Due to the widespread application of pesticides and herbicides in agricultural industries, these substances have been highlighted as emerging contamination of natural ground and surface water resources. Conventional water treatment processes are only effective in removing emerging contaminants in water. The mechanism of degradation of organic impurities present in water using ozone is known to either directly involve the ozone molecule or to occur by the indirect effect of free hydroxyl radicals (•OH). The latter are produced in the radical chain reaction of ozone decomposition. A series of experiments were carried out to investigate the effects of particle sizes of nano-ZnO catalysts on removal of atrazine (ATZ). Nano-ZnO catalysts increase the rate of ozone decomposition and atrazine removal by production of hydroxyl radicals as oxidative intermediates. However, different particle sizes have a minimal effect on the rate of ozone decomposition and atrazine removal. It is believed that molecular ozone is adsorbed on the surface of nano-ZnO followed by the oxidation of the ozone molecule. This leads to the production of OH radicals. Therefore, it is reasonable to assume that reaction is carried out in the bulk of the solution and the rate is independent of catalyst’s surface area. This is probably the reason for similar reaction rates of different particle sizes of nano-Zno catalysts. Additionally three different metal oxides (ZnO, Mn2O3 and Fe2O3) loaded on ƴ-alumina and ƴ-alumina (metal oxide-free) were used in catalytic ozonation of aquatic atrazine samples. The findings substantiate the strong influence of molecular ozone on degradation of ATZ and the partial involvement of hydroxyl radicals in the mechanism. Based on adsorption studies, atrazine has a low affinity towards adsorption on the surface of the catalysts. It is logical to assume that ozone reacts with the hydroxyl groups of the catalyst to form a highly reactive metal-ozone complex. This layer could react with a molecule of atrazine through an electron-transfer mechanism. The residual concentration of ATZ and total organic carbon (TOC) were determined by High Performance Liquid Chromatography (HPLC) and Total Organic Carbon (TOC) analyses.

Call number: LD2668 .T4 1978 B69 / Master of Science

Thesis (MScAgric)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The herbicide atrazine (ATZ, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) has been identified as an environmental endocrine disruptor and possible human carcinogen. The presence of atrazine, along with its degradation products, in soils and water supplies therefore raises concern. Atrazine biodegradation in soils is well-covered to date, however, atrazine degradation by abiotic mineral surfaces, and the chemical mechanism by which it occurs, is not fully understood. Furthermore, with a changing global climate, the effects of wetting and drying cycles on soil processes (e.g. atrazine degradation) is largely unknown, but increasing in importance. This study therefore investigated atrazine degradation on six common soil mineral surfaces, namely birnessite, goethite, ferrihydrite, gibbsite, Al3+-saturated smectite and quartz, as well as the effects that drying these surfaces has on atrazine degradation. In the first part, a comparison was conducted between the reactivity of fully hydrated and drying mineral surfaces toward atrazine, by reacting atrazine-mineral mixtures under both moist and ambient drying conditions, in parallel, for 14 days. Under moist conditions, none of the mineral surfaces degraded atrazine, but under drying, birnessite and goethite degraded atrazine to non-phytotoxic hydroxyatrazine (ATZ-OH, 2-hydroxy-4-ethylamino-6-isopropylamino-1,3,5-triazine) as major product and phytotoxic deethylatrazine (DEA, 2-chloro-4-amino-6-isopropylamino-1,3,5-triazine) as minor product. The mineral surface reactivity was birnessite (66% degradation) > goethite (18% degradation) >> other mineral surfaces (negligible degradation), indicating possible atrazine oxidation. In the second part, the effects of drying rate were investigated on birnessite only (the most reactive surface), by conducting the drying (1) gradually at ambient rates, (2) rapidly under an air stream, and (3) gradually in the absence of water using only