Thesis (Ph. D.)--Jyväskylä Yliopisto, 1980. / Includes bibliographical references (p. 46-57).

Thesis (Ph. D.)--Jyväskylä Yliopisto, 1980. / Bibliography: p. 46-57.

Yes / Adsorption and controlled release of agrochemicals has been studied widely using different nanomaterials and a variety of formulations. However, the potential for application of high surface-area metal-organic frameworks (MOFs) for the controlled release of agrochemicals has not been thoroughly explored. Herein, we report controlled and sustainable release of a widely used herbicide (2-methyl-4-chlorophenoxyacetic acid, MCPA) via incorporation in a range of zirconium-based MOFs and their biodegradable polymer composites. Three Zr-based MOFs, viz., UiO-66, UiO-66-NH2, and UiO-67 were loaded with MCPA either postsynthetically or in situ during synthesis of the MOFs. The MCPA-loaded MOFs were then incorporated into a biodegradable polycaprolactone (PCL) composite membrane. All three MOFs and their PCL composites were thoroughly characterized using FT-IR, TGA, SEM, PXRD, BET, and mass spectrometry. Release of MCPA from each of these MOFs and their PCL composites was then studied in both distilled water and in ethanol for up to 72 h using HPLC. The best performance for MCPA release was observed for the postsynthetically loaded MOFs, with PS-MCPA@UiO-66-NH2 showing the highest MCPA concentrations in ethanol and water of 0.056 and 0.037 mg/mL, respectively. Enhanced release of MCPA was observed in distilled water when the MOFs were incorporated in PCL. The concentrations of herbicides in the release studies provide us with a range of inhibitory concentrations that can be utilized depending on the crop, making this class of composite materials a promising new route for future agricultural applications. / L.A.M.M. and S.N. acknowledge funding for a studentship by the Erasmus+ KA107 Student Mobility programme. V.P.T and L.R.T. acknowledge funding from the EPSRC (EP/R01650X/1)

Avec l’ère industrielle sont venus les polluants environnementaux. Ils sont de plus en plus pointés du doigt pour une variété d’effets indésirables en particulier pour leur potentiel à affecter la santé humaine. Les pesticides font partie de ces polluants et leurs usages ne font que croître depuis une vingtaine d’années. Ces produits qui servent à améliorer la production agricole en éliminant les pestes qui ravagent les récoltes sont souvent peu étudiés à long terme avant d’être homologués. L’effet perturbateur au niveau cellulaire et les effets à long terme de ces pesticides sont peu connus. Pour ce projet de maîtrise, nous avons observé l’effet de deux pesticides, l’imidaclopride et l’acide 2-methyl-4-chlorophenoxyacetic (MCPA), sur les voies de signalisation du récepteur à la dioxine (AhR) et du récepteur aux androgènes (AR). L’imidaclopride est un insecticide de la famille des néonicotinoïdes, une classe de plus en plus utilisée. Ce pesticide est surtout connu pour être en lien avec le déclin des colonies d’abeilles depuis une décennie. Le MCPA est un des herbicides les plus utilisés au Québec, il est persistant et souvent retrouvé dans les eaux de la province. Nous avons traité des cellules du cancer du sein et des cellules du cancer de la prostate avec ces pesticides et nous avons vérifié si leur présence perturbait les deux voies de signalisation cellulaire à l’étude. Le récepteur AhR est un facteur de transcription activé par un ligand. Le TCDD, une dioxine, est le meilleur ligand exogène connu à ce jour de ce récepteur. Par contre, ses ligands naturels, des dérivés du tryptophane ou des facteurs de virulence de bactéries, l’activent de façon beaucoup moins forte. Lors de l’activation de la voie AhR, les gènes CYP1A1 et CYP1B1 sont transcrits et codent pour des enzymes du cytochrome P450 qui transforment les ligands en produits plus facilement éliminables. Dans un contexte où de l’œstradiol (E2) est présent dans les cellules, il y a une interaction croisée entre le récepteur à l’œstrogène (ER) et le récepteur AhR, qui fait en sorte que l’expression de CYP1A1 est réprimée. Cela se traduit en un ratio d’enzyme CYP1A1 à CYP1B1 différent qui pourrait augmenter la possibilité d’une accumulation de métabolites génotoxiques. En effet, CYP1B1 hydroxyle le ligand d’AhR mais aussi l’œstradiol en 4-hydroxyœstradiol (4-OHE), dont l’accumulation peut amener des mutations dans l’ADN alors que l’enzyme CYP1A1 l’hydroxyle en 2-hydroxyœstradiol (2-OHE), qui n’as aucun effet néfaste répertorié sur la cellule. Dans les cellules du cancer du sein, le MCPA appliqué en champs induisait fortement l’expression de CYP1B1 comparable à l’échantillon traité au témoin positif (TCDD), alors que CYP1A1 l’était que très légèrement par rapport au témoin non-traité. Au niveau protéique, CYP1A1 n’était qu’exprimée dans le témoin positif (TCDD) et ce, en quantité moindre lorsqu’il y avait présence d’œstradiol. CYP1B1 était fortement exprimée dans l’échantillon de TCDD, ce qui était attendu, mais aussi dans tous les échantillons traités au MCPA de NuFarm. Ces effets ne sont pas notés avec l’ingrédient actif du MCPA. La présence d’un ou plusieurs autres produits ajoutés dans le MCPA de la compagnie NuFarm en combinaison avec l’ingrédient actif pourrait activer la voie de signalisation d’AhR et causer ce débalancement dans l’expression des gènes CYP1A1 et CYP1B1. Nos résultats indiquent que plusieurs concentrations de l’ingrédient actif de l’imidaclopride ne perturbe pas les voies cellulaires d’AhR ni AR, alors que, le MCPA perturbe ces deux voies cellulaires. Par contre, c’est seulement celui produit par la compagnie NuFarm qui est utilisé en champs. Cette formulation appliquée en terrain agricole inclut l’ingrédient actif ainsi que les antigels, les surfactants et les adjuvants qui permettent au produit d’être plus efficace. L’ingrédient actif du MCPA seul n’affectait pas les deux voies. Le récepteur aux androgènes (AR) est aussi un facteur de transcription qui se lie à l’ADN afin de réguler l’expression des gènes et il est particulièrement important pour le développement et le maintien du phénotype masculin. Depuis une vingtaine d’années, des problèmes de baisse de libido et de fertilité s’accentuent dans notre société et semblent être reliés à la baisse de testostérone des hommes (Travison et al. 2007). Cette molécule est d’ailleurs un des deux ligands du récepteur AR, le deuxième étant la 5-dihydrotestostérone (DHT). Le facteur environnemental plutôt que le mode de vie semble être un facteur déterminant dans l’étude qui portait sur ce déclin. Les pesticides ont déjà été soupçonnés pour avoir un potentiel anti-androgénique, mais aucune étude ne fait un lien de causalité direct. Dans le projet de maitrise présenté dans ce document, l’expression des gènes marqueurs PSA (antigène spécifique de la prostate) et PCA3 (antigène du cancer de la prostate) a été quantifiée pour savoir si les pesticides ont un effet perturbateur sur la voie du récepteur AR. Dans les cellules du cancer de la prostate, l’expression de PSA et PCA3 était semblable au non-traité dans l’échantillon traité au MCPA (NuFarm), et ce, même après l’ajout de DHT, qui active l’expression de ces deux gènes. Cette fois-ci, l’ingrédient actif seul faisait en sorte que les deux gènes marqueurs étaient moins exprimés lors de l’ajout de la DHT, par rapport au témoin. Il semblerait que l’ingrédient actif est à la base de ce changement d’expression de nos gènes marqueurs. Donc, le MCPA pourrait avoir un effet anti-androgénique dans les cellules du cancer de la prostate. Donc, le MCPA est un pesticide qui affecte les voies de signalisation cellulaires AhR et AR. Il est particulier de noter que le pesticide appliqué en champ perturbe nettement plus les voies cellulaires. Il sera important de continuer à étudier les effets des pesticides sur l’homme au niveau cellulaire et de comprendre comment ils pourraient contribuer au développement du cancer.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2006. / Härtill 4 uppsatser.

Prior to full-scale implementation of process modifications at the Brantford WTP, a pilot-scale treatability study was conducted to investigate intermediate ozonation/AOP and to determine the most suitable granular media (anthracite, GAC, and Filtralite®) for deep-bed biological filtration. The primary objectives of this research were to provide insight into the destruction of natural and synthetic organics and assess ozonated and halogenated DBP formation. Ozone alone was unable to achieve the 1-log removal target for geosmin or MCPA, unless disinfection-level dosages were applied. No improvement was observed when adding hydrogen peroxide. A major obstacle to the implementation of ozonation in bromide-laden source waters is the formation of bromate. There is a direct correlation between ozone dose and bromate formation and by applying ozone dosages at disinfection levels, bromate is likely to exceed regulatory limits. However, adding hydrogen peroxide reduced the amount of bromate formed, and in most cases levels fell below regulatory limits. A linear correlation was established between bromate inhibition and increasing H2O2/O3 ratio at constant ozone dose. Amongst the three filtration media investigated, only GAC achieved 1-log removal for geosmin and MCPA. The superiority of GAC over anthracite and Filtralite® was attributed to its adsorption affinity. Filtralite® and anthracite media were both ineffective for MCPA removal due to its non-biodegradable nature under conventional water treatment conditions. At a 1 mg/L-ozone dose, GAC and Filtralite® filters achieved a 1-log geosmin removal. In contrast, a 1.44 mg/L ozone dose was required to meet this target with anthracite. The tandem of ozone followed by biological filtration was very effective for the control of distribution system TTHM production regardless of filter media, with levels well below current and anticipated provincial regulatory limits. The combination of intermediate ozonation followed by deep-bed biological filtration is well suited for treating Grand River water. Scale-up considerations include pairing the proper filter media to the size of the ozone generator. The best two treatment scenarios were: Option 1: select GAC media and size the ozone generator to produce a 1 mg/L dose. Option 2: select anthracite media and size the ozone generator to deliver a 2 mg/L dose.

The main aim of this research is to provide a low cost and sustainable biochar for the removal of organic pollutants from aqueous solution. Wastewater pollution by organic contaminants of emerging concern has become a subject of intense discussion. Removing these contaminants from aqueous solution is paramount to improve water quality for both humans and animal consumption. Traditional adsorption techniques using activated carbon are universal and fast, however, they are very costly. This dissertation therefore seeks to find an alternative low cost adsorbent which can be used to adsorb contaminants from aqueous solution. In chapter one, an overview of some of the selected organic contaminants of emerging concern is given. Pharmaceutical and pesticide entry into the environment, their fate and ecotoxicity are highlighted. Available techniques for the removal of contaminants from aqueous solution are also given. Chapter two is a study on the adsorption of some selected pharmaceuticals using a fast pyrolysis low cost biochar produced from pinewood feedstocks. The pinewood biochar used as the adsorbent in this study was made by fast pyrolysis in an augered reactor at a temperature of 425 oC and a residence time of 20-30 s during bio-oil production. In chapter three, switchgrass biochar has been tested for its potential for remediating water that is contaminated with two phenoxy herbicides, 2,4-dichlorophenoxyacetic (2,4-D) acid and 2-methyl-4-chloro-phenoxyacetic acid (MCPA). The adsorption capacity was remarkable when compared to commercial activated carbon per unit of measured surface area. Furthermore, in chapter four, magnetic and non-magnetic low cost biochars have been tested for the removal of the herbicide metribuzin from aqueous solution under different experimental conditions. The magnetic biochar synthesized from raw switchgrass biochar does not show a detrimental effect on the adsorption capacity. Additional value of this magnetic biochar is the ease of separation from contaminated solution following adsorption.

A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications.

A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications.