Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O presente trabalho estudou o uso de processo oxidativo avanÃado para a remoÃÃo do agrotÃxico organofosforado clorpirifÃs. Para tanto, sistema de reator em escala laboratorial e escala piloto foram estudados. Na primeira etapa, em escala laboratorial, foram realizados estudos dos parÃmetros temperatura, pH e dosagem do perÃxido de hidrogÃnio, concentraÃÃo do agrotÃxico e efeito inibitÃrio de Ãnions. Os resultados indicaram que uma temperatura de 45 oC propicia melhor remoÃÃo do agrotÃxico usando apenas a radiaÃÃo UV, contudo, para o sistema combinado UV/H2O2, a temperatura nÃo afetou o rendimento do processo. A influÃncia do pH foi estudada para os sistemas H2O2 e UV/H2O2 e foi verificado que o pH nÃo influenciou na eficiÃncia do sistema UV/H2O2, entretanto, em pH 10 ocorreu um melhor rendimento para o sistema H2O2 na remoÃÃo do agrotÃxico. Entre as dosagens de perÃxido de hidrogÃnio estudadas, a de 1,5g/L foi a mais eficiente na remoÃÃo do agrotÃxico. O efeito inibitÃrio dos Ãnions, cloreto, nitrato, sulfato e carbonato nÃo se mostrou efetivo na remoÃÃo do agrotÃxico durante 480 minutos, contudo, o Ãnion bicarbonato provocou em 60 minutos a total conversÃo do clorpirifÃs em um composto desconhecido. A segunda etapa foi realizada no reator de escala piloto e foram estudados trÃs vazÃes, 1,5; 2,0 e 3,0 L/min. As concentraÃÃes residuais do agrotÃxico ao final de 480 minutos de experimento para os trÃs vazÃes foram 0,30; 0,43 e 0,5 mg/L, respectivamente. A remoÃÃo de turbidez e cor foram eficientes para as vazÃes estudadas, em contraste com a remoÃÃo de DQO. / This study investigated to advanced oxidation process (POA) for removal of organophosphorus pesticide chlorpyrifos. Reactor system, in laboratory and pilot scale, have been studied. In the first stage, in laboratory scale, were performed studies of the parameters temperature, pH, dosage of hydrogen peroxide, pesticide concentration and inhibitory effects of anions. The results indicated that a temperature of 45 oC showed a better pesticide removal using only UV radiation, however, for the system UV/H2O2, the temperature did not affect the process. The pH effect was studied for H2O2 and UV/H2O2 systems and was observed that pH did not affect the efficiency of the system UV/H2O2. In addition, at pH 10 a better performance for the system H2O2 on the removal of pesticide was observed. Hydrogen peroxide dosage also was studied, and 1,5g/L dosage was most efficient in the pesticide removal. The inhibitory effect of the anions, such as chloride, nitrate, sulfate and bicarbonate was not significantive in the pesticide removal at a time of 480 minutes. In contrast, presence of carbonate anion at 60 minutes, there was a total transformation of chlorpyrifos in an unknown compound. The second stage was conducted on a pilot scale, and flow rate were studied (1.5; 2.0 and 3.0 L/min). The final concentration of pesticide at 480 minutes, for the three flow, were 0.30; 0.43 and 0.5 mg/L, respectively. The turbidity and color removal was efficient for all flows studied, in contrast with the DQO removal.

Chlorpyrifos is a widely used organophosphate insecticide, functioning through the inhibition of acetylcholinesterase. Recent studies report negative long-lasting biochemical and behavioral effects at levels without acetylcholinesterase inhibition. Our lab studies have identified the endocannabinoid system as a target for OP low-dose neurotoxicity. This thesis identifies the proteins and their associated neurotransmitter systems in the hippocampus that have been affected by low dose developmental exposure to the OP insecticide CPF. Male rat pups were treated from postnatal day 10 (PND) - PND16 with either corn oil (vehicle), 0.75 mg/kg of CPF, or 0.02 mg/kg of PF-04457845, a specific fatty acid amide hydrolase (FAAH) inhibitor. On PND38, rats were sacrificed for hippocampal extraction, and shotgun proteomics was used for protein expression. DAVID and Ingenuity Pathway Analysis software detected differentially expressed proteins such as Neuroligin-2 and Synaptotagmin 2, and disrupted signaling pathways such as ephrin B signaling, synaptogenesis signaling, and glutamate receptor signaling. Taken together, our data suggests that CPF reduces glutaminergic signaling pathways, greatly reducing long-term potentiation, prohibiting proper synapse formation, and therefore disrupting the proper functioning of the hippocampus.

Le maintien et le renouvellement des populations de poissons coralliens dépendent en grande partie du recrutement larvaire, c’est-à-dire de l’installation des larves pélagiques dans les habitats récifaux adultes, et de leur survie après s’être métamorphosées en juvéniles. De plus en plus d’études révèlent que les changements de composition de l’eau, causés par le changement climatique et la pollution, peuvent altérer les capacités sensorielles des poissons coralliens, diminuant leurs aptitudes à localiser des habitats propices (maximisant leur croissance et diminuant leur mortalité) lors de l’installation. Cependant, les mécanismes internes à l’origine de ces phénomènes sont méconnus. Lors de cette thèse, j’ai examiné le recrutement larvaire du poisson chirurgien bagnard Acanthurus triostegus et mis en évidence que les changements écologiques, morphologiques, physiologiques et comportementaux qui s’y déroulent correspondent à une métamorphose contrôlée par les hormones thyroïdiennes (HT). J’ai ensuite analysé comment des stress d’origine anthropique, tels que l’élévation des températures de surface et la pollution par un pesticide d’origine agricole, peuvent perturber sa métamorphose. Lors de cette étape clé de leur cycle de vie, ces perturbations diminuent les taux d’HT, altérant la maturation de leurs organes sensoriels, leurs capacités sensorielles, et augmentant leur mortalité. Cette thèse est donc une analyse holistique de l’impact des perturbations anthropiques sur les processus moléculaires, et les changements histologiques, anatomiques et comportementaux du recrutement larvaire des poissons coralliens. Elle souligne l’importance du système thyroïdien, et invite à une meilleure compréhension des processus endocriniens du recrutement larvaire, dans l’optique d’une amélioration de la conservation des récifs coralliens. / The persistence and sustainability of coral-reef fish populations depends on the continued larval recruitment, i.e. successful settlement by pelagic larvae into adult reef habitats and post-settlement survival through metamorphosis to a juvenile stage. There is growing evidence that changes to water conditions due to global change and waterborne pollution can impair coral-reef fish sensory abilities to locate settlement habitats that maximize growth while minimizing mortality risk. However, the inner mechanisms of such impairments remain unknown. In this thesis, I have examined the recruitment phase of the convict surgeonfish Acanthurus triostegus, and determined that the ecological, morphological, physiological and behavioral changes occurring at recruitment correspond to a metamorphosis mediated by thyroid hormones (TH). Then, I investigated whether this metamorphosis is prone to endocrine disruption under anthropogenic disturbances such as elevated sea water temperature and agricultural pesticide pollution. I demonstrated that such pressures can reduce TH levels at a critical developmental stage in coral-reef fishes, impairing their metamorphic processes such as intestine remodeling, sensory organ maturation, and sensory abilities acquisition, further increasing their mortality rates. Overall, this thesis is a holistic analysis that addresses molecular, histological, anatomical, and behavioral assays of multiple stressors affecting coral-reef fish recruitment. It indicates the importance of a proper endocrine function during coral-reef fish recruitment, highlighting the need for a better understanding of these processes for coral-reef conservation.

Thesis (MScAgric)--Stellenbosch University, 2004. / ENGLISH ABSTRACT: Colonies of Planococcus ficus (Signoret) were reared from three different areas, Hex River Valley, Robertson and Stellenbosch. An insectary colony and a table grape colony from Nietvoorbij experimental farm were also included in the study. A range of concentrations of chlorpyrifos was applied topically to individuals from the different colonies. The Stellenbosch population had the lowest LDso, although it was not significantly different from that of the insectary and Robertson colonies. The Hex River Valley and table grape colonies had a significantly higher LDso than the Robertson, Stellenbosch and insectary colonies, although the relative tolerance was 1.5, which would probably not result in significant control failure in the field. However, this does indicate that there is potential for the development of resistance to chlorpyrifos in the vine mealybug in South Africa. / AFRIKAANSE OPSOMMING: Kolonies van Planococcus ficus (Signoret), is versamel en geteel uit drie verskillende areas, Hex.riviervallei, Robertson en Stellenbosch. 'n Bestaande insektarium kolonie van die Lanbou Navorsings Raad en 'n tafeldruif kolonie vanaf Nietvoorbij proefplaas is ook ingesluit in die studie. 'n Reeks konsentrasies van chlorpyrifos is topikaal aangewend aan individue van die verskillende kolonies. Die Stellenbosch populasie het die laagste LDso getoon alhoewel dit nie betekenisvol verskil het van die LDso van die insektarium - en Robertson kolonies nie. Die Hexriviervallei en tafeldruif kolonies se LDso was betekenisvol hoër as die Robertson, Stellenbosch and insektarium kolonies. Alhoewel die relatiewe weerstand 1.5 was, sal dit waarskynlik nie tot 'n aansienlike beheermislukking in die veld lei nie. Nogtans dui dit op die potensiaal vir moontlike ontwikkeling van weerstand teen chlorpyrifos in die wingerdwitluis.

No description available.

The intensification of agricultural production in the Mekong Delta has faced serious challenges with respect to increased use of agrochemicals and especially pesticides. The indiscriminate use of pesticide could potentially impact on the long-term food production, environmental and human health in the delta. The aim of this thesis was to investigate the negative side effects of the current use of pesticides on climbing perch (Anabas testudineus) in rice fields using brain acetylcholinesterase (hereafter referred to as AChE) activity as a biomarker. The empirical work, on which this thesis is based, includes structured questionnaires, laboratory and field experiments. First, a field survey using questionnaires was carried out to gain a better understanding of the current state of rice farming systems, the use of pesticides and attitude to pest management strategies among rice and rice-fish farmers, as well as to provide basic information for the set-up of the laboratory and field experiments. Secondly, laboratory studies were conducted to clarify if the selected insecticides applied alone and in mixtures caused negative side effects on climbing perch fingerlings. Thirdly, further toxicity studies were carried out, under rice field conditions, to further investigate the toxicity effects of the insecticides, applied alone, in mixtures and under sequential applications, on climbing perch fingerlings. The results showed that although there were a more selective use of pesticides and an increased awareness among farmers of the negative side effects of pesticides in 2007 as compared to 1999, the current use of pesticide in the Mekong Delta still cause many problems to the environment and human health. Chlorpyrifos ethyl (hereafter referred to as CPF) was found to cause a significant and more prolonged inhibition on the brain AChE activity in climbing perch than fenobucarb (hereafter referred to as F). The inhibition by the mixture of CPF and F were significantly higher than the inhibition by only F, but less prolonged and significant lower than the inhibition by only CPF. The results suggest that the combined effect from a mixture of F and CPF can create both additive effects initially and later antagonistic effects. CPF and F applied at concentrations used by farmers, either as separate doses, in a mixture or in sequential doses, decreased the brain AChE activity, growth and survival rates in climbing perch. The results demonstrate that brain AChE activity in climbing perch is a relevant biomarker for monitoring of exposure to, and sub-lethal impacts from organophosphates and carbamates under tropical conditions. The result also shows that 2-PAM re-activate the brain AChE activity, and can be used as an alternative method to assess the AChE inhibition level in organisms recently exposed to OP’s, in situation where it may be difficult to find unexposed individuals as controls. In conclusion, this thesis shows that the current use of pesticides in the Mekong Delta has a negative effect on climbing perch living in rice fields. It indicates that a sustained long-term food production in the Mekong Delta must be based on ecological principles, taking advantages of ecosystem biodiversity and productivity, and not through intensified use of pesticides. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 5: Submitted.</p>

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Master of Science / Department of Grain Science and Industry / Bhadriraju Subramanyam / The insecticides, β-cyfluthrin and chlorpyrifos-methyl plus deltamethrin, are approved in the United States for treating empty bin surfaces. Chlorpyrifos-methyl plus deltamethrin and spinosad insecticides are approved for direct treatment of wheat. The efficacy of commercial formulations of β-cyfluthrin and chlorpyrifos-methyl plus deltamethrin at labeled rates was evaluated against adults of 16 field strains of the red flour beetle, Tribolium castaneum (Herbst); seven strains of sawtoothed grain beetle, Oryzaephilus surinamensis (L.); and two strains of the lesser grain borer, Rhyzopertha dominica (F.). Concrete arenas in plastic Petri dishes (9 cm diameter) were used to simulate the concrete floor of empty bins. The time for ~100% knockdown and mortality of adults of laboratory strains of the three species was first established by exposing them to insecticide-treated concrete surfaces for 1 to 24 h. Adults of field strains of each species were exposed to specific established insecticide-time combinations. Mortality of all species was lower than knockdown, suggesting recovery after seven days when placed on food. Chlorpyrifos-methyl plus deltamethrin did not control all R. dominica and most O. ]surinamensis field strains. β-cyfluthrin was extremely effective against R. dominica but ineffective against T. castaneum and O. surinamensis field strains, even at four times the high labeled rate. Field strains of R. dominica were highly susceptible to spinosad and chlorpyrifos-methyl plus deltamethrin at labeled rates on hard red winter wheat. Strains of T. castaneum and O. surinamensis were susceptible only to the latter insecticide. Dose-response tests with spinosad on the two least susceptible field strains of each species showed the lethal dose for 99% mortality (LD[subscript]99) for T. castaneum and R. dominica field strains were similar to that of the corresponding laboratory strains. Corresponding values for the two O. surinamensis field strains were significantly greater (~6 times) than the laboratory strain. The effective dose for progeny reduction (ED[subscript]99) of only one R. dominica field strain was significantly greater (~2 times) than that of the laboratory strain. The baseline susceptibility data of field strains of three insect species to spinosad will be useful for monitoring resistance development once this product is commercially released as a grain protectant.

In this Thesis either advanced oxidation or reductive processes are investigated for the degradation of two pesticides considered persistent in the environment: amicarbazone (AMZ) and chlorpyrifos (CP). In chapter I, different advanced oxidation processes (AOPs) driven by sulfate (SO4o-) and hydroxyl radicals (oOH) were applied to the degradation of AMZ. In the first study, several persulfate (PS) activated reactions were explored for AMZ degradation, namely activation with UVA radiation, Fe(II) and H2O2, as well as the combination of UVA radiation with Fe(II), Fe(III) and Fe(III)-complexes. Here, the influence of different reaction variables, such as solution pH, reactants and pesticide initial concentrations, addition of a second oxidant (H2O2) and the addition of different iron catalysts were also investigated. Control experiments regarding the photolysis of iron species in the absence of PS captured our interest and, with the aim of exploring more deeply this process on AMZ degradation, a second investigation was carried out. In this second study, a Doehlert experimental design was applied to investigate the simultaneous effects of two variables on AMZ degradation: pH and Fe(III):carboxylate ratio, where the carboxylate could be oxalate, citrate or tartrate. A response surface model for the observed degradation rate (kobs) as a function of pH and Fe(III):carboxylate ratio was obtained. The processes explored in both aforementioned studies revealed to be effective for AMZ removal, although nothing is known yet about their effectiveness regarding toxicity removal. Given that, a third study was carried out, where the toxicity of AMZ solutions, before and after submission to the processes studied was evaluated towards five microorganisms: Vibrio fischeri (acute toxicity), Tetrahymena thermophile, Chlorella vulgaris (chronic toxicity), Escherichia coli and Bacilus subtilis (antimicrobial activity). The last investigation detailed in chapter I is related with the application of zero-valent-metals on PS activation, which is a subject that links this chapter with the following one. For that, zero-valent-iron (ZVI) was investigated as a PS activator and the influence of variables that help to assess the environmental applicability of this process. In general, organochlorine pesticides reveal a higher resistance to oxidation than reduction, the latter process preferred when the aim is to degrade that important class of contaminants. Therefore, in chapter II the reductive degradation of CP by means of zero-valent-metals and bimetallic particles was investigated. ZVI has been extensively applied for that purpose. However, besides iron, other zero-valent metals can be potential reactive materials for reductive degradation and hence, in this study, the effectiveness of Zn0 and Cu0 was also explored in comparison to that widely reported for ZVI. Furthermore, two different ways of enhancing metals reactivity were here explored: i) by coating ZVI or Zn0 with a more noble metal (Cu), in order to analyze the copper catalytic effect on the bimetallic system; ii) by different surface pretreatments. / Na presente Tese de Doutorado foram abordados tanto processos oxidativos avançados (POA), como processos redutivos por metais de valência zero, na degradação de dois pesticidas considerados persistentes no meio ambiente: amicarbazona (AMZ) e clorpirifós (CP). No capítulo I são apresentados os estudos realizados com diversos POA, mediados por radicais sulfato (SO4o-) e hidroxila (oOH), aplicados da AMZ. Num primeiro estudo foi explorada a ativação do oxidante persulfato (PS), de diferentes formas, tais como radiação UVA, H2O2 e Fe(II), assim como a combinação de radiação UVA com Fe(II), Fe(III) e complexos de Fe(III). Aqui também foram investigados os efeitos de diversas variáveis reacionais, tais como pH, concentração inicial de reagentes e de pesticida, adição de um segundo oxidante (H2O2) e adição de diferentes espécies de ferro. Os testes realizados, para efeito de controle, referentes à irradiação das espécies de Fe(III) na ausência de PS, despertaram o interesse para um estudo mais aprofundado sobre o efeito da fotólise destas espécies na degradação da AMZ, surgindo assim o segundo trabalho. Neste utilizou-se um projeto experimental de Doehlert, para avaliar o efeito de duas variáveis em simultâneo quanto à degradação da AMZ: pH e proporção Fe(III): ligante, sendo o ligante um dos seguintes carboxilatos: oxalato, citrato ou tartarato. Um modelo de superfície de resposta, que correlaciona a taxa de degradação observada (kobs) em função do pH e proporção Fe(III):ligante foi obtido para cada um dos complexos de Fe(III) estudados. Os processos explorados, tanto no primeiro como no segundo estudo, se mostraram eficazes na remoção da AMZ, porém nada se sabe acerca da remoção da toxicidade. Para tal, foi desenvolvido um terceiro estudo dedicado à avaliação da toxicidade da solução de AMZ, antes e após a aplicação de cada um dos processos anteriormente abordados, contra cinco micro-organismos: Vibrio fischeri (toxicidade aguda); Tetrahymena thermophila, Chlorella vulgaris (toxicidade crônica); Escherichia coli e Bacilus subtilis (atividade antimicrobiana). O último estudo abordado no capitulo I é referente à aplicação de metais de valência zero também nos POA, correlacionado assim o capítulo I e o capítulo II. Como tal, foi feito um estudo de ativação de PS por meio de ferro de valência zero (Fe0), em que se investigou a influência de diversas variáveis por forma a inferir sobre a aplicabilidade prática deste processo. Pesticidas organoclorados apresentam maior resistência à degradação por processos oxidativos do que redutivos, sendo preferível o último na degradação desta importante classe de contaminantes. Como tal, o capítulo II se refere à degradação redutiva, por meio de diferentes metais de valência zero e partículas bimetálicas, do pesticida organoclorado CP. Além do amplamente explorado Fe0, outros metais podem ser aplicados neste processo, pelo que, neste estudo, explorou-se a potencialidade de Zn0 e Cu0 comparativamente ao primeiro. Ainda neste estudo foram investigadas duas formas de aumentar a reatividade dos metais: i) no caso do Fe0 e Zn0, revestindo com um metal mais nobre (Cu), por forma a observar o efeito catalisador do último no sistema bimetálico; ii) realizando um pré-tratamento à superfície dos metais.

Submitted by Eunice Novais (enovais@uepg.br) on 2018-08-15T17:01:17Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Lillian Caroline Fernandes.pdf: 1580382 bytes, checksum: e37251c84c29f43f323382ed3a322f10 (MD5) / Made available in DSpace on 2018-08-15T17:01:17Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Lillian Caroline Fernandes.pdf: 1580382 bytes, checksum: e37251c84c29f43f323382ed3a322f10 (MD5) Previous issue date: 2018-02-23 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O aumento progressivo da população e da produção de alimentos torna o uso de agrotóxicos essencial. O Brasil tem notoriedade à nível mundial na quantidade desses produtos comercializados, sendo destaque desde 2008. As classes mais utilizadas são os herbicidas, fungicidas e inseticidas. Sabe-se que esses produtos apresentam risco a saúde humana, podendo afetar múltiplos sistemas. Além disso, alguns estudos estão demonstrando efeitos neurotóxicos e comportamentais causados por esses agentes, no entanto, o mecanismo desse efeito permanece incerto. Os pesticidas têm diferentes mecanismos de ação e ainda, podem apresentar efeitos sinérgicos entre si. Com isso, o presente estudo busca avaliar se a exposição ao Paraquat, que é um herbicida, amplamente utilizado devido ao seu baixo curso e amplo espectro de forma isolada e as associações com Mancozeb, que é um fungicida e com o Clorpirifós, que é um inseticida são capazes de produzir efeitos comportamentais. Para isso, foram utilizados 48 ratos machos da linhagem Wistar divididos em 4 grupos de acordo com o agente de exposição: Controle/Água (N=12), Paraquat 1mg/kg (N=12), Paraquat 1mg/kg e Mancozeb 3 mg/kg (N=12), Paraquat 1mg/kg e Clorpirifós 0,3 mg/kg (N=12). A exposição ocorreu diariamente durante 28 dias por via oral (gavagem). Após o período de exposição, foram realizados os testes de preferência à sacarose, reconhecimento social, campo aberto, reconhecimento de objetos, labirinto em cruz elevado e natação forçada. Como resultado têm-se que os animais submetidos ao tratamento apresentaram déficit na memória social e declarativa, evidenciado pelo teste de reconhecimento social e de objetos. Além disso, apresentaram também sinais do tipo ansiogênicos e depressivos demonstrado pelo teste de labirinto em cruz elevado e natação forçada. Além dos sinais não motores os animais também apresentaram comprometimento motor, evidenciado pelo teste de campo aberto. Como conclusão, demonstramos que a exposição ao Paraquat e associações com Mancozeb e Clorpirifós causou alterações comportamentais nos animais submetidos a exposição com Paraquat e associação com Mancozeb e Clorpirifós. / The progressive increase in population and food production makes the use of agrochemicals essential. Brazil is known worldwide in the quantity of these products marketed, being highlighted since 2008. The classes most used are herbicides, fungicides and insecticides. It is known that these products pose a risk to human health and can affect multiple systems. In addition, some studies are demonstrating neurotoxic and behavioral effects caused by these agents, however, the mechanism of this effect remains uncertain. Thus, the present study aims to evaluate whether exposure to Paraquat, which is a herbicide, widely used because of its low cost and broad spectrum in isolation and as associations with Mancozeb, which is a fungicide and with Chlorpyrifos, which is an insecticide are capable of producing effects. For this, 48 male Wistar rats divided into 4 groups according to the exposure agent: Control/Water (N= 12), Paraquat 1mg/kg (N=12), Paraquat 1mg/kg and Mancozeb 3 mg/kg (N = 12), Paraquat 1 mg/kg and Chlorpyrifos 0.3 mg/kg (N = 12). The exposure occurred daily for 28 days orally (gavage). After the exposure period, sucrose preference tests, social recognition, open field, object recognition, elevated plus maze and forced swimming were performed. As a result, the animals submitted to the treatment had deficits in the social and declarative memory, evidenced by the test of social recognition and objects. In addition, they also presented anxiogenic and depressive signs, demonstrated by the elevated plus maze test and forced swimming. In addition to non-motor signals, the animals also presented motor impairment, evidenced by the open field test. As a conclusion, we demonstrated that exposure to Paraquat and associations with Mancozeb and Chlorpyrifos caused behavioral changes in animals submitted to Paraquat exposure and associated with Mancozeb and Chlorpyrifos.