M.Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology / Water contaminated with non-biodegradable organics is becoming increasing problematic as it has a hazardous effect on human health and the aquatic environment. Therefore, the removal of organic contaminants is of importance and an active heterogeneous Fenton catalyst is thus required. The literature indicates that a bimetallic oxide Fenton catalyst is more active than an iron oxide catalyst. This study focused on increasing the activity of iron-based Fenton catalysts with the addition of transition metals such as manganese, cobalt and copper and optimizing the preparation method. In this study, bimetallic oxide (Fe-Cu, Fe-Mn, Fe-Co) and monometallic oxide (Fe, Cu, Mn,Co) catalysts supported on silica SiO2 where prepared by incipient wetness impregnation. The total metal oxide contents were kept constant. The catalysts where calcined in two different ways, in a conventional oven and in a microwave. These catalysts were characterized with XRD, XPS and CV and were tested for the degradation of methylene blue dye at 27°C. The catalysts calcined in a microwave oven had a higher catalytic activity than those prepared in a conventional oven. The bimetallic oxide catalysts outperformed the mono- metallic oxide catalysts in the degradation of methylene blue. The Fe2MnOx prepared by microwave energy were the most active catalyst yielding the highest percentage of degradation of methylene blue dye (89.6%) after 60 minutes. The relative amounts of manganese and iron oxide were varied while keeping the total metal content in the catalyst the same. The optimum ratio of Fe to Mn was 1:7.5 since it yielded the most active catalyst. A 96.6 % removal of methylene blue was achieved after 1 hour of degradation. Lastly this ratio 1Fe:7.5Mn was prepared by varying different microwave power (600, 700 and 800 W) and irradiation time (10, 20 and 30 min). The optimum microwave power and irradiation time was 800W and 10 min with the methylene blue percentage removal of 96.6 % after 1 hour of degradation.

Inorganic arsenic is a potent carcinogen and toxicant associated with numerous adverse health outcomes, and is number one on the Agency for Toxic Substances and Disease Registry Substance Priority List. Uranium is also a carcinogen and nephrotoxicant, however health effects at levels experienced by general populations is unclear. Chronic exposure to inorganic arsenic (As) and uranium (U) in the United States (US) occurs from unregulated private wells and federally regulated community water systems (CWSs). Geogenic arsenic contamination typically occurs in groundwater as opposed to surface water supplies. Groundwater is a major source for many CWSs in the US. Although the US Environmental Protection Agency sets the maximum contaminant level (MCL enforceable since 2006: 10 µg/L) for arsenic in CWSs, private wells are not federally regulated. The contribution of drinking water from private wells and regulated CWSs to total inorganic arsenic and uranium exposure is not clear.In the United States (US), type 2 diabetes (T2D) affects approximately 37.3 million people (11.3% of the population), with the highest burden in American Indian communities. Toxic metal exposures have been identified as risk factors of T2D. Most studies rely on biomarkers, which could be affected by early disease processes. Studies directly measuring metals in drinking water in US populations have been limited. In Chapter 2, we evaluated county-level associations between modeled values of the probability of private well arsenic exceeding 10 µg/L and CWS arsenic concentrations for 2,231 counties in the conterminous US, using time invariant private well arsenic estimates and CWS arsenic estimates for two time periods. Nationwide, county-level CWS arsenic concentrations increased by 8.4 µg/L per 100% increase in the probability of private well arsenic exceeding 10 µg/L for 2006 – 2008 (the initial compliance monitoring period after MCL implementation), and by 7.3 µg/L for 2009 – 2011 (the second monitoring period following MCL implementation) (1.1 µg/L mean decline over time). Regional differences in this temporal decline suggest that interventions to implement the MCL were more pronounced in regions served primarily by groundwater. The strong association between private well and CWS arsenic in Rural, American Indian, and Semi Urban, Hispanic counties suggests that future research and regulatory support are needed to reduce water arsenic exposures in these vulnerable subpopulations. This comparison of arsenic exposure values from major private and public drinking water sources nationwide is critical to future assessments of drinking water arsenic exposure and health outcomes. In Chapter 3, we aimed to determine the association between drinking water arsenic estimates and urinary arsenic concentrations in the 2003-2014 National Health and Nutrition Examination Survey (NHANES). We evaluated 11,088 participants from the 2003-2014 NHANES cycles. For each participant, we assigned private well and CWS arsenic levels according to county of residence using estimates previously derived by the U.S. Environmental Protection Agency and U.S. Geological Survey. We used recalibrated urinary dimethylarsinate (rDMA) to reflect the internal dose of estimated water arsenic by applying a previously validated, residual-based method that removes the contribution of dietary arsenic sources. We compared the adjusted geometric mean ratios and corresponding percent change of urinary rDMA across tertiles of private well and CWS arsenic levels, with the lowest tertile as the reference. Comparisons were made overall and stratified by census region and race/ethnicity. Overall, the geometric mean of urinary rDMA was 2.52 (2.30, 2.77) µg/L among private well users and 2.64 (2.57, 2.72) µg/L among CWS users. Urinary rDMA was highest among participants in the West and South, and among Mexican American, Other Hispanic, and Non-Hispanic Other participants. Urinary rDMA levels were 25% (95% confidence interval (CI): 17-34%) and 20% (95% CI: 12-29%) higher comparing the highest to the lowest tertile of CWS and private well arsenic, respectively. The strongest associations between water arsenic and urinary rDMA were observed among participants in the South, West, and among Mexican American and Non-Hispanic White and Black participants. Both private wells and regulated CWSs are associated with inorganic arsenic internal dose as reflected in urine in the general U.S. population. In Chapter 4, our objective was to evaluate regional and sociodemographic inequalities in water arsenic exposure reductions associated with the US Environmental Protection Agency’s Final Arsenic Rule, which lowered the arsenic maximum contaminant level to 10 µg/L in public water systems. We analyzed 8,544 participants from the 2003-14 National Health and Nutrition Examination Survey (NHANES) reliant on community water systems (CWSs). We estimated arsenic exposure from water by recalibrating urinary dimethylarsinate (rDMA) to remove smoking and dietary contributions. We evaluated mean differences and corresponding percent reductions of urinary rDMA comparing subsequent survey cycles to 2003-04 (baseline), stratified by region, race/ethnicity, educational attainment, and tertile of CWS arsenic assigned at the county level. The overall difference (percent reduction) in urine rDMA was 0.32 µg/L (9%) among participants with the highest tertile of CWS arsenic, comparing 2013-14 to 2003-04. Declines in urinary rDMA were largest in regions with the highest water arsenic: the South [0.57 µg/L (16%)] and West [0.46 µg/L, (14%)]. Declines in urinary rDMA levels were significant and largest among Mexican American [0.99 µg/L (26%)] and Non-Hispanic White [0.25 µg/L (10%)] participants. Reductions in rDMA following the Final Arsenic Rule were highest among participants with the highest CWS arsenic concentrations, supporting legislation can benefit those who need it the most, although additional efforts are still needed to address remaining inequalities in CWS arsenic exposure. In Chapter 5, we examined the contribution of water As and U to urinary biomarkers in the Strong Heart Family Study (SHFS), a prospective study of American Indian communities, and the Multi-Ethnic Study of Atherosclerosis (MESA), a prospective study of racially/ethnically diverse urban US communities. We assigned residential zip code-level estimates in CWSs (µg/L) and private wells (90th percentile probability of As >10 µg/L) to up to 1,485 and 6,722 participants with dietary information and urinary biomarkers in the SHFS (2001-2003) and MESA (2000-2002; 2010-2011), respectively. Total inorganic As exposure was estimated as the sum of inorganic and methylated species in urine (urine As). We used linear mixed-effects models to account for participant clustering and removed the effect of dietary sources of As and U via regression adjustment. The median (interquartile range) urine As was 5.32 (3.29, 8.53) and 6.32 (3.34, 12.48) µg/L for SHFS and MESA, respectively, and urine U was 0.037 (0.014, 0.071) and 0.007 (0.003, 0.018) µg/L. In a mixed-effects meta-analysis of pooled effects across the SHFS and MESA, urine As was 11% (95% CI: 3, 20%) higher and urine U was 35% (5, 73%) higher per 2-fold higher CWS As and U, respectively. In the SHFS, CWS and private well As explained >40% of variability in urine As and CWS U explained >20% of urine U. In MESA, CWS As and U explained >50% of urine As and U. Water from public water supplies and private wells represents a major contributor to inorganic As and U exposure in diverse US populations. In Chapter 6, we examined the association of arsenic exposures in community water systems (CWS) and private wells with T2D incidence in the Strong Heart Family Study (SHFS), a prospective cohort of American Indian communities, and the Multi-Ethnic Study of Atherosclerosis (MESA), a prospective study of racially/ethnically diverse urban US communities, to evaluate direct associations between drinking water metal exposures and T2D risk. We evaluated adults in the SHFS free of T2D at baseline (2001-2003) and followed through 2010, with available private well and CWS arsenic (N=1,791) estimates assigned by residential zip code. We also evaluated adults in the MESA free of T2D at baseline (2000-2002) and followed through 2019, with available zip code level CWS arsenic (N=5,577) estimates. We used mixed effects Cox models to account for clustering by family and residential zip code, with adjustment for sex, baseline age, body mass index (BMI), smoking status, and education. T2D incidence in the SHFS was 24.4 cases per 1,000 people (mean follow-up 5.6 years) and T2D incidence in MESA was 11.2 per 1,000 people (mean follow-up 6.0 years). In a meta-analysis of pooled effects across the SHFS and MESA, the corresponding hazard ratio (95% confidence interval) per 2-fold increase in water arsenic was 1.09 (1.01, 1.16). Differences were observed by BMI category and sex; positive associations were observed among participants with BMI <25 kg/m2 and among female participants. In categorical analyses, >10% probability of private well arsenic (<10% reference) in the SHFS and >1 µg/L of CWS arsenic (<1 µg/L reference) in MESA were associated with increased diabetes risk. Low to moderate water arsenic levels in unregulated private wells and federally regulated CWSs were associated with T2D incidence in the SHFS and MESA. In supplementary analyses, we also observed that CWS uranium was associated with T2D risk among SHFS and MESA participants with BMI<25 kg/m2.

Excessive nitrates in drinking water pose a human health threat, especially to infants. Methemoglobinemia, or blue-baby syndrome, is a potentially fatal condition that inhibits the ability of red blood cells to bind and transport oxygen. Nitrates/nitrites have also been linked to such conditions as cancer, birth defects, and behavioral and developmental abnormalities. Nitrates are frequently found in wells in rural farming areas because synthetic fertilizers (containing nitrates) leach from the soil into the groundwater. The Lower Umatilla Basin (LUB) in Morrow and Umatilla counties of Oregon represents an intensively farmed and irrigated area in which relatively high amounts of nitrates are present in the groundwater and domestic well water. This study investigated population demographics for the rural Lower Umatilla Basin, comparing these data to identified well-water nitrate levels for the purpose of estimating nitrate exposures and potential risk of adverse health effects in the survey area. Results of the investigation revealed that 25 percent of the domestic-use wells in the survey area had nitrate levels that were in excess of the 10 ppm nN MCL for drinking water, as established by the U.S. Environmental Protection Agency. From access to these wells, 23 percent of the surveyed population was exposed to nitrate concentrations in excess of the MCL standard. However, resident infants were neither exposed to well-water nitrates in excess of the standard, nor were they exposed to illness that could have increased the risk of methemoglobinemia. The LUB survey population was generally older than the populations from cities in the LUB or the combined populations of rural areas of Morrow and Umatilla counties. The population included few women of childbearing age, and it was not subject to an appreciable increase in the proportion of younger to older families. These factors reduced the likelihood of a significant increase in the infant population, which also minimized the risk of methemoglobinemia to this population. Even though the risk of methemoglobinemia to infants was low in the LUB area, it is recommended that exposures to well-water nitrates be prevented, if possible even for adults, to reduce the potential for chronic, adverse health effects from excess nitrate ingestion. Continued monitoring of private wells by state agencies is recommended, with attention directed at domesticuse wells with nitrate levels in excess of 10 ppm nN. This information should be shared with local health departments for follow-up, investigation, and educational efforts as needed. Future studies by the Oregon DEQ, or other agencies which seek to document the sources of well-water nitrate contamination in the LUB, should include an investigation of the influence of local sources of nitrate contamination. / Graduation date: 1993

Thesis (M. Tech. (Environmental Health)) -- Central University of technology, Free State, 2013 / Introduction: Drinking water of poor quality can cause a variety of diseases and may even result in death. The impact of poor drinking water is a course for concern even in South Africa. Therefore, the physical, chemical and microbiological drinking water quality was investigated in the peri-urban area of Bainsvlei and the Woodlands Hills Estate in Bloemfontein, Free State. Materials and Methods: The water quality was assessed in 20 identified sampling sites for three series with ten weeks apart. These sites use treated municipal and untreated borehole water for drinking. The determinants analysed for were pH, electrical conductivity (EC), turbidity, temperature, Ca, Mg, Na, F, Cl, N, SO₄,N, Free chlorine, Al, As, CN, Fe, Mn, Pb, Hg, total coliforms and E. coli. The water samples were collected and analysed on site and in the laboratory. Both the physical and chemical determinants were measured using standard methods whereas the microbiological determinants were measured using the Defined Substrate Technology (DST) method. The measurements were first compared to the SANS 241 (2011) for compliance. The ANOVA tests were used to investigate if any seasonal variations existed in the water quality as well as to compare the levels of the determinants between borehole and municipal water. In the assessment of the overall drinking water quality of different water sampling sites the water quality index (WQI) was used. Results and Discussions: Significant effects were believed to exist if the p-values of the ANOVA and Scheffe tests were at a significance level of 5% (p < 0.05). The study results revealed that of the four physical determinants that were measured turbidity exceeded the standard in many sampling sites in the three series. Of all the chemical determinants, nitrates exceeded the standard. In the same way coliforms exceeded the standard in a number of sampling sites while E. coli was found in a few sampling sites in the first series. ANOVA tests revealed that seasonal variations existed between pH, EC, temperature, cyanide and iron at a significant level of 5% (p < 0.05) while the Post-hoc Scheffe test further revealed the series in which the effect existed. Similarly, the ANOVA tests revealed that the levels of the determinants between municipal versus borehole varied in pH, EC, Ca, Mg, Na, F, Cl, N, and SO₄ at a significant level of 5% (p < 0.05). The WQI showed that in all the series when combining the good and excellent category season 2 had the highest percentage of 80%, followed by season 3 with 79% and season 1 with 70%. Only borehole sampling sites were found in the poor, very poor and unsuitable categories. Similarly all the highest WQI values were found in borehole sampling sites. Conclusion: This study revealed that the water quality is of good quality in the Bainsvlei and Woodlands Hills Estate of the Mangaung metropolitan municipality in Bloemfontein, in the Free State, South Africa. The presence of E. coli, though found in a few sampling sites and the high levels of turbidity, nitrates and coliforms are of concern to public health.

O estuário de Santos abriga o maior porto da América Latina e um dos maiores complexos industriais do Brasil. Na década de 1970 foi considerado um dos maiores exemplos de degradação ambiental em ambientes costeiros, e apesar da melhora na qualidade ambiental observada nos últimos anos algumas áreas deste estuário apresentam sedimentos ainda altamente contaminados com compostos tóxicos e genotóxicos, especialmente os Hidrocarbonetos Policíclicos Aromáticos (HPA). Operações de dragagem para manutenção das atividades portuárias são necessárias e consequentemente durante este processo pode ocorrer a ressuspensão de contaminantes presentes nesses sedimentos, tornando-os disponíveis novamente na coluna d\'água. Desta forma é interessante ter uma estratégia eficiente e aplicável no monitoramento da qualidade dessas águas. O Blue rayon (BR) é um adsorvente seletivo para compostos policíclicos com três ou mais anéis fundidos em sua molécula e tem sido utilizado com sucesso no monitoramento de HPA e atividade mutagênica em ambientes aquáticos. Este trabalho teve como objetivo padronizar o uso da técnica de Blue rayon in situ ancorado, onde as fibras são fixas a uma distância padronizada dos sedimentos, associada ao teste de Salmonella/microssoma em microssuspensão a ser aplicada no monitoramento das águas desse estuário. Foram selecionados três pontos de amostragem com diferentes características e sedimentos com variados níveis de contaminação. As duas campanhas iniciais foram realizadas com o objetivo de avaliar a eficiência do BR e de escolher a linhagem de Salmonella mais sensível aos compostos mutagênicos possivelmente presentes nos extratos obtidos bem como verificar a presença de HPA. As cinco campanhas posteriores foram realizadas para verificar o comportamento e a eficiência da estratégia previamente definida no monitoramento das águas desse estuário utilizando experimentos de dose resposta. Os resultados obtidos nas duas primeiras campanhas mostraram que as águas do ponto 1, que contém os sedimentos mais contaminados e recebe os efluentes da COSIPA, apresentam maior contaminação por HPA e atividade genotóxica mais elevada que o ponto 2. Também foi possível determinar que a linhagem de Salmonella YG1041 foi a mais sensível para detectar atividade mutagênica tanto no ponto 1 quanto no ponto 2. Nas cinco campanhas subsequentes as maiores potências mutagênicas foram também observadas no ponto 1 com valores máximos de 5.100 e 36.000 revertentes/g de BR para a linhagem YG1041 na ausência e na presença de ativação metabólica (S9) respectivamente. Nos pontos 2 e 3 as potências observadas foram similares entre si, com valores em torno de 1.000 revertentes/g de BR. Com base nos resultados obtidos nas duas etapas deste trabalho pode-se concluir que a o Blue rayon utilizado in situ a uma distância padronizada dos sedimento associado ao teste de Salmonella/microssoma em microssuspensão com a linhagem YG1041 na presença e na ausência de ativação metabólica (S9) é uma ferramenta que pode ser aplicada no monitoramento da qualidade do estuário de Santos. / Santos estuary is the major Latin American harbor and one of the largest industrial complex of Brazil. In the 1970s, it was considered one of the major examples of coastal degradation. Due to enforcement actions the quality of the environment has improved in the last years in relation to the chemical parameters and toxicity but unfortunately the sediment is still contaminated with toxic and genotoxic compounds especially Polycyclic Aromatic Hydrocarbons (PAHs). For the maintenance of the port activities sediment dredging is needed and during this process contaminants resuspension can occur, leading to the contamination of the water column. Therefore it is interesting to have an efficient strategy that can be used for the water quality monitoring of this area. The Blue rayon is a selective adsorbent to polycyclic compounds containing three or more fused rings and has been successfully used in the monitoring of PAHs and mutagenic activity in aquatic environments. The objective of this work was to evaluate a modified blue rayon hanging technique, denominated in this work \"Blue rayon anchored technique\", where the fibers are placed at a fixed distance from the sediment, associated with the Salmonella/microsome microsuspension assay in order to monitor the water quality of Santos estuary. Three sites with different sources and sediment contamination levels were selected in this study. Two initial samplings were performed in order to evaluate the efficiency of the BR modified technique and find the most sensitive strain of Salmonella typhimurium to the mutagens possibly present in the those waters as well as verify the presence of PAHs. Five subsequent samplings were performed to verify the performance and efficiency of the defined strategy in the estuary water quality monitoring using dose response experiments. In the two initial samplings, the water from the site containing the most contaminated sediment and under influence of COSIPA (site 1) presented higher mutagenic activity and higher levels of PAHs. It was also possible to verify the highest sensitivity of the YG1041 strain in the detection of the mutagenic activity in both sites analyzed. In the subsequent five samplings, higher mutagenic potencies were again observed for site 1, reaching 5,100 and 36,000 revertants per gram of BR for the YG1 041 strain in the absence and presence of S9 respectively. Sites 2 and: presented similar potencies, around 1000 revertants per gram of BR. Based on the obtained results we can conclude that the Blue rayon anchored technique associated with the Salmonella/microsome microsuspension assay with the YG1041 strain in the presence and absence of S9 is an suitable tool to monito Santos estuarine waters.

Indium-gallium-zinc oxide (IGZO) and zinc-tin oxide (ZTO) are investigated for thin-film transistor (TFT) applications. Negative bias illumination stress (NBIS) is employed for electrical stability assessment. Unpassivated IGZO and ZTO TFTs suffer from severe NBIS instabilities. Zinc-tin-silicon oxide is found to be an effective passivation layer for IGZO and ZTO TFTs, significantly improving the NBIS stability. NBIS instabilities in unpassivated TFTs are attributed to an NBIS-induced desorption of chemisorbed oxygen from the channel layer top surface, exposing surface oxygen vacancies. A ZTSO layer protects the channel layer top surface from adsorbed gas interactions and also appears to reduce the density of oxygen vacancies. The best device architectures investigated with respect to TFT electrical performance are found to be staggered with aluminum electrodes for unpassivated TFTs and coplanar with ITO electrodes for ZTSO-passivated TFTs. Annealing in wet-O₂ is not found to be effective for improving the performance of IGZO or ZTO TFTs or for reducing the post-deposition annealing temperature. / Graduation date: 2012

Submitted by Guacira de Figueiredo Eufrasio Pauly null (guafe@yahoo.com.br) on 2018-03-22T19:42:28Z No. of bitstreams: 1 Avaliação da toxicidade de misturas Irgarol e contaminantes ambientais comumente observados em áreas costeiras.pdf: 1773405 bytes, checksum: d022473735b82f51e6340d000b00e009 (MD5) / Approved for entry into archive by Disleide Silvia Valerio Gounella null (disleide@clp.unesp.br) on 2018-03-23T18:54:19Z (GMT) No. of bitstreams: 1 pauly_gfe_me_svic.pdf: 1773405 bytes, checksum: d022473735b82f51e6340d000b00e009 (MD5) / Made available in DSpace on 2018-03-23T18:54:19Z (GMT). No. of bitstreams: 1 pauly_gfe_me_svic.pdf: 1773405 bytes, checksum: d022473735b82f51e6340d000b00e009 (MD5) Previous issue date: 2018-02-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Alguns contaminantes encontrados no ambiente costeiro incluem os princípios ativos de tintas anti-incrustantes, entre os quais se destaca o Irgarol. O Irgarol pode interagir com outros contaminantes comuns em áreas litorâneas antropizadas, tais como a amônia e os surfactantes, sendo que os efeitos dessas combinações são desconhecidos. O objetivo do presente trabalho foi avaliar a toxicidade de misturas binárias do biocida Irgarol com amônia e surfactante Alquil. Benzeno Sulfonado Linear - LAS, além das toxicidades dessas substâncias isoladas. Essa avaliação foi realizada em duas etapas. Na primeira etapa, náuplios de Artemia sp., copépodo Nitocra sp. e embriões de ouriço do mar Echinometra lucunter, foram expostos às concentrações isoladas de Irgarol, amônia e LAS, para definição dos níveis tóxicos dessas substâncias às espécies testadas. Na segunda etapa, náuplios de Artemia sp. foram expostos a uma mistura binária de contaminantes (i.é. Irgarol + amônia; ou Irgarol + LAS) a fim de se avaliar se as toxicidades das misturas seguem o padrão aditivo, sinérgico ou antagônico. Os dados obtidos da primeira etapa dos testes realizados com náuplios de Artemia sp. expostos à amônia, LAS e Irgarol apresentaram CL50-48h 122,85 mg/L, 21,21 mg/L, e 1,81 mg/L, respectivamente, e CEO de 100 mg/L, 81 mg/L e 10 mg/L, respectivamente. Para os testes realizados com os copépodos Nitocra sp., as respectivas CI50-7d foram estimadas em 27,89 mg/L, 4,61 mg/L, e 0,13 mg/L, enquanto as CEO foram 100 mg/L, 8,1 mg/L, e 10 mg/L. A CE50-42h obtida nos testes com embriões de Echinometra lucunter expostos à amônia foi de 0,32 mg/L, enquanto a CEO foi de 0,1 mg/L. Todas as concentrações de exposição ao LAS foram tóxicas para os embriões de Echinometra lucunter, e não foi observada toxicidade do Irgarol. Ambas as misturas binárias de Irgarol e amônia e Irgarol e LAS apresentaram melhor ajuste para o modelo IA (ação independente), com efeitos antagônicos e sinérgicos, respectivamente. As ferramentas utilizadas foram úteis para prever o padrão de respostas das misturas químicas sobre as espécies. / Contaminants found in the coastal environment include antifouling biocides, such as the Irgarol, ammonia and surfactants, among others. Since they can occur together in the environment, they can interact with each other and the resulting toxicities of their combinations are unknown. The aim this work was to evaluate the toxicity of binary mixtures of Irgarol with ammonia and the surfactant Linear Alkyl-Benzene Sulfonate - LAS, as well as the toxicity these single substances. This investigation was made in two steps. In the first step, nauplii of Artemia sp., the marine organisms Nitocra sp. (Copepoda), and embryos of the sea urchin Echinometra lucunter, were exposed to concentrations of Irgarol, ammonia and LAS, in order to define the toxic levels of each chemical to marine species. In the second step, nauplii of Artemia sp. were exposed to binary mixtures of the contaminants (Irgarol + ammonia; or Irgarol + LAS) in order to evaluate if the toxicities of the mixtures follow addictive, synergistic or antagonistic patterns. To nauplii Artemia sp. exposed to ammonia, LAS and Irgarol, the LC50-48h values were 122.85 mg/L, 21.21 mg/L, and 1.81 mg/L, respectively, and the LOECs were 100 mg/L, 81 mg/L and 10 mgl/L, respectively. The respective IC50-7d obtained in the tests with the copepod Nitocra sp., were 27.89 mg/L, 4.61 mg/L and 0.13 mg/L, while the LOECs were 100 mg/L, 8.1 mg/L and 10 mg/L. For the E. lucunter embryos, the EC50-42h of ammonia was 0.32 mg/L, while the LOEC was 0.1 mg/L. All the tested concentrations of LAS were toxic to the embryos of E. lucunter, where Irgarol did not caused toxicity to these organisms. Both binary mixtures of Irgarol and ammonia and Irgarol and LAS showed better fit to the model IA (Independent Action), with antagonistic and synergistic effects, respectively. The used tools were useful to predict the toxicities of chemical mixtures to marine tropical species. / 4693520

CAPES / Muitos estudos demonstram que ocupações irregulares, descartes inadequados de resíduo e ineficiência no tratamento de efluentes, têm reduzido a qualidade dos corpos hídricos. Além das altas concentrações de nutrientes, baixas concentrações de oxigênio e elevadas cargas de matéria orgânica, os rios da região de Curitiba também estão contaminados com diversos micro poluentes orgânicos. Os contaminantes emergentes começaram a ser detectados recentemente, em baixas concentrações, mas são comprovadamente tóxicos aos seres vivos, devido à exposição constante. A fim de conhecer a situação atual do rio Barigui foram realizadas duas coletas, uma sazonal e outra de 24 h. Na sazonal foram coletadas amostras de água em 3 pontos do rio, nos meses de março, junho e novembro de 2015 e foram analisados cafeína, fenofibrato, genfibrozila, paracetamol, ibuprofeno, diclofenaco, naproxeno, cetoprofeno, ácido acetilsalicílico, ácido salicílico, estrona, estradiol, etinilestradiol, metilparabeno, etilparabeno, propilparabeno, butilparabeno, benzilparabeno e triclosan. Na de 24 h foram monitorados dois pontos, um à montante e outro à jusante da Estação de Tratamento de Esgoto (ETE) Santa Quitéria, em junho de 2016. Nesta foram estudados, na água, diversos parâmetros físicos e químicos, matéria orgânica, nutrientes, todos as substâncias citadas acima, progesterona, octocrileno, etilhexil metoxicinamato e 4-metilbenzelideno cânfora. Entre as concentrações máximas obtidas, o ácido salicílico foi o que apresentou a maior concentração e maior variação entre a coleta sazonal (2,38 μg L-1 ) e a de 24 h (31,85 μg L-1 ). A cafeína apresentou detecção de 100 %, comprovando sua presença constante no ambiente. Ela também apresentou boa correlação com nitrogênio amoniacal (r = 0,87; p < 0,0001; n = 24) e os demais contaminantes apresentaram boas correlações entre si, como por exemplo paracetamol e o ácido salicílico (r = 0,9434; p < 0,0001; n = 24). Os estrogênios tiveram detecção baixa, e não foram quantificados na maioria dos pontos. O estudo dos parabenos e dos filtros UV foi interessante para avaliar os picos de maior produção de esgoto. As maiores concentrações foram detectadas à jusante da ETE às 15 h, que equivale às 7 h, considerando o tempo de detenção hidráulica da estação. As correlações obtidas e as maiores concentrações no ponto BA-J, sugerem que esses compostos têm uma fonte em comum, sendo provavelmente efluentes clandestinos e/ou provenientes das ETEs. Sendo assim, a melhoria nos tratamentos de efluentes é imprescindível, a fim de reduzir a concentração dessas substâncias no ambiente. É importante também um estudo de priorização de contaminantes, levando em consideração as concentrações de exposição e toxicidade, para inseri-los em legislações futuras com limites de lançamento nos corpos aquáticos. Além disso, há necessidade de estudar o comportamento dessas substâncias no meio ambiente e de aprimorar as técnicas analíticas, a fim de conseguir monitorar simultaneamente metabólitos e substâncias com concentrações ainda mais baixas, de maneira automatizada e rápida, com sensibilidade e seletividade. / Many studies have demonstrated that irregular occupations, inadequate waste disposal, inefficiency in the treatment of effluents, have reduced the quality of water bodies. In addition to the high concentrations of nutrients, low concentration of oxygen and high organic matter loads, the rivers in the Curitiba region are also contaminated with several organic micro pollutants. The emerging contaminants (EC) recently began to be detected in low concentrations, but they are proven toxic to living beings due to constant exposure. In order to know the current situation of the Barigui River, two samplings were made, a seasonal and another of 24 hours. In the seasonal sampling, water samples were collected at 3 points in the river, in the months of March, July and November of 2015. In addition, were analyzed caffeine, fenofibrate, gemfibrozil, acetaminophen, ibuprofen, diclofenac, naproxen, ketoprofen, acetylsalicylic acid, salicylic acid, estrone, estradiol, ethinylestradiol, methyl paraben, ethyl paraben, propyl paraben, butyl paraben, benzyl paraben and triclosan. At the 24 h sampling, two points were monitored, one upstream and one downstream from the Santa Quitéria Wastewater Treatment Plant (WWTP), in June 2016. In this sampling, several physical and chemical parameters, organic matter, nutrients, all substances mentioned above, progesterone, octocrylene, ethylhexyl methoxycinnamate and 4-methylbenzelidene camphor were studied in the water. Among the maximum concentrations of EC in the water, salicylic acid presented the highest concentration and a greater variation between the seasonal sampling (2.38 μg L-1 ) and the 24 h sampling (31.85 μg L-1 ). Caffeine presented 100% of detection, confirming its constant presence in the environment. It also presented good correlation with ammoniacal nitrogen (r = 0.87, p <0.0001, n = 24) and the other contaminants showed good correlations with each other, such as paracetamol and salicylic acid (r = 0.9434; <0.0001; n = 24). Estrogens presented low detection, and were not quantified at most points. The study of parabens and UV filters was interesting to evaluate the peaks of higher sewage production. The highest concentrations were detected downstream from WWTP at the 15 h, which is equivalent to the 7 h, considering the hydraulic holding time of the treatment plant. The correlations obtained and the highest concentration values in the BA-J point suggest that these compounds have a common source, probably been clandestine effluents and/or derived from the WWTPs. Therefore, the improvement on effluent treatment is indispensable to reduce the concentration of these substances on the environment. A prioritization study of contaminants is also important, considering the exposure concentrations and toxicity, to incorporate them into future legislation and establish release limits on aquatic bodies. In addition, it is necessary to study the behavior of these substances in the environment and improve analytical techniques. In order to be able to simultaneously monitor metabolites and substances with even lower concentrations, in a fast, automated way, with sensitivity and selectivity.

CAPES / Muitos estudos demonstram que ocupações irregulares, descartes inadequados de resíduo e ineficiência no tratamento de efluentes, têm reduzido a qualidade dos corpos hídricos. Além das altas concentrações de nutrientes, baixas concentrações de oxigênio e elevadas cargas de matéria orgânica, os rios da região de Curitiba também estão contaminados com diversos micro poluentes orgânicos. Os contaminantes emergentes começaram a ser detectados recentemente, em baixas concentrações, mas são comprovadamente tóxicos aos seres vivos, devido à exposição constante. A fim de conhecer a situação atual do rio Barigui foram realizadas duas coletas, uma sazonal e outra de 24 h. Na sazonal foram coletadas amostras de água em 3 pontos do rio, nos meses de março, junho e novembro de 2015 e foram analisados cafeína, fenofibrato, genfibrozila, paracetamol, ibuprofeno, diclofenaco, naproxeno, cetoprofeno, ácido acetilsalicílico, ácido salicílico, estrona, estradiol, etinilestradiol, metilparabeno, etilparabeno, propilparabeno, butilparabeno, benzilparabeno e triclosan. Na de 24 h foram monitorados dois pontos, um à montante e outro à jusante da Estação de Tratamento de Esgoto (ETE) Santa Quitéria, em junho de 2016. Nesta foram estudados, na água, diversos parâmetros físicos e químicos, matéria orgânica, nutrientes, todos as substâncias citadas acima, progesterona, octocrileno, etilhexil metoxicinamato e 4-metilbenzelideno cânfora. Entre as concentrações máximas obtidas, o ácido salicílico foi o que apresentou a maior concentração e maior variação entre a coleta sazonal (2,38 μg L-1 ) e a de 24 h (31,85 μg L-1 ). A cafeína apresentou detecção de 100 %, comprovando sua presença constante no ambiente. Ela também apresentou boa correlação com nitrogênio amoniacal (r = 0,87; p < 0,0001; n = 24) e os demais contaminantes apresentaram boas correlações entre si, como por exemplo paracetamol e o ácido salicílico (r = 0,9434; p < 0,0001; n = 24). Os estrogênios tiveram detecção baixa, e não foram quantificados na maioria dos pontos. O estudo dos parabenos e dos filtros UV foi interessante para avaliar os picos de maior produção de esgoto. As maiores concentrações foram detectadas à jusante da ETE às 15 h, que equivale às 7 h, considerando o tempo de detenção hidráulica da estação. As correlações obtidas e as maiores concentrações no ponto BA-J, sugerem que esses compostos têm uma fonte em comum, sendo provavelmente efluentes clandestinos e/ou provenientes das ETEs. Sendo assim, a melhoria nos tratamentos de efluentes é imprescindível, a fim de reduzir a concentração dessas substâncias no ambiente. É importante também um estudo de priorização de contaminantes, levando em consideração as concentrações de exposição e toxicidade, para inseri-los em legislações futuras com limites de lançamento nos corpos aquáticos. Além disso, há necessidade de estudar o comportamento dessas substâncias no meio ambiente e de aprimorar as técnicas analíticas, a fim de conseguir monitorar simultaneamente metabólitos e substâncias com concentrações ainda mais baixas, de maneira automatizada e rápida, com sensibilidade e seletividade. / Many studies have demonstrated that irregular occupations, inadequate waste disposal, inefficiency in the treatment of effluents, have reduced the quality of water bodies. In addition to the high concentrations of nutrients, low concentration of oxygen and high organic matter loads, the rivers in the Curitiba region are also contaminated with several organic micro pollutants. The emerging contaminants (EC) recently began to be detected in low concentrations, but they are proven toxic to living beings due to constant exposure. In order to know the current situation of the Barigui River, two samplings were made, a seasonal and another of 24 hours. In the seasonal sampling, water samples were collected at 3 points in the river, in the months of March, July and November of 2015. In addition, were analyzed caffeine, fenofibrate, gemfibrozil, acetaminophen, ibuprofen, diclofenac, naproxen, ketoprofen, acetylsalicylic acid, salicylic acid, estrone, estradiol, ethinylestradiol, methyl paraben, ethyl paraben, propyl paraben, butyl paraben, benzyl paraben and triclosan. At the 24 h sampling, two points were monitored, one upstream and one downstream from the Santa Quitéria Wastewater Treatment Plant (WWTP), in June 2016. In this sampling, several physical and chemical parameters, organic matter, nutrients, all substances mentioned above, progesterone, octocrylene, ethylhexyl methoxycinnamate and 4-methylbenzelidene camphor were studied in the water. Among the maximum concentrations of EC in the water, salicylic acid presented the highest concentration and a greater variation between the seasonal sampling (2.38 μg L-1 ) and the 24 h sampling (31.85 μg L-1 ). Caffeine presented 100% of detection, confirming its constant presence in the environment. It also presented good correlation with ammoniacal nitrogen (r = 0.87, p <0.0001, n = 24) and the other contaminants showed good correlations with each other, such as paracetamol and salicylic acid (r = 0.9434; <0.0001; n = 24). Estrogens presented low detection, and were not quantified at most points. The study of parabens and UV filters was interesting to evaluate the peaks of higher sewage production. The highest concentrations were detected downstream from WWTP at the 15 h, which is equivalent to the 7 h, considering the hydraulic holding time of the treatment plant. The correlations obtained and the highest concentration values in the BA-J point suggest that these compounds have a common source, probably been clandestine effluents and/or derived from the WWTPs. Therefore, the improvement on effluent treatment is indispensable to reduce the concentration of these substances on the environment. A prioritization study of contaminants is also important, considering the exposure concentrations and toxicity, to incorporate them into future legislation and establish release limits on aquatic bodies. In addition, it is necessary to study the behavior of these substances in the environment and improve analytical techniques. In order to be able to simultaneously monitor metabolites and substances with even lower concentrations, in a fast, automated way, with sensitivity and selectivity.

O estuário de Santos abriga o maior porto da América Latina e um dos maiores complexos industriais do Brasil. Na década de 1970 foi considerado um dos maiores exemplos de degradação ambiental em ambientes costeiros, e apesar da melhora na qualidade ambiental observada nos últimos anos algumas áreas deste estuário apresentam sedimentos ainda altamente contaminados com compostos tóxicos e genotóxicos, especialmente os Hidrocarbonetