Os poluentes orgânicos emergentes (POE) são compostos químicos presentes numa variedade de produtos comerciais como medicamentos, produtos de higiene, agrotóxicos, surfactantes, dentre outros, podendo ser encontrados em matrizes ambientais e biológicas. Esses poluentes não são usualmente monitorados ou ainda não possuem legislação regulatória correspondente, mas apresentam risco à saúde humana e ao meio ambiente. Dentre esses POE, podemos destacar o nonilfenol etoxilado, um surfactante não-iônico utilizado no desengraxe alcalino da indústria de galvanoplastia. Esse surfactante possui uma recalcitrância e toxidade que aumenta com a diminuição do número de grupos etoxilados, processo que ocorre quando ele é biodegradado. Alguns dos produtos da biodegradação são o nonilfenol com 4, 3, 2 ou 1 grau de etoxilação e nonilfenol, este considerado disruptor endócrino imitando o hormônio natural 17β-estradiol. Tratamentos convencionais de efluentes e água não são eficientes para degradação completa desses compostos. O emprego de processos mais eficientes, como processos oxidativos e oxidativos avançados tais como a Eletrólise (E), Fotólise direta (F), Fotocatálise heterogênea (FH) e a fotoeletrooxidação (FEO), tecnologias limpas que utilizam o elétron e o fóton como reagentes, têm sido proposto como opção para a degradação desses compostos, evitando assim a contaminação dos recursos hídricos. Este trabalho foi realizado com uma solução baseada na composição de um efluente industrial contendo nonilfenol etoxilado com 4 graus de etoxilação. Os ensaios de FEO foram realizados em triplicata, variando-se a densidade de corrente, potência de lâmpada e o tempo de tratamento. Além disso, foram realizados, para efeito de comparação e elucidação de mecanismos, ensaios de eletrólise, fotólise direta e fotocatálise heterogêna. As amostras coletadas antes e após os processos oxidativos foram caracterizadas por diferentes métodos analíticos e por toxicidade. Verificou-se que no tempo de tratamento de 240 minutos as diferentes configurações de FEO não foram suficientemente eficazes na degradação de todo o poluente que se encontra na solução inicial, entretanto, a configuração FEO3 não gerou metabólitos mais tóxicos, não apresentou diferença de germinação e de crescimento de raiz, não apresentando também citotoxicidade e genotoxicidade em alface e em cebola, apresentando toxicidade apenas em peixes em uma concentração de 70,71%, o que pode ser evitado com o aumentando do tempo de tratamento, à vista disso, o processo de FEO torna-se uma opção na degradação do nonilfenol etoxilado e de outros POE, evitando assim que esses atinjam os recursos hídricos. / The emerging organic pollutants (POE) are chemical compounds present in a variety of commercial products such as medicines, toiletries, pesticides, surfactants, among others, can be found in environmental and biological matrices. These pollutants are usually not monitored or have no corresponding regulatory legislation, but present risk to human health and the environment. POE Among these, we highlight the nonylphenol ethoxylate, one non-ionic surfactant used in degreasing alkaline electroplating industry. This surfactant has a recalcitrance and toxicity increases with the decrease of the number of ethoxylate groups, a process which occurs when it is biodegraded. Some of the products of biodegradation are nonylphenol with 4, 3, 2 or 1 degree of ethoxylation of nonylphenol and this considered endocrine disruptor mimicking the natural hormone 17β -estradiol. Conventional treatment of sewage and water are not efficient for complete degradation of these compounds. The use of more efficient processes, such as oxidation and advanced oxidation processes such as direct photolysis (F), Electrolysis (E), heterogeneous photocatalysis (FH) and photoelectrooxidation (FEO), clean technologies that utilize the electron and photon reagents have been proposed as an option to the degradation of such compounds, thereby avoiding the contamination of water resources. This work was carried out with a solution based on the composition of an industrial effluent containing nonylphenol ethoxylate with 4 degrees of ethoxylation. FEO assays were performed in triplicate, by varying the current density lamp power and treatment time. In addition, we performed, for comparison and elucidation of mechanisms, testing electrolysis, photolysis and photocatalysis heterogenous. The samples collected before and after the oxidative processes were characterized by different analytical methods and toxicity. It was found that treatment time of 240 minutes, the FEO different configurations were not efficient enough to degrade any pollutants that is in the initial solution, however, the configuration FEO3 not more toxic metabolites generated no significant difference in seed germination and root growth, no significant cytotoxicity and genotoxicity also in lettuce and onion, showing toxicity on fish only at a concentration of 70.71 %, which can be avoided by increasing treatment time, the sight, the process of FEO becomes an option in the degradation of nonylphenol ethoxylate and other POE, thus preventing it reaches the water.

Os poluentes orgânicos emergentes (POE) são compostos químicos presentes numa variedade de produtos comerciais como medicamentos, produtos de higiene, agrotóxicos, surfactantes, dentre outros, podendo ser encontrados em matrizes ambientais e biológicas. Esses poluentes não são usualmente monitorados ou ainda não possuem legislação regulatória correspondente, mas apresentam risco à saúde humana e ao meio ambiente. Dentre esses POE, podemos destacar o nonilfenol etoxilado, um surfactante não-iônico utilizado no desengraxe alcalino da indústria de galvanoplastia. Esse surfactante possui uma recalcitrância e toxidade que aumenta com a diminuição do número de grupos etoxilados, processo que ocorre quando ele é biodegradado. Alguns dos produtos da biodegradação são o nonilfenol com 4, 3, 2 ou 1 grau de etoxilação e nonilfenol, este considerado disruptor endócrino imitando o hormônio natural 17β-estradiol. Tratamentos convencionais de efluentes e água não são eficientes para degradação completa desses compostos. O emprego de processos mais eficientes, como processos oxidativos e oxidativos avançados tais como a Eletrólise (E), Fotólise direta (F), Fotocatálise heterogênea (FH) e a fotoeletrooxidação (FEO), tecnologias limpas que utilizam o elétron e o fóton como reagentes, têm sido proposto como opção para a degradação desses compostos, evitando assim a contaminação dos recursos hídricos. Este trabalho foi realizado com uma solução baseada na composição de um efluente industrial contendo nonilfenol etoxilado com 4 graus de etoxilação. Os ensaios de FEO foram realizados em triplicata, variando-se a densidade de corrente, potência de lâmpada e o tempo de tratamento. Além disso, foram realizados, para efeito de comparação e elucidação de mecanismos, ensaios de eletrólise, fotólise direta e fotocatálise heterogêna. As amostras coletadas antes e após os processos oxidativos foram caracterizadas por diferentes métodos analíticos e por toxicidade. Verificou-se que no tempo de tratamento de 240 minutos as diferentes configurações de FEO não foram suficientemente eficazes na degradação de todo o poluente que se encontra na solução inicial, entretanto, a configuração FEO3 não gerou metabólitos mais tóxicos, não apresentou diferença de germinação e de crescimento de raiz, não apresentando também citotoxicidade e genotoxicidade em alface e em cebola, apresentando toxicidade apenas em peixes em uma concentração de 70,71%, o que pode ser evitado com o aumentando do tempo de tratamento, à vista disso, o processo de FEO torna-se uma opção na degradação do nonilfenol etoxilado e de outros POE, evitando assim que esses atinjam os recursos hídricos. / The emerging organic pollutants (POE) are chemical compounds present in a variety of commercial products such as medicines, toiletries, pesticides, surfactants, among others, can be found in environmental and biological matrices. These pollutants are usually not monitored or have no corresponding regulatory legislation, but present risk to human health and the environment. POE Among these, we highlight the nonylphenol ethoxylate, one non-ionic surfactant used in degreasing alkaline electroplating industry. This surfactant has a recalcitrance and toxicity increases with the decrease of the number of ethoxylate groups, a process which occurs when it is biodegraded. Some of the products of biodegradation are nonylphenol with 4, 3, 2 or 1 degree of ethoxylation of nonylphenol and this considered endocrine disruptor mimicking the natural hormone 17β -estradiol. Conventional treatment of sewage and water are not efficient for complete degradation of these compounds. The use of more efficient processes, such as oxidation and advanced oxidation processes such as direct photolysis (F), Electrolysis (E), heterogeneous photocatalysis (FH) and photoelectrooxidation (FEO), clean technologies that utilize the electron and photon reagents have been proposed as an option to the degradation of such compounds, thereby avoiding the contamination of water resources. This work was carried out with a solution based on the composition of an industrial effluent containing nonylphenol ethoxylate with 4 degrees of ethoxylation. FEO assays were performed in triplicate, by varying the current density lamp power and treatment time. In addition, we performed, for comparison and elucidation of mechanisms, testing electrolysis, photolysis and photocatalysis heterogenous. The samples collected before and after the oxidative processes were characterized by different analytical methods and toxicity. It was found that treatment time of 240 minutes, the FEO different configurations were not efficient enough to degrade any pollutants that is in the initial solution, however, the configuration FEO3 not more toxic metabolites generated no significant difference in seed germination and root growth, no significant cytotoxicity and genotoxicity also in lettuce and onion, showing toxicity on fish only at a concentration of 70.71 %, which can be avoided by increasing treatment time, the sight, the process of FEO becomes an option in the degradation of nonylphenol ethoxylate and other POE, thus preventing it reaches the water.

Os poluentes orgânicos emergentes (POE) são compostos químicos presentes numa variedade de produtos comerciais como medicamentos, produtos de higiene, agrotóxicos, surfactantes, dentre outros, podendo ser encontrados em matrizes ambientais e biológicas. Esses poluentes não são usualmente monitorados ou ainda não possuem legislação regulatória correspondente, mas apresentam risco à saúde humana e ao meio ambiente. Dentre esses POE, podemos destacar o nonilfenol etoxilado, um surfactante não-iônico utilizado no desengraxe alcalino da indústria de galvanoplastia. Esse surfactante possui uma recalcitrância e toxidade que aumenta com a diminuição do número de grupos etoxilados, processo que ocorre quando ele é biodegradado. Alguns dos produtos da biodegradação são o nonilfenol com 4, 3, 2 ou 1 grau de etoxilação e nonilfenol, este considerado disruptor endócrino imitando o hormônio natural 17β-estradiol. Tratamentos convencionais de efluentes e água não são eficientes para degradação completa desses compostos. O emprego de processos mais eficientes, como processos oxidativos e oxidativos avançados tais como a Eletrólise (E), Fotólise direta (F), Fotocatálise heterogênea (FH) e a fotoeletrooxidação (FEO), tecnologias limpas que utilizam o elétron e o fóton como reagentes, têm sido proposto como opção para a degradação desses compostos, evitando assim a contaminação dos recursos hídricos. Este trabalho foi realizado com uma solução baseada na composição de um efluente industrial contendo nonilfenol etoxilado com 4 graus de etoxilação. Os ensaios de FEO foram realizados em triplicata, variando-se a densidade de corrente, potência de lâmpada e o tempo de tratamento. Além disso, foram realizados, para efeito de comparação e elucidação de mecanismos, ensaios de eletrólise, fotólise direta e fotocatálise heterogêna. As amostras coletadas antes e após os processos oxidativos foram caracterizadas por diferentes métodos analíticos e por toxicidade. Verificou-se que no tempo de tratamento de 240 minutos as diferentes configurações de FEO não foram suficientemente eficazes na degradação de todo o poluente que se encontra na solução inicial, entretanto, a configuração FEO3 não gerou metabólitos mais tóxicos, não apresentou diferença de germinação e de crescimento de raiz, não apresentando também citotoxicidade e genotoxicidade em alface e em cebola, apresentando toxicidade apenas em peixes em uma concentração de 70,71%, o que pode ser evitado com o aumentando do tempo de tratamento, à vista disso, o processo de FEO torna-se uma opção na degradação do nonilfenol etoxilado e de outros POE, evitando assim que esses atinjam os recursos hídricos. / The emerging organic pollutants (POE) are chemical compounds present in a variety of commercial products such as medicines, toiletries, pesticides, surfactants, among others, can be found in environmental and biological matrices. These pollutants are usually not monitored or have no corresponding regulatory legislation, but present risk to human health and the environment. POE Among these, we highlight the nonylphenol ethoxylate, one non-ionic surfactant used in degreasing alkaline electroplating industry. This surfactant has a recalcitrance and toxicity increases with the decrease of the number of ethoxylate groups, a process which occurs when it is biodegraded. Some of the products of biodegradation are nonylphenol with 4, 3, 2 or 1 degree of ethoxylation of nonylphenol and this considered endocrine disruptor mimicking the natural hormone 17β -estradiol. Conventional treatment of sewage and water are not efficient for complete degradation of these compounds. The use of more efficient processes, such as oxidation and advanced oxidation processes such as direct photolysis (F), Electrolysis (E), heterogeneous photocatalysis (FH) and photoelectrooxidation (FEO), clean technologies that utilize the electron and photon reagents have been proposed as an option to the degradation of such compounds, thereby avoiding the contamination of water resources. This work was carried out with a solution based on the composition of an industrial effluent containing nonylphenol ethoxylate with 4 degrees of ethoxylation. FEO assays were performed in triplicate, by varying the current density lamp power and treatment time. In addition, we performed, for comparison and elucidation of mechanisms, testing electrolysis, photolysis and photocatalysis heterogenous. The samples collected before and after the oxidative processes were characterized by different analytical methods and toxicity. It was found that treatment time of 240 minutes, the FEO different configurations were not efficient enough to degrade any pollutants that is in the initial solution, however, the configuration FEO3 not more toxic metabolites generated no significant difference in seed germination and root growth, no significant cytotoxicity and genotoxicity also in lettuce and onion, showing toxicity on fish only at a concentration of 70.71 %, which can be avoided by increasing treatment time, the sight, the process of FEO becomes an option in the degradation of nonylphenol ethoxylate and other POE, thus preventing it reaches the water.

Surfactants are one of the more ubiquitous contaminants in aquatic systems. Their importance as toxic components of pesticide formulations has, however, been largely overlooked. Amphibians particularly, as inhabitants of shallow, temporary and often lentic aquatic environments may be at risk from exposure to these chemicals when they enter aquatic systems. This thesis presents data on the toxicity of surfactants to amphibians. Several experimental exposures were conducted with embryo-larval, tadpole and adult developmental stages of the Australian species- Crinia insignifera, Helcioporus eyrei, Limnodynastes dorsalis and Litoria moorei and the exotic species- Bufo marinus and Xenopus laevis. Animals were variously exposed to glyphosate formulations that contain a high proportion of nonionic surfactants, or commercial pesticide wetting agents (alcohol alkoxylate and nonylphenol ethoxylate (NPE) surfactants). Feeding stage tadpoles of C.insignifera, H. eyrei, L. dorsalis and L. moorei were exposed to three commercial glyphosate formulations, glyphosate isopropylamine and glyphosate acid in static-renewal acute toxicity tests. The 48-h LC50 values for Roundup Herbicide (MON 2139) tested against tadpoles of C. insignifera, H. eyrei, L. dorsalis and L. moorei ranged between 8.1 and 32.2 mg/L (2.9 and 11.6 mg/L glyphosate acid equivalent (ae)), while the 48-h LC50 values for Roundup Herbicide tested against adult and newly metamorphosed C. insignifera ranged from 137-144 mg/L (49.4-51.8 mg/L ae). / Touchdown Herbicide (4 LC-E) tested against tadpoles of C. insignifera, H. eyrei, L. dorsalis and L. moorei was slightly less toxic than Roundup with 48-h LC50 values ranging between 27.3 and 48.7 mg/L (9.0 and 16.1 mg/L ae). Roundup Biactive (MON 77920) was practically non-toxic to tadpoles of the same four species producing 48-h LC50 values of 911 mg/L (328 mg/L ae) for L. moorei and >1000 mg/L (>360 mg/L ae) for C. insignifera, H. eyrei and L. dorsalis. Glyphosate isopropylamine was practically non-toxic producing no mortality amongst tadpoles of any of the four species over 48 h, at concentrations between 503 and 684 mg/L (343 and 466 mg/L ae). The toxicity of technical grade glyphosate acid (48-h LC50, 81.2-121 mg/L) is likely to be due to acid intolerance. Feeding stage tadpoles of B. marinus, X laevis, C. insignifera, H.eyrei, L. dorsalis and L. moorei were exposed to NPE and alcohol alkoxylate in static renewal acute toxicity tests. All species exhibited non-specific narcosis following exposure to both these surfactants. The 48-h EC50 values for NPE ranged between 1.1 mg/L (mild narcosis) and 12.1 mg/L (full narcosis). The 48-h EC50 values for alcohol alkoxylate ranged between 5.3 mg/L (mild narcosis) and 25.4 mg/L (full narcosis). Xenopus laevis was the most sensitive species tested. The sensitivity of the other five species was size dependent with larger species displaying greater tolerance. Replicate acute toxicity tests with B. marinus exposed to NPE at 30 degrees celsius over 96 hours indicated that the narcotic effects were not particularly time dependant. / The mean 24, 48, 72 and 96-h EC50 (mild narcosis) were 3.6, 3.7, 3.5 and 3.5 mg/L respectively. The mean 24, 48, 72, and 96-h EC50 (full narcosis) values were 4.0, 4.1, 4.2 and 4.0 respectively. Acute toxicity tests with B. marinus exposed to NPE at 30 degrees celsius under conditions of low dissolved oxygen (0.8-2.3 mg/L) produced a two to threefold increase in toxicity. The 12-h EC50 values ranged from 1.4 to 2.2 mg/L. The embryotoxicity of NPE was determined in X. laevis, L. adelaidensis and C. insignifera using a Frog Embryo Teratogenesis assay-Xenopus (FETAX). The 96-h LC50, EC50 and MCIG (LOEC) values for X. laevis were 3.9 to 5.4 mg/L, 2.8 to 4.6 mg/L and 1.0 to 3.0 mg/L respectively. The 140-h LC50, ECSO and MCIG values for L. adelaidensis were 9.2 mg/L, 8.8 mg/L and 5.1 to 6.0 ing/L respectively. The 134-h LC50, EC50 and MCIG values for C. insignifera were 6.4 mg/L, 4.5 mg/L and 4.0 mg/L respectively. Teratogenicity indices for the three species ranged between 1.0 and 1.6 indicating either no or low teratogenicity. Xenopus laevis was the more sensitive of the three species and the only species that displayed indisputable terata. The acute toxicity data indicated that the amphibian species tested were of similar sensitivity to fish and some invertebrates. Developmental retardation and oestrogenic effects following exposure to nonylphenol ethoxylate were indicated by sublethal toxicity tests. Crinia insignifera embryos were exposed during early embryogenesis to sublethal concentrations of NPE. / Exposure to NPE did not affect either weight nor size (snout-vent length) at metamorphosis. Exposure to 5.0mg/L NPE resulted in a significant delay in the time required to reach metamorphosis. Also, exposure to 3.0 mg/L NPE for the first 6 days of embryonic development or exposure to 5.0 mg/L NPE from day 2 to day 6 resulted in a statistically significant predominance in the female phenotype amongst metamorphosing froglets. Exposure for the first five days to 1.5 ing/L or 3.0 mg/L NPE had no effect on sex ratio. The results indicated that exposure to NPEs has endocrine disruptive effects in this species and that a narrow window of susceptibility exists for the induction of predominantly female phenotype. This study has also followed the degradation of a mixture of NPE oligomers and the concomitant formation of individual oligomers in static die-away tests with and without illumination in freshwater. Over 33 days in darkness there was a progressive and complete loss of long chain oligomers (NPEO(subscript)8-17), transient increases and subsequent loss of short to medium chain oligomers (NPE0(subscript)4-7), and large persistent increases (approximately 1000%) in short chain oligomers (NPE0(subscript)1-3). In the presence of illumination, biodegradation was retarded and heterotrophic bacterial proliferation was inhibited. After 33 days there was complete loss of long chain oligomers (NPE0(subscript)9-17), incomplete loss of medium chain oligomers (NPE0(subscript)6.8) and increases in short chain oligomers (NPE0(subscript)1-5). / This thesis discusses the importance of persistent metabolites of NPE degradation as it pertains to the habitat, developmental time frame and ecology of amphibians. Degradation of NPE is likely to occur over a time frame that is longer than that required for complete embryogenesis and metamorphosis of many species of amphibians, and may easily encompass those critical stages of development during which oestrogenic metabolites can affect development.