A atrazina (ATZ) é um herbicida utilizado em larga escala no Brasil de forma intensiva em culturas de cana-de-açúcar, milho e sorgo. A ATZ possui caráter persistente e recalcitrante, de forma que os tratamentos convencionais de efluentes não são capazes de removê-lo. Nesse contexto, os processos oxidativos avançados, como a fotocatálise heterogênea, têm se mostrado eficientes para remoção deste poluente. Este trabalho tem por objetivo avaliar o desempenho dos fotocatalisadores TiO2 P25 e C-TiO2 Kronos vlp 7000 modificado com carbono para a degradação do pesticida atrazina em solução aquosa, utilizando um reator fotoquímico com coletor parabólico composto irradiado por um simulador solar. Os catalisadores TiO2 P25 e C-TiO2 Kronos foram caracterizados por meio de difração de raios-X, espectroscopia de infravermelho, área superficial específica BET e análise de reflectância difusa. As concentrações de TiO2 P25 e C-TiO2 Kronos empregadas foram 500 e 100 mg L&-1, respectivamente. Os resultados obtidos mostraram significativa remoção de ATZ ao final de 120 minutos (100; 98; 98; 93; 86% para concentrações iniciais de ATZ de 1; 5; 10; 20 e 30 mg L-1, respectivamente) com emprego do catalisador TiO2 P25. No entanto, as análises de carbono orgânico total (COT) indicaram que não houve mineralização significativa da ATZ, com valores inferiores a 20% com o uso do TiO2 P25. Para o catalisador C-TiO2 Kronos não se obteve remoção importante da ATZ ao final de 120 minutos de experimento, quando comparado com o TiO2 P25. Neste caso, o catalisador C-TiO2 Kronos permitiu obter remoções do pesticida de 37; 35; 38; 39 e 45%, aproximadamente, para as concentrações iniciais de ATZ de 1; 5; 10; 20 e 30 mg L-1, respectivamente. Apesar disso, o catalisador C-TiO2 Kronos apresentou melhor desempenho em mineralizar a ATZ a CO2 e H2O em relação ao proporcionado pelo TiO2 P25, com aproximadamente 38% de mineralização. O modelo de Langmuir-Hinshelwood (LH) constitui uma aproximação adequada para a cinética de degradação da atrazina para ambos os catalisadores estudados, com valores de Kr e Kads iguais a 1,54 mg L-1 min-1 e 15,47 L mg-1, respectivamente, para o catalisador TiO2 P25 e de 1,34 mg L-1 min-1 e 132,95 L mg-1, respectivamente para o catalisador C-TiO2 Kronos vlp 7000. / Atrazine (ATZ) is a widely used herbicide in Brazil, where it is intensively applied in sugarcane, corn and sorghum cultivations. However, conventional wastewater treatments are not able to remove ATZ due to its persistent and recalcitrant properties. Advanced oxidation processes, such as heterogeneous photocatalysis, have been proved effective for the removal of this pollutant. This study aims to evaluate the performance of TiO2 P25 and carbon-modified TiO2 Kronos vlp 7000 photocatalysts in the degradation of ATZ in aqueous systems using a tubular photochemical reactor equipped with a compound parabolic collector (CPC) irradiated by simulated solar light. Catalysts TiO2 P25 and C-TiO2 Kronos were characterized by X-ray diffraction, infrared spectroscopy, BET analysis and diffuse reflectance analysis. The concentrations of TiO2 P25 and C-TiO2 Kronos were 500 and 100 mg L-1, respectively. For TiO2 P25, the results showed significant ATZ removals after 120 minutes of irradiation (100; 98; 98; 93; 86% for initial ATZ concentrations of 1; 5; 10; 20, and 30 mg L-1, respectively). In contrast, the total organic carbon (TOC) analyses indicated that no significant ATZ mineralization occurred, with values lower than 20% for TiO2 P25. In comparison with TiO2 P25, C-TiO2 was not able to completely remove ATZ at the end of 120 minutes of irradition. In this case, pesticide removals of about 37; 35; 38; 39 and 45% were obtained for initial ATZ concentrations of 1; 5; 10; 20, and 30 mg L-1, respectively. Nevertheless, C-TiO2 Kronos showed better performance for ATZ mineralization to CO2 and H2O in comparison with TiO2 P25, with approximately 38% total carbon organic removal. The Langmuir-Hinshelwood (LH) model was shown to be an appropriate approximation for the degradation kinetics of atrazine for both catalysts, with values of Kr and Kads equal to 1.54 mg L-1 min-1 and 15.47 mg L-1, respectively, for the P25 TiO2 and 1.34 mg L-1 min-1 and 132.95 mg L-1, respectively, for C-TiO2 Kronos vlp 7000.

Indiana University-Purdue University Indianapolis (IUPUI) / The transport of excess nutrients, sediment, and other contaminants to surface waters has been shown to cause a number of environmental and human health concerns. An understanding of the export pathways that these contaminants follow to surrounding water bodies is crucial to the anticipation and management of peak concentration events. Several studies have demonstrated that the majority of annual contaminant loading in the Midwest occurs during periods of elevated discharge. However, many studies use a limited number of sampling points to determine concentration patterns, loadings, and fluxes which decreases accuracy. Through high-resolution storm sampling conducted in a 2945 km2 (1137 mi2) area of central Indiana’s Upper White River Watershed, this research has documented the complex concentration signals and fluxes associated with a suite of cations, nutrients, and contaminants and isolated their primary transport pathways. Additionally, by comparing the results of similar studies conducted on smaller areas within this watershed, differences in concentration patterns and fluxes, as they relate to drainage area, have also been documented. Similar to the results of previous studies, NO3- concentrations lacked a well-defined relationship relative to discharge and was attributed to primarily subsurface contribution. DOC was exported along a shallow, lateral subsurface pathway, TP and TSS via overland flow, and TKN through a combination of both. Near or in-channel scouring of sediment increased DOC, TKN, TP, and TSS concentrations during Storm 2. Atrazine export was attributed to a combination of overland and subsurface pathways. 2-MIB and geosmin derived from different sources and pathways despite being produced by similar organisms. 2-MIB concentration patterns were characterized by dilution of an in-stream source during Storm 1 and potential sediment export during Storm 2 while in-stream concentrations or a sediment source of geosmin was rapidly exhausted during Storm 1. Many of the concentration patterns were subject to an exaggerated averaging effect due to the mixing of several larger watersheds, especially during Storm 1. This research illustrates the need for high-frequency sampling to accurately quantify contaminant loads for total maximum daily load (TMDL) values, developing best management practices (BMPs), and confronting the challenges associated with modeling increasingly larger-scale watersheds.

Les herbicides sont des polluants suscitant de grandes inquiétudes en raison de leur ubiquité environnementale résultant de leur usage intensif dans l’agriculture moderne et de leur persistance dans les sols et les eaux. Les herbicides peuvent être dégradés par des microorganismes, des plantes ou d’autres processus naturels, produisant alors une vaste gamme de métabolites dont l’impact sur les écosystèmes reste méconnu. Dans un contexte d’évaluation des risques environnementaux, l’étude de la réponse des plantes à des mélanges complexes de xénobiotiques est importante pour estimer les effets des contaminations, notamment dans le cas de pollution résiduelle. Afin d’étudier l’impact de cette diversité de polluants, les mécanismes de réponse et les cibles impliquées, la plante modèle Arabidopsis thaliana a été confrontée à des doses variables de molécules de la famille des triazines constituant une série chimique cohérente : atrazine, herbicide encore largement utilisé au niveau mondial, déséthylatrazine, métabolite chloré de l’atrazine, et hydroxyatrazine, métabolite de déchloration de l’atrazine. Ce travail montre que l’exposition de courte durée à des doses variables d’atrazine, de déséthylatrazine et d’hydroxyatrazine, au niveau racinaire, affecte de manière spécifique et dose-dépendante la croissance précoce et le développement de la plante. La caractérisation d’effets directs et multiples sur la respiration et la croissance racinaire a permis de révéler des mécanismes d’action non-canoniques, distincts de l’action classiquement décrite des triazines sur le photosystème II. Afin d’identifier ces mécanismes, activés en absence de dommages cellulaires, une analyse transcriptomique au niveau du génome entier a été effectuée. Les trois triazines induisent des changements coordonnés et spécifiques dans l’expression des gènes. L’analyse fonctionnelle des gènes différentiellement exprimés et de leur promoteur révèle que les voies de signalisation liées à la fois aux hormones végétales, à la perception de faibles niveaux d’énergie, aux stress environnementaux ainsi qu’aux interactions biotiques sont impliquées dans la réponse aux faibles doses de triazines. Les triazines affectent, en particulier, l’expression de gènes connus pour être régulés par les cytokinines. De manière intéressante, cette famille d’hormones végétales montre des caractéristiques chimiques similaires à celles des triazines. Des études développementales utilisant différentes modalités d’exposition aux triazines et aux cytokinines ont alors été effectuées sur des génotypes sauvages et sur des mutants de la voie de signalisation des cytokinines. L’identification d’interactions spécifiques entre les triazines et les composants de la signalisation des cytokinines a alors mis en évidence des mécanismes potentiels de compétition et/ou d’antagonisme. La caractérisation de ces perturbations au niveau de la transduction du signal pourra permettre à terme d’évaluer l’efficacité des herbicides sur les cultures ainsi que l’impact des contaminations xénobiotiques sur les communautés végétales naturelles. Enfin, l’identification des interactions entre stress xénobiotique, biotique et abiotique approfondira les connaissances sur les effets croisés de la pollution chimique et des stress liés au changement climatique. / Herbicides are pollutants of high concern due to their environmental ubiquity resulting from extensive use in modern agriculture and persistence in soil and water. Degradation events on active molecules mediated by microorganisms, by plants and by natural processes give rise to a plethora of herbicide metabolites of unknown impact on ecosystems. Study of plant behavior toward such complex mixtures of xenobiotic structures is important to evaluate the effects of contaminations, especially in the context of residual pollution. In order to understand the mechanisms underlying the action of this diversity of compounds, the model plant Arabidopsis thaliana was confronted to variable doses of the widely-used triazine herbicide atrazine, and of two of its metabolites, desethylatrazine and hydroxyatrazine. Short exposure to varying concentrations of atrazine, desethylatrazine and hydroxyatrazine was found to affect early growth and development in various dose-dependent and distinct manners. These differential effects pointed out to the multiple involvement of non-canonical mechanisms, directly affecting respiration and root development. In order to identify these mechanisms, which are activated in the absence of major adverse physiological effects, a genome-wide transcriptomic analysis was carried out. All of the triazines under study induced coordinated and specific changes in gene expression. Functional analysis of differentially expressed genes and of their promoters revealed that signaling pathways related to plant hormones, low energy sensing, environmental stresses and biotic interactions were involved in low-dose triazine responses. In particular, triazines affected the expression of genes known to be regulated by cytokinins. Interestingly, this family of plant hormones shares similar chemical features with triazine compounds. Developmental studies on plants bearing mutations in cytokinin sensing and signaling pathways were then carried out under variable triazine exposures. The identification of specific interactions between triazine compounds and cytokinin-signaling components highlighted potential mechanisms of competition and/or antagonism. The characterization of such signal transduction modifications and perturbations will be useful to assess herbicide efficiency in crop systems and xenobiotic contamination impact on natural plant communities. Finally, the identification of crosstalk processes between xenobiotic, abiotic and biotic stress signaling gives novel insights into the interplay between chemical pollution and climate change stressors.

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

The teratogenic potential of commercial formulations of atrazine (40.8%) and 2,4-D was evaluated using FETAX (frog embryo teratogenic assay--Xenopus). Because these herbicides have been detected in ground and surface water, this study was designed to determine the adverse effects in buffer and natural water for both herbicides. All treatments showed a significant concentration-response effect on exposed embryos, except for the 2,4-D natural water sample. Atrazine (solubility of the commercial formula used 70 mg/L at 20 degrees C), compared to 2,4-D (solubility = 311 mg/L at pH = 1 and 25 degrees C), had a significantly greater teratogenic effect in both the buffer (atrazine EC50 = 33 mg/L, LC50 = 100 mg/L, TI = 3.03; 2,4-D EC50 = 245 mg/L, LC50 = 254 mg/L, TI = 1.04) and natural water samples (atrazine EC50 < 8 mg/L, LC50 = 126 mg/L; 2,4-D EC50 and LC50 > 270 mg/L). The 2,4-D EC50 and LC50 values for the buffer were similar at 245 mg/L and 254 mg/L. These similar values and the teratogenic index (TI) of 1.04 suggested that 2,4-D was more embryotoxic than teratogenic to frog embryos at high concentrations. Atrazine in natural water demonstrated a significantly greater EC50 (100% abnormality at 8 mg/L, the lowest test concentration) to frog embryos than the buffer experiment (EC50 = 33 mg/L). The extrapolated lowest observable adverse effect concentration (LOAEC) for the natural water experiment was 1.1 mg/L. These results suggest that atrazine toxicity is enhanced by the synergistic or additive effects of some component of the water or atrazine was already present in the sample. In contrast to atrazine, 2,4-D was less toxic in natural water than buffer. These results suggest that both atrazine and 2,4-D pose little threat, since their embryotoxicity and teratogenicity to frog embryos occur at high concentrations approaching their maximum solubility levels in water.

Στην εργασία αυτή μελετήθηκε η ρόφηση και η εκρόφηση του παρασιτοκτόνου ατραζίνη (atrazine) σε πρότυπες εδαφικές ουσίες καθώς και σε ένα τυπικό δείγμα εδάφους, τόσο σε αντιδραστήρες διαλείποντος έργου (batch) όσο και σε πληρωμένες κλίνες (bed). Ως πρότυπες ουσίες επιλέχθηκαν η πυριτία (silica-gel, SiO2), η αλούμινα (γ-alumina, Al2O3), το ανθρακικό ασβέστιο (calcite, CaCO3) και το χουμικό οξύ (humic acid). Η ατραζίνη ροφείται σημαντικά στο χουμικό οξύ στην πυριτία και στο έδαφος, όμως βρέθηκε ότι έχει πολύ μεγαλύτερη συγγένεια για το χουμικό οξύ σε σύγκριση με την πυριτία. Η ατραζίνη δεν έδειξε να ροφείται στη γ-αλούμινα και το CaCO3, ανεξαρτήτως από τις πειραματικές συνθήκες που χρησιμοποιήθηκαν. Σε όλες τις περιπτώσεις, η κινητική μελέτη έδειξε δύο διακριτά στάδια: ένα πρώτο γρήγορο στάδιο ρόφησης της ατραζίνης, διαδεχόμενο από ένα δεύτερο πιο αργό στάδιο. Η κινητική της ρόφησης υπακούει ικανοποιητικά στο μοντέλο Elovich. Στα χρονικά πλαίσια που μελετήθηκε η ρόφηση και η εκρόφηση, η διεργασία είναι αντιστρεπτή και η ατραζίνη εκροφείται ποσοτικά. Οι ισόθερμοι ρόφησης της ατραζίνης λήφθηκαν σε διαφορετικές τιμές ιοντικής ισχύος, pH και θερμοκρασίας και υπακούουν στο μοντέλο Freundlich. Σε όλες τις περιπτώσεις που μελετήθηκαν, η αύξηση της ιοντικής ισχύος του διαλύματος προκάλεσε αύξηση της ροφημένης ποσότητας της ατραζίνης. Η ρόφηση της ατραζίνης μειώνεται καθώς το pH του διαλύματος αυξάνεται. Όσον αφορά στην πυριτία, η ρόφηση της ατραζίνης φαίνεται ότι γίνεται κυρίως μέσω δεσμών υδρογόνου με τις υδροξυλομάδες της επιφάνειας. Όσον αφορά στο χουμικό οξύ, το σημαντικότερο ρόλο στη ρόφηση παίζει η διάχυση της ατραζίνης προς το εσωτερικό του στερεού όπου η ρόφηση επιτυγχάνεται κυρίως μέσω υδρόφοβων αλληλεπιδράσεων. Η προσρόφηση της ατραζίνης στην πυριτία αυξάνεται σημαντικά καθώς αυξάνεται η θερμοκρασία του διαλύματος, μια τάση που δεν παρατηρείται κατά τη ρόφηση της ατραζίνης στο χουμικό οξύ. Η θερμοδυναμική ανάλυση έδειξε ότι η ρόφηση στα μοντέλα εδάφους είναι φυσική αφού παρατηρήθηκαν τιμές της ενθαλπίας ρόφησης στην περιοχή των 10 kJ mol-1. Οι λαμβανόμενες ισόθερμοι ρόφησης από τα πειράματα σε πληρωμένες κλίνες ήταν σε καλή συμφωνία με αυτές που λήφθηκαν από τα πειράματα στους αντιδραστήρες διαλείποντος έργου. Η παρουσία χουμικού οξέος στις κλίνες προκαλεί με το χρόνο δραστική μείωση της διαπερατότητας. / Adsorption and desorption of the herbicide atrazine was investigated on the principal inorganic constituents of soil, as well as on a typical Greek soil sample. The studies were conducted both in batch, stirred reactors and in packed beds. Silica-gel (SiO2), γ-alumina (Al2O3) and calcite (CaCO3), were selected as model inorganic substances. Humic acid was selected as a model substance representative of the organic part of soil. Significant adsorption of atrazine was measured on the humic acid, silica and on the soil suspensions in electrolyte solutions. Atrazine exhibited higher affinity for humic acid rather than for silica. Atrazine did not adsorb on γ-alumina and on CaCO3 regardless the experimental conditions (pH range or total solid available for adsorption). In all cases, kinetic results have shown two distinct features: a first, fast sorption step, followed by a second, slow step. The kinetics data of atrazine uptake on both substrates yielded satisfactory fit to the Elovich model. Atrazine was found to be completely desorbed from both the humic acid and the silica substrates. Adsorption isotherms for atrazine were obtained at different values of ionic strength, pH and temperature. The adsorption data gave the best fit to the Freundlich model. In all cases investigated, the amount of adsorbed atrazine increased upon increasing the ionic strength of the solution. The adsorption of atrazine decreased with increasing solution pH. The adsorption of atrazine on silica was primarily dominated by the formation of hydrogen bonds with the surface hydroxyl groups. In the case of humic acid, the diffusion of atrazine to the interior of the solid seemed to play the most significant role. Inside the organic substance particles, sorption took place mainly through hydrophobic interactions. The sorption of atrazine on silica surface increased considerably with increasing temperature, a trend not found in the case of humic acid. The thermodynamic analysis yielded adsorption energy values of the order of 10 kJ mol-1 suggesting physical adsorption. The isotherms obtained from the packed bed experiments were in a good agreement with those obtained from batch experiments. Finally, humic acid grains, mixed with silica in packed beds, were found to change morphology upon hydration which resulted to swelling. The humic substances clogged a large portion of the pores of the packed beds, decreasing drastically their permeability.

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

No description available.

No description available.

Studies in the USA have reported that species of meiobenthic copepods can be used as bioindicators of sediment-associated contaminants. The main objective of this research project was to develop and validate methods to assess the effects of estuarine pollution, using the marine benthic copepod Robertsonia propinqua as a bioindicator of environmental health in New Zealand intertidal / estuarine areas. Cultures of R. propinqua were set up and maintained in the laboratory and individuals used in 96h acute and full life-cycle chronic bioassays using the pre-selected contaminants atrazine and zinc sulphate. From the 96h acute experiments it was found that the lethal doses at which 50% mortality occurred (LC50) for exposed nauplii and adult individuals were 7.5 mg/L and 31.8 mg/L, respectively for atrazine and 1.7 mg/L and 2.7 mg/L, respectively for zinc sulphate. This indicated that the nauplii life stage was more sensitive than were the adult life stages for exposure to both contaminants. Based on the 'trigger' values reported (atrazine = 0.013 mg/L, zinc = 0.015 mg/L) in the Australian and New Zealand guidelines for fresh and marine water quality, which provide values at which concentrations of contaminants can occur in the environment before they begin causing effects on aquatic fauna, it is unlikely that the calculated LC50s in the current research will induce biological effects in exposed copepods in the short-term. The calculated LC50 results were then used to further investigate the effects of chronic exposure of sediment-associated contaminants on the complete life-cycle (egg-reproductive adult) of R. propinqua. In a laboratory-based full life-cycle toxicity test, field-collected sediments from polluted sites in the Auckland and Bay of Plenty regions reduced reproductive output (nauplii and copepodite production) of R. propinqua individuals, but the number of males and females, gravid females, clutch size per female and the number of eggs produced were not affected by either the polluted or non-polluted (reference) sediment samples from both field regions. Field investigations of meiofauna community composition in polluted and non-polluted field sites were carried out in 2004 in the Auckland and Bay of Plenty field regions in New Zealand. Greater sediment organic content and a correspondingly deeper redox potential discontinuity layer occurred in all polluted field sites compared with the non-polluted sites. However, species composition could not be used to characterise polluted and non-polluted sites, as there were no dominant taxa which were representative of these sites. The results presented in this thesis indicate that R. propinqua has strong potential to be a good candidate species as a bioindicator of environmental contamination. Furthermore, the full life-cycle toxicity test could be used as a rapid test to detect immediate changes in individual reproduction and development as well as long-term population effects. The technologies developed as part of this research may eventually provide additional tools for commercial environmental consultancies and may compliment existing standard operating procedures for environmental assessments involving pollution of estuarine ecosystems.