organic solvent. After 30 days of ambient drying, 90% of the atrazine was degraded to ATZ-OH and DEA, but the same extent of degradation was achieved after only 4 days of rapid drying with an air stream. Thirty days of gradual drying using only organic solvent did not increase atrazine degradation compared to the water-moist drying surface. In each case, degradation initiated at a critical moisture content of 10% of the original moisture content. In the third part, the degradation mechanism was further investigated. To test for the possible oxidation of atrazine by the birnessite surface, moist atrazine-birnessite mixtures were dried under a nitrogen (N2) stream to eliminate possible oxidation by atmospheric oxygen (O2). Dissolved Mn2+ was extracted at the end of the experiment to observe any reduction of birnessite. Under N2, the same products were formed as before, with no appreciable Mn2+ production, indicating non-oxidative atrazine degradation by birnessite. The final part investigated the effects ultraviolet (UV) radiation has on the degradation of atrazine by drying mineral surfaces. The UV-radiation enhanced the degradation of atrazine, but no other degradation products were formed. It was therefore concluded that atrazine degradation on redox-active soil mineral surfaces is enhanced by drying, via a net non-oxidative mechanism. Furthermore, this drying-induced degradation is an atrazine detoxification mechanism which could be easily applied through agricultural practices such as windrowing, ploughing and any other practice that (rapidly) dries a Mn- or Fe-oxide rich agricultural soil. / AFRIKAANSE OPSOMMING: Die onkruiddoder atrasien (ATS, 2-chloro-4-etielamino-6-isopropielamino-1,3,5-triasien) is as 'n omgewings endokriene versteurder en moontlike menslike karsinogeen geidentifiseer. Die teenwoordigheid van atrasien, tesame met sy afbreekprodukte, in grond en water toevoere wek dus kommer. Die bio-afbreking van atrasien in gronde is tot dusver goed gedek, maar die afbreking van atrasien deur abiotiese mineraaloppervlaktes, en die chemiese meganisme waarmee dit plaasvind, word nie heeltemal verstaan nie. Verder, met 'n veranderende globale klimaat, is die effekte van benatting- en drooging-siklusse op grondprosesse (bv. atrasien afbreking) grootliks onbekend, maar toenemend belangrik. Daarom het hierdie studie atrasien afbreek op ses algemene mineraaloppervlaktes, naamlik birnessiet, goethiet, ferrihidriet, gibbsiet, Al3+-versadigde smektiet en kwarts, ondersoek, asook die effekte wat drooging van hierdie oppervlaktes op atrasien afbreking het. In die eerste deel, was 'n vergelyking gedoen tussen die reaktiwiteit van volgehidreerde en droëende mineraaloppervlaktes teenoor atrasien, deur atrasien-mineraal mengsels, in parallel, onder albei nat en omliggende droogings toestande te reageer vir 14 dae. Onder nat toestande, het geeneen van die mineraaloppervlaktes atrasien afgebreek nie, maar onder drooging het birnessiet en goethiet atrasien afgebreek na nie-fitotoksiese hidroksieatrasien (ATS-OH, 2-hidroksie-4-etielamino-6-isopropielamino-1,3,5-triasien) as hoofproduk en fitotoksiese deetielatrasien (DEA, 2-chloro-4-amino-6-isopropielamino-1,3,5-triasien) as minder-produk. Die mineraaloppervlakte-reaktiwiteit was birnessiet (66% afbreking) > goethiet (18% afbreking) >> ander mineraaloppervlaktes (geringe afbreking), wat moontlike atrasien oksidasie aandui. In die tweede deel, is die effekte van droogingstempo ondersoek, op birnessiet alleenlik (die mees reaktiewe oppervlak) deur drooging by (1) 'n omliggende geleidelike tempo, (2) 'n versnelde tempo onder 'n lugstroom, en (3) 'n geleidelike tempo in die afwesigheid van water, deur slegs gebruik te maak van 'n organiese oplosmiddel. Na 30 dae se geleidelike drooging, is 90% van die atrasien afgebreek na ATS-OH en DEA, maar dieselfe hoeveelheid afbreking is bereik na slegs 4 dae onder versnelde drooging met die lugstroom. Dertig dae van geleidelike drooging met slegs organiese oplosmiddel het nie atrasien afbreking vermeerder in vergelyking met die water-nat droëende oppervlak nie. In elke geval, is afbreking geïnisieer by 'n kritiese water inhoud van 10% van die oorspronklike water inhoud. In die derde deel is die afbrekingsmeganisme verder ondersoek. Om te toets vir die moontlike oksidasie van atrasien deur die birnessiet oppervlak, is nat atrasien-birnessiet mengsels onder stikstof (N2) gedroog, om die moontlike oksidasie deur atmosferiese suurstof (O2) te verhoed. Opgeloste Mn2+ was teen die einde van die eksperiment geekstraëer om enige reduksie van birnessiet waar te neem. Onder N2 is dieselfde produkte as voorheen gevorm, met geen aansienlike Mn2+ produksie nie, aanduidend van 'n nie-oksideerende afbreek van atrasien deur birnessiet. Die laaste deel het die effekte van ultraviolet (UV) straling op die afbreek van atrasien op droëende mineraaloppervlaktes ondersoek. Die UV-straling het atrasien afbreek vermeerder, maar geen ander afbreek-produkte is gevorm nie. Die gevolgtrekking is dus dat atrasien afbreking op redoks-aktiewe mineraal-oppervlaktes verhoog word met drooging, deur 'n netto nie-oksidasie meganisme. Verder is hierdie drooging-geinduseerde afbreking 'n atrasien ontgiftingsmeganisme wat eenvoudig toegepas kan word deur landboupraktyke soos windrying, ploeg en ander praktyke wat (vinnig) 'n Mn- of Fe-oksied ryke landbou grond verdroog. / National Research Foundation (NRF)

Neste trabalho buscou-se produzir filmes de nanopartículas de dióxido de titânio e de nanopartículas de dióxido de titânio contendo o complexo sintetizado undecatungstofosfatomanganês(melamina) suportados em cela tubular de vidro borossiliacato e testar sua reatividade como fotocatalisadores frente à atrazina. Os ensaios de fotodegradação da atrazina foram realizados através de um reator fotocatalítico tendo como fonte de irradiação ultravioleta uma lâmpada de vapor de mercúrio de alta pressão de potência de 125 W desprovida do bulbo externo. A degradação da atrazina ocorrida nos experimentos de fotocatálise heterogênea foram acompanhados através da técnica de Espectroscopia de Absorção na Região do Ultravioleta e Visível (UV-vis) e para as amostras inicíais e finais de cada ensaio foram realizadas medidas de teor de Carbono Orgânico Total (TOC). Assim, foi possível estimar a porcentagem de degradação parcial e de mineralização da atrazina. As porcentagens de degradação obtidas para soluções contendo concentração inicial de 10 ppm de atrazina foram: no caso de filmes de nanopartículas de dióxido de titânio, obteve-se porcentagem de degradação parcial da atrazina de 42,2% a partir da análise de UV-vis e 21,8% de mineralização através da análise de TOC. Para o mesmo sistema após 72 horas, as porcentagens de degradação parcial chegaram a 71,5% a partir da análise de UV-vis e 55,5% de mineralização pela análise de TOC. Para o filme de nanopartículas de dióxido de titânio contendo undecatungstofosfatomanganês(melamina) através da técnica de UV-vis obteve-se uma degradação parcial da atrazina de 44,7% ao final de 12 horas e através da análise de TOC obteve-se 22,4% de mineralização. / In this work, films of titanium oxide nanoparticles and of titanium oxide nanoparticles containing the complex undecatungstophosphatemanganese(melamine) immobilized in a borosilicate glass cylindrical cell were prepared and their reactivity as photocatalyst for atrazine were tested. The photodegradation essays of atrazine were made in a phocatalytic reactor where the ultraviolet irradiation source was one mercury vapor lamp of 125 W without the external bulb. The atrazine degradation in heterogeneous photocatalysis experiments were checked by Ultraviolet and visible spectroscopy (UV-vis) and for first and last samples for each essay were made analysis of Total Organic Carbon (TOC). So, it was possible to estimate the percentage of the partial degradation and mineralization of atrazine. The partial degradation percentages obtained for solutions with initial concentration of 10 ppm of atrazine were: In the case for films of titanium oxide nanoparticles, the partial degradation percentage for atrazine was 42,2% in UV-vis analysis and 21,8% of mineralization obtained by TOC analysis. For the same system after 72 hours, the partial degradation percentages were 71,5% in UV-vis analysis and 55,5% of mineralization obtained by TOC analysis. For the film with titanium oxide nanoparticles containing the complex undecatungstophosphatemanganese(melamine), after 12 hours, the partial degradation of atrazine was 44,7% in UV-vis analysis and 22,4% of mineralization obtained by TOC analysis.

Uma alternativa para o destino dos resíduos urbanos é a reciclagem através da compostagem e vermicompostagem (produção de húmus). A falta de padrão de qualidade destes materiais tem prejudicado o desenvolvimento dessa alternativa, tendo prejuízos, produtores e consumidores. Neste trabalho procurou-se parâmetros que pudessem ser utilizados para padronização. Por Ressonância Paramagnética Eletrônica (EPR) as amostras com nível de radicais livres semiquinona de 1017 spin/g de amostra e 1018 spin/g de carbono, ou superior, indicaram melhor qualidade do produto, no que se refere ao grau de humificação. Com o objetivo de avaliar o potencial de sorção do húmus e seu possível efeito catalítico na degradação e fotodegradação do herbicida Atrazina (AT), realizou-se vários experimentos. Resultados de espectroscopia no Ultravioleta e Visível (UV-Vis) mostraram que, para pH\'s próximos do pKa da AT (1,68) o húmus possui similar efeito catalítico que ácidos húmicos e fúlvicos na degradação da AT. Em pH neutro não foi observado degradação da AT, mesmo para altas concentrações de húmus e longos períodos de interação (262 dias). A partir de dados de Polarografia de Pulso Diferencial (PPD) em conjunto com dados de UV-Vis, observou-se uma curva de sorção da AT com máximo (20%) em torno de pH 4,0, decaindo para menos de 5% de sorção para os demais pH\'s utilizados (2,0; 6,0; 7,0; 8,0 e 10,0). Dados de EPR não mostraram reações de transferência de elétrons entre a AT e o húmus. Assim, considerando a forma da curva de sorção, observada por PPD, o mecanismo de reação mais importante entre a AT e o húmus é via ligação hidrofóbica. Experimentos de fotodegradação da AT com luz UV-Vis (300-450 nm) mostraram maior eficiência no processo quando da presença do húmus. Isto ocorreu, provavelmente, devido a ação de agentes fotooxidantes da AT, formados a partir do húmus excitado pela radiação UV. Observou-se também, uma dependência com a concentração de húmus, sendo que, dentro do intervalo de 10 a 1800 mg houve maior fotodegradação da AT para valores em torno de 300 mg.L-1. / One alternative to disposal of urban residues is recycling through composts and earthworm composts (humus production). The absence of a quality standard of these materials however brings limitations to commercial development with damage to producers and consumers. In this work was proposed a strategic parameter to be used as standard. From Electron Paramagnetic Resonance (EPR) analysis samples of humus with level semiquinone free radicals of 1017 spin/g of sample and 1018 spin/g of carbon, or higher, indicated good quality of product, with adequate humification degree. Also were studied mechanisms of interaction between humus and the herbicide Atrazine (AT). The proposal was evaluate potential of AT sorption by humus and possible catalytic effect in the degradation and photodegradation of this herbicide. Data from Ultraviolet and Visible Spectroscopy (UV-Vis) showed that for pH\'s close to AT pKa (1.68) the humus showed catalytic effect in degradation of AT similar as those observed in literature with purified humic and fulvic acids. However for neutra1 pH\'s AT degradation was not observed even in the presence of high humus concentrations and long periods of interaction (262 days). Using Differential Pulse Polarography (DPP), combined with data of UV-Vis Spectroscopy, an AT sorption curve on humus was obtained showing a maximum value of 20% around pH 4.0, decreasing for less than 5% of sorption for other pH\'s analyzed (2.0; 6.0; 7.0; 8.0 and 10.0). Data from EPR gave no evidence of electron transfer reaction. So from the kind of sorption curve, obtained by DPP, the major mechanism of reaction between AT and humus was suggested to be hydrophobic bonding. Experiments of AT photodegradation using UV-Vis light (300-450 nm) showed larger efficiency of the process in the presence of the humus. This occurred probably due action of photo-oxidants on AT, originated from excitation of humus by the UV radiation. It was also observed, dependence with the humus concentration, and in the range 10 to 1800 mg.L-1 there was larger photodegradation of the AT for values around 300 mg.L-1.

Made available in DSpace on 2014-06-11T19:22:15Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-07-29Bitstream added on 2014-06-13T20:09:10Z : No. of bitstreams: 1 perim_l_me_botfca.pdf: 642600 bytes, checksum: 3f26247a69a07b1413c3746c23e76085 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O uso de adjuvantes é adotado em todo o mundo, a fim de melhorar a eficácia das formulações de defensivos agrícolas, independente do tipo de alvo. Existem duas maneiras principais em que adjuvantes podem melhorar o desempenho final do produto. Em primeiro lugar, aumentando a quantidade de ingrediente ativo retido pelo alvo e, por outro, melhorando a sua absorção. O objetivo do presente trabalho foi avaliar os efeitos de óleos minerais e vegetais nas características físicas e químicas da calda de aplicação e na ação do herbicida atrazina (Gesaprim 500® SC). Os tratamentos estudados foram: atrazina, atrazina + Natur’l Óleo®; atrazina + Agr’Óleo®; atrazina + Assist® e testemunhas. Todos os adjuvantes foram acionados na proporção de 0.5% do volume da calda aplicada. As plantas indicadoras utilizadas nos estudos sobre os efeitos dos adjuvantes sobre a ação da atrazina foram: Ipomoea grandifolia,Brachiaria plantaginea, Merremia cissoides e Euphorbia heterophylla. Os parâmetros estudados foram: tensão superficial, pH, efeito do tempo de preparo da calda e do pH sobre a tensão superficial, evaporação da calda, tamanho de gotas, eficácia de controle de plantas daninhas, influência da chuva no controle da atrazina e a velocidade de absorção da atrazina com o uso do fluorômetro. O delineamento experimental utilizado foi em bloco casualizados, com quatro repetições. Portanto com os resultados obtidos pode-se concluir que uso de óleos vegetais ou minerais influenciou positivamente nas características físicas e químicas da calda de aplicação agindo diretamente na ação de herbicidas apresentando uma alta eficiência de controle das espécies estudadas / The adjuvants are used all over the world in order to improve the effectiveness of the herbicides formulations, independent of target. There are two main ways in which adjuvants can improve the performance of the final product. First, increasing the amount of active ingredient retained by the target and secondly, promoting its absorption. The objective of this study was to evaluate the effects of mineral and vegetable oils in physical and chemical characteristics of the application and action of the herbicide Gesaprim 500® (atrazine). The treatments studied were: atrazine; atrazine + Natur'l Óleo®; atrazine + Agr'Óleo®; atrazine + Assist® and check. All adjuvants were used at a rate of 0.5% of the volume of spray applied. The indicator plants used in studies on the effects of adjuvants on the action of atrazine were: Ipomoea grandifolia, Brachiaria plantaginea, Merremia cissoides and Euphorbia heterophylla. The parameters studied were: surface tension, pH, effect of time preparing the solutions and pH on surface tension, evaporation of the solution, droplet size, effective weed control, rain influence in weed control, the active ingredient absorption velocity using the fluorometer method. The experimental design was randomized blocks with four replications. So with the results we can conclude that the use of vegetable or mineral oils had a positive influence on physical and chemical characteristics and at the application acts the treatments showed a highly efficient control of the studied species

Pesticide use has steadily increased in the United States and throughout the world since the development of more highly effective agrichemicals dating back to World War II. While many of these compounds are considered to have little to no detrimental environmental impact with relatively low toxicity and potential for causing adverse health effects in humans, many recent studies examining the toxicological properties and health outcomes associated with exposure to a variety of pesticides suggest otherwise. In heavily agricultural-based regions, particularly where row crops predominate, large amounts of herbicides and insecticides are used in activities involving pest management annually. The high volume of chemical applications to agricultural fields is cause for concern due their potential for leaching into soil following application events and subsequent transport to water systems. Pesticide-contaminated ground and surface water systems may pose a threat to public health by the presence and persistent elevated concentrations of chemicals found in both public and private drinking water. The herbicides atrazine and glyphosate are and have been the two most heavily applied pesticides in the U.S. Many studies have examined occupational exposures to these compounds and related health outcomes, yet very few have evaluated low-level exposures to more susceptible rural populations. This thesis will examine state-of-the- science behind atrazine and glyphosate, evaluate drinking water quality measurements in relation to herbicide usage estimates in Iowa, and finally, make recommendations for future atrazine and glyphosate exposure assessment studies in rural Iowa populations.

Microbial biofilms are significant in a variety of settings including the human microbiome, infectious disease, industrial processes, and environmental remediation. Due to the ubiquitous nature of biofilms, there is a great interest in understanding cellular activities within the biofilm matrix. Biofilm cells are able to better withstand environmental stress, experience increased horizontal gene transfer, and live longer. The purpose of this research is to grow Pseudomonas sp. strain ADP as a biofilm and examine the chemical and physical characteristics the microbe undertakes in a sticky extracellular matrix. ADP is the organism of choice because of its ability to metabolize atrazine. Cells are grown in a drip biofilm reactor and flow cells under varying time lapse to gain insight to biofilm formation. Some cells are grown with atrazine as the sole nitrogen source, while others are grown in a nutrient-rich medium to compare cells response under nutrient-limited conditions with atrazine particles in the matrix. As a positive control, Escherichia coli are grown in a similar manner. Raman spectroscopy was the main analytical technique used to evaluate the chemical and molecular characteristics of this system. Scanning electron microscopy is used to examine cellular distribution, and several assays are performed for molecular composition analysis. Raman analysis in the fingerprint region revealed distinct differences between free cells and cells in biofilm. Soluble extracellular polymeric substances (EPS) were found to be more prevalent than tightly bound EPS and lightly bound EPS in the biofilm matrix. Comparison of relative peak intensity ratios suggests that it is possible to track atrazine degradation by means of intermediates using Raman spectroscopy. SEM micrographs revealed EPS role as an immobilizing agent when in contact with compounds, such as atrazine. Further research is needed to determine if atrazine can bind to EPS fractions outside the presence of cells and whether its affinity to EPS is mostly attributed to physical conditions, due to the architecture of biofilm, or chemical, based on functional groups presents. The results obtained from this research will contribute to the development of a less invasive microscale approach to address the acquisition and induction of biotransformation activity occurring in xenobiotic degrading systems. The extracellular interactions observed can be used to further characterize biofilm-mediated bioremediation. Results have contributed to the Raman spectra library for microorganisms and organic compounds. .

Movement of atrazine in response to furrow irrigations was studied using the samples of Timpanogos silt loam soil. Distribution in soil profile of surface applied herbicide was determined by drawing samples of water extracts through porous cylinders. Atrazine quantity was determined by spectrophotometer. It was observed that the herbicide found in the water extracts was an indication of the quantity present in the soil. The herbicide moved readily with the applied water. Irreversible thermodynamic model could not be applied because of the initial and final boundary conditions. The pattern of movement was in conformity with the chromatographic theory.

Graduation date: 1995