil and oily products contamination by natural and anthropogenic ecotoxicants, namely pesticides, polychlorinated biphenyls, polyaromatic hydrocarbons, phthalates, foreign impurities of organic and inorganic origin, and food additives. The standardized method of determining wax-like substances has been improved. The distribution of pesticides of various classes in sunflower seed and products of its processing has been experimentally investigated. Scientifically grounded methods of pesticide determination have been developed including their simultaneous presence. A priority method for determination of migrating phthalates from PET packaging in vegetable oils and fat-containing products has been developed. The necessity of using methods for determining the fatty acid, acylglycerol (including individual) and composition of the sterol fraction for the identification of oils and fats, in particular for the foreign impurities detection of mineral (mineral oils) and organic (nonfood chicken fat) origin, i.e. for goals of falsification, has been grounded scientifically and theoretically. A scientific and methodological basis for establishing a national standard for controlling the content of preservatives in fatty products has been created. Practical recommendations for improving the schemes of technochemical control of raw materials and finished products in the sunflower oil production, including packed in plastic containers, margarine products, mayonnaise, salad dressings and blended oils have been developed.

L’objectif de cette thèse a consisté en la synthèse d’un polymère à empreinte moléculaire (MIP) permettant l’extraction du phosmet, un pesticide organophosphoré largement utilisé en oléiculture. La recherche du monomère fonctionnel (MF) disposant de la meilleure capacité à interagir de manière non-covalente avec le phosmet en présence du solvant porogène le plus approprié a été réalisée pour la toute première fois au moyen d’un capteur à acétylcholinestérase. Cette stratégie innovante a permis une meilleure compréhension des mécanismes cinétiques à l’œuvre lors de l’interaction MF-molécule cible. De par l’importance de son rôle dans la détermination de la structure d’un MIP, le choix d’un agent réticulant aux caractéristiques physico-chimiques adéquates a permis de sélectionner le meilleur MIP en s’appuyant sur l’étude des isothermes d’adsorption selon les modèles de Freundlich et Langmuir. La procédure d’extraction du phosmet selon la procédure MISPE (Molecularly Imprinted Solid Phase Extraction) a été effectuée par le biais d’une cartouche SPE dont la capacité a été évaluée à partir d’une solution standard. La validation du choix des réactifs de MIP sélectionnés a été confortée par la réalisation d’une expérience de réactivité croisée appliquée à une molécule analogue au phosmet. L’extraction du phosmet de l’huile d’olive a pu être effectuée avec succès selon un protocole d’extraction en flux inverse optimisé. Cette étude ouvre ainsi la voie à la recherche de nouvelles interactions MFs-molécules cibles au moyen de biocapteurs enzymatiques inhibant des composés toxiques tels que les herbicides, fongicides et autres pesticides
The objective of this thesis has been the synthesis of a molecularly imprinted polymer (MIP) for the extraction of phosmet, an organophosphorus pesticide widely used in olive growing. The search for the functional monomer (FM) having the best ability to interact non-covalently with phosmet in the presence of the most suitable pore-forming solvent was carried out for the first time by means of an acetylcholinesterase sensor. This innovative strategy allowed us to better understand the kinetic mechanisms of FM-template interaction. Because of the importance of its role in determining the structure of a MIP, the selection of a crosslinking agent with adequate physicochemical characteristics made it possible to select the best MIP, whose adsorption isotherms were studied according to Freundlich and Langmuir models. Extraction of phosmet using a Molecularly Imprinted Solid Phase Extraction (MISPE) procedure was carried out via an SPE cartridge, whose capacity was evaluated from a standard solution. The choice of reagents and experimental conditions were validated by carrying out selectivity assays using another organophosphorus insecticide. Extraction of phosmet from olive oil was successfully carried out according to an optimized reverse flow extraction protocol. This work opens new opportunities for studying new FM-template interactions by means of enzymatic biosensors capable of detecting other inhibitors such as herbicides, fungicides and other pesticides

碩士
國立臺灣海洋大學
食品科學系
94
Organochlorine pesticides are low volatile, hydrophobic compounds which are not easily decomposed in environment. United Nations Environment Programme (UNEP) defined 12 persistent organic pollutants（POPs）, including organochlorine pesticides (aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, BHC, mirex, and toxaphene) and other three kinds of organochlorine industry products and byproducts (PCBs, dioxin and furans) which had been either banned or subjected to severe use restrictions since 2001. Organochlorine pesticides, due to their environmental persistence, could accumulate in biological lipid tissue through food chain. The food, including eggs, meats and edible fat and oils, having high lipid levels become one of the routes for human exposing to organochlorine pesticides. To investigate 14 kinds of organochlorine pesticide residues in food, the methods were developed to analyze the residues in eggs, meats and edible fat and oils. Briefly, sample lipid was extracted by solvent, cleaned up by cartridge, analyzed by GC-ECD and conformed by GC-MS-MS. The studies showed that the sensitivities of the methods in both qualification and quantification were good. Two hundred samples were analyzed by the developed methods and the results showed all tested eggs were not detected; 9 meat samples contained 4,4’-DDE (0.018 – 0.516 µg/g lipid); 10 edible oil samples contained 4,4’-DDE (0.002 – 0.063 µg/g lipid), 4,4’-DDT(0.012 – 0.14 µg/g lipid), lindane (0.002 – 0.006 µg/g lipid), α-BHC (0.008 µg/g lipid) and β-BHC (0.003 µg/g lipid). The organochlorine pesticide residues in egg samples and meat samples were in compliance with the regulation of Department of Health. The organochlorine pesticide residues were also in compliance with the criteria of US national standards. Although the organochlorine pesticide residues were found in food in this study, the residue levels have no health impact on human.

A comprehensive evaluation of the effects of an nC24 agricultural mineral oil (AMO) on tritrophic interactions between French bean Phaseolus vulgaris cv. Redlands Pioneer [Fabales : Fabaceae ], two spotted mite (TSM) Tetranychus urticea Koch [Acari: Tetranychidea] and the predatory mite Phytoseiulus persimilus Atheus-Henriot [Acari: Phytoseiidae] was conducted under laboratory conditions.
Doctor of Philosophy (PhD)

A comprehensive evaluation of the effects of an nC24 agricultural mineral oil (AMO) on tritrophic interactions between French bean Phaseolus vulgaris cv. Redlands Pioneer [Fabales : Fabaceae ], two spotted mite (TSM) Tetranychus urticea Koch [Acari: Tetranychidea] and the predatory mite Phytoseiulus persimilus Atheus-Henriot [Acari: Phytoseiidae] was conducted under laboratory conditions.

Tese de Doutoramento em Ciências - Especialidade em Biologia
The development of biopesticides follows a strong rising trend over the last two decades, and a continued growth of the global biopesticides market is forecasted. This phenomenon is largely supported by the growing awareness to environmentally friendly food production and the introduction of restrictive regulations for pesticides. In light of their multiples advantage over synthetic pesticides, biopesticides appear economical, eco-friendly and less prone to the development of resistance, and hence are expected to provide more environmentally sustainable methods of biocontrol (Czaja et al., 2015). In fact, biopesticides have been integrated in several pest and vector management programs. As a complementary approach or alternative to synthetic pesticides, phytochemicals, namely essential oils (EOs) and volatile compounds are incorporated into crop protection products, as well as repellent formulations (Regnault- Roger et al., 2012). The best market opportunities have been assigned to EO-based pesticides, owing to the great availability, GRAS status, chemical simplicity, relatively low toxicity to vertebrates and specific mode-of-action of their constituents (Isman & Akhtar, 2007; Shaaya & Rafaeli, 2007). In this context, the Apiaceae (=Umbelliferae) family, which comprised economically important plants species, presents a wide variety of bioactive compounds being also an important source of EOs and volatile compounds distributed by several distinct chemicals classes. Aware of their traditional use, their relatively large worldwide production and the bioactive potential described by many authors, we proposed to perform an appraisal of the biopesticidal potential of well-known Apiaceae species, whose experimental approach, results and discussion are here reported. In a few words, this work consisted in: (1) the characterization of EOs extracted from different plant parts of four species [Anethum graveolens (dill), Cuminum cyminum (cumin), Foeniculum vulgare var. vulgare (bitter fennel), Petroselinum crispum (plain leaf parsley)] and (2) the toxicological evaluation of some EOs and individual constituents, using as target organisms a mosquito (Anopheles atroparvus), a lepidopteran (Pseudaletia unipuncta) and a freshwater snail (Radix peregra). The anti-nematode properties of bitter fennel EOs and two phenylpropanoids against Meloidogyne javanica was also evaluated. EOs were isolated by hydrodistillation and chemically characterized by GC and GC-MS. Quantitative data were obtained using GC-FID and the identification of constituents was achieved with the help of spectra libraries and determination of their KI. The overall identification of their content ranged between 88 and 99.5%. The EOs content (ranging between 0.10-3.45%) and chemical profiles were highly variable depending of the organ type, developmental stage and origin of the material. The development of dill umbels from the pre-flowering to the ripe fruit stage was accompanied by a significant increase of (S)- carvone (from 4 to 61% of the EO content) and a reduction of α-phellandrene and dill ether contents. Bitter fennel infrutescences and leaves plus stems EOs were mainly composed by estragole (64 and 28%, respectively), followed by α-phellandrene, α-pinene and fenchone. We also identified intra-individual variations in the cultivated population of bitter fennel. Concerning cumin EOs, all fruit samples and the commercial EO were mainly constituted by cuminaldehyde (28-39 %), followed by variable amounts of pmentha- 1,4-dien-7-al, p-mentha-1,3-dien-7-al, β-pinene, p-cymene and γ-terpinene. EOs from parsley were the most complex of the four species, being characterized by a high percentage of hydrocarbon monoterpenes and several phenylpropenes (myristicin, apiole, elemicin and/or allyltetramethoxybenzene). The activity of EOs and individual compounds was assessed against A. atroparvus (3rd instar larvae), P. unipuncta (eggs and larvae) and R. peregra (eggs, juveniles and adults). Bitter fennel EOs were also tested against eggs and juveniles of M. javanica. Whenever possible, mortality (%) was recorded for a range of optimized concentrations or at different times of exposure, and the lethal parameters for 50 % and 90% (lethal concentrations, LCs, and/or lethal times, LTs) were estimated by Log-Probit analysis. EOs from parsley, cumin and bitter fennel (leaves more stems) were highly active towards the snail (both eggs and adults) and the mosquito larvae. Estimated LC50 against adult snails varied from 13.7 to 46.5 mg L-1 (48 h), and from 16 to 143 mg L-1 (24 h) against the mosquito larvae, with parsley fruit EO being the most doseeffective one in both situations. A short-time exposure (8 h) to bitter fennel EOs was also effective for snail control. Regarding assays performed on P. unipuncta, dill, cumin and parsley EOs, as well as the compounds (S)-carvone, cuminaldehyde and myristicin, showed satisfactory egg hatching inhibition, and acute contact toxicity to the 4th instar larvae (24 h-LC50 ranging from 108 to 197 μg cm-2). Dill, cumin and bitter fennel EOs and some of their constituents were effective by fumigation (≥80%). In addition, the EO from parsley fruits, trans-anethole and cuminaldehyde displayed significant feeding deterrence and growth inhibition (FDI and GI >70%), when performing the no-choice assay with treated corn leaves, causing significant negative impact on the metabolism of this lepidopteran. Parsley fruits EO was of great efficacy against P. unipuncta, acting as ovicide, larvicide (by contact), feeding deterrent and growth inhibitor. Its constituents myristicin and apiole (purified by CC) showed similar effectiveness in several assays. Besides, we distinguish the phenylpropanoid trans-anethole (a constituent of bitter fennel EOs) for its acute insecticidal, nematicidal and molluscicidal activities, being more active than its isomer (estragole). The present study demonstrates that EOs from the four studied Apiaceae species, along with some of their major compounds, have moderate to strong anti-insect and molluscicidal properties. EOs and compounds showed distinct performances depending on the type of assay, the exposure period, the tested organism and/or its developmental stage. In general, the reproductive organs (umbels-bearing fruits and eventually ripen fruits) were optimum sources of EOs containing the highest percentage of biologically active compounds (except bitter fennel). As a whole, the results demonstrates that the four plant species are promising sources of botanical biopesticides in the context of the biochemical control of phytophagous insects and vectors of human and animal diseases.
O desenvolvimento de biopesticidas tem progredido consistentemente ao longo das duas últimas décadas e as previsões apontam para uma tendência de crescimento contínuo do mercado global destes produtos. Este fenômeno é explicado essencialmente por uma maior consciencialização para a produção de alimentos de um modo sustentável e pela introdução de regulamentações mais restritivas ao uso de pesticidas. Em virtude das suas múltiplas vantagens relativamente aos pesticidas sintéticos, os biopesticidas afiguram-se económicos, ecológicos e menos propensos ao desenvolvimento de resistências constituindo, portanto, métodos de biocontrolo ambientalmente mais sustentáveis (Czaja et al, 2015). Com efeito, os biopesticidas têm sido integrados em vários programas de gestão de pragas e vetores. Como abordagem complementar ou alternativa aos pesticidas sintéticos, os fitoquímicos, nomeadamente óleos essenciais (OE) e seus constituintes voláteis, são incorporados em produtos de proteção das culturas bem como em formulações repelentes (Shaaya & Rafaeli, 2007; Regnault-Roger et al, 2012). Existe uma grande oportunidade de mercado para os pesticidas à base de OEs ou seus constituintes, em virtude da sua grande disponibilidade, da sua classificação GRAS, da simplicidade estrutural das moléculas, da relativa baixa toxicidade para os vertebrados e modos de ação específicos (Isman & Akhtar, 2007; Shaaya & Rafaeli, 2007). Neste contexto, a família Apiaceae (= Umbelliferae), que compreende espécies de plantas economicamente importantes, apresenta uma ampla variedade de compostos bioativos, sendo ainda uma importante fonte de OEs e compostos voláteis pertencentes a diversas classes químicas. Com fundamento nas suas utilizações tradicionais, na importante produção mundial e no potencial bioativo descrito por muitos autores, propusemos realizar uma avaliação do potencial biopesticida de espécies de Apiaceae bem conhecidas. Em resumo, este trabalho consistiu na: (1) caracterização dos OEs de diferentes partes de planta de quatro espécies [Anethum graveolens (aneto), Cuminum cyminum (cominho), Foeniculum vulgare var. vulgare (funcho amargo), Petroselinum crispum (salsa)] e (2) na avaliação toxicológica de alguns OEs, bem como de alguns constituintes, usando uma espécie de mosquito (Anopheles atroparvus), um lepidóptero (Pseudaletia unipuncta) e um caracol de água doce (Radix peregra) como organismos alvo. As propriedades anti-nemátode dos OEs de funcho amargo e dois fenilpropanoides contra Meloidogyne javanica foram igualmente avaliadas. Os OEs foram isolados por hidrodestilação e caracterizados quimicamente por GC e GC-MS. Os dados quantitativos foram obtidos através de GC-FID sendo a identificação dos constituintes concretizada com base na consulta de bibliotecas espectrais e na determinação dos KI. A identificação abrangeu 88 a 99,5% do conteúdo total. Os teores em OE (compreendidos entre 0,10 a 3,45% w/w) e os perfis químicos variaram consideravelmente em função do órgão, do estágio de desenvolvimento e da origem do material. O desenvolvimento de inflorescências de aneto desde a prefloração à maturação dos frutos foi acompanhado por um aumento significativo de (S)-carvona (de 4 a 61% do teor dos OEs) e uma redução dos teores de α-felandreno e anetofurano. Por seu lado, os OEs de infrutescências e caules do funcho amargo eram maioritariamente constituídos por estragole (64 e 28%, respetivamente), seguida de α-felandreno, α-pineno e fenchona. Também identificamos a ocorrência de variações intra-individuais na população cultivada de funcho amargo. Em relação aos OEs do cominho, todas as amostras de frutos e o OE comercial foram maioritariamente constituídos por cuminaldeído (28-39%), e quantidades variáveis de p-menta-1,4-dien-7-al, p-menta-1,3-dien-7-al, β-pineno, pcimeno e γ-terpineno. De entre as quatro espécies os OEs de salsa foram os mais complexos, sendo caracterizados por uma elevada percentagem de hidrocarbonetos monoterpénicos e vários fenilpropenos (miristicina, apiole, elemicina e/ou alil-tetrametoxibenzeno). Posteriormente, foi investigada a atividade dos OEs e alguns compostos individuais sobre A. atroparvus (larvas de terceiro ínstar), P. unipuncta (ovos e larvas) e R. peregra (ovos, jovens e adultos). Os OEs do funcho amargo foram ainda testados contra ovos e jovens de M. javanica. Sempre que possível, a mortalidade (%) foi registrada para uma gama de concentrações otimizadas ou em diferentes tempos de exposição, sendo os parâmetros letais para 50% e 90% (concentrações letais, CLs e/ou tempos letais, TLs) estimadas por análise Log-Probit. Os OEs de salsa, cominho e funcho amargo (folhas e caules) foram extremamente ativos contra as formas embrionária e adulta do caracol, assim como nas larvas de mosquito. As CL50 estimadas para os caracóis adultos variaram entre 13,7 a 46,5 mg L-1 (48 h), e entre 16 a 143 mg L-1 par as larvas do mosquito, sendo evidenciada a maior eficácia do OE de frutos de salsa na dose-resposta, contras ambos os organismos. A exposição de curta duração (8 h) aos OEs do funcho amargo foi também eficaz no controlo dos caracóis. Nos ensaios realizado com P. unipuncta, os OEs de aneto, cominho e salsa, bem como os compostos (S)-carvona, cuminaldeído e miristicina mostraram acentuados efeitos inibitórios na eclosão dos ovos, e uma aguda toxicidade por contacto sobre as larvas no quarto instar (as CL50 às 24 h variaram entre 108 a 197 μg cm-2). Os OEs de aneto, cominho e funcho e alguns dos seus constituintes foram eficazes por fumigação (≥80%). Além disso, o OE de frutos de salsa, o trans-anetole e o cuminaldeído apresentaram efeitos inibitórios agudos no consumo de folhas de milho tratadas e no crescimento das larvas (FDI e GI> 70%), revelando um impacto negativo no metabolismo deste lepidóptero muito significativo. O OE dos frutos da salsa foi de grande eficácia ovicida, larvicida, fago-repelente, e inibidor do crescimento larvar. Os constituintes miristicina e apiole, ambos purificados do OE de frutos de salsa por CC, mostraram eficácia similar em alguns ensaios. Além disso, distinguimos o phenylpropanoid trans-anetole (constituinte do OE de funcho) pela sua forte atividade inseticida, nematicida e moluscicidas, sendo mais ativo que o seu isómero (estragole). O presente estudo demonstra que os OEs das quatro espécies de Apiaceae, e alguns dos compostos testados, apresentam propriedades anti-inseto e moluscicidas moderadas a elevadas. Os OEs e compostos apresentaram desempenhos distintos, dependendo do tipo de ensaio, do período de exposição, do organismo testado e/ ou do seu estágio de desenvolvimento. Em geral, os órgãos reprodutivos destas plantas (infrutescências, eventualmente frutos maduros) foram ótimas fontes de OEs contendo percentagens superiores de compostos biologicamente ativos (exceto o funcho amargo). No seu todo, os resultados demonstram que as quatro espécies de plantas são promissoras fontes de biopesticidas botânicos no contexto do controlo bioquímico de insetos fitófagos e vetores transmissores de doenças em humanos e animais.

Large burrowing owl (Aihene cunicularia) populations exist in areas of intensive agriculture in California, and pesticide exposure has been identified as a potential threat to population persistence. I evaluated breeding season use of agricultural fields by adult male owls using radio telemetry, and examined egg contaminant residues to estimate population-level effects on reproduction and survival. Reproduction and survival were estimated annually, and an index of diet was inferred from pellet samples. A total of 11 adult males in 1998 and 22 in 1999 were successfully radio-tracked. Mean fixed kernel home range sizes were 172 ha (SE=68) in 1998 and 98 ha (SE=16) in 1999. Pellet analyses indicated a substantial increase in the numbers of rodents consumed in 1999, associated with an observed population explosion of California voles (Microtus calfornicus). Distance to the nest was the most important factor in differentiating between foraging and random locations, and there was no tendency to select or avoid any cover type. Owls did forage in agricultural fields, but I failed to find evidence of selection or avoidance of fields recently treated with pesticides. A total of 92 eggs were collected over 5 years. Egg contaminants were generally limited to the presence of p,p'DDE, which fluctuated by 4 orders of magnitude among years, from 0.05 ug/g to 33 ug/g fresh weight p,p'DDE. There was a general pattern of decline in egg residues over time for individual birds. The levels of p,p'DDE I documented did not appear to have any effect on either productivity or survival of adult females, nor were they clearly related to diet. I modeled the effects of various pesticide exposure impacts on demographic rates and determined that exposure rates based on field data would lead to relatively minor declines in population growth rate. An elasticity analysis of burrowing owl demographic parameters revealed a variable pattern, but generally indicated that factors influencing anyone of the demographic parameters of burrowing owls can have a substantial impact on population growth rate.
Graduation date: 2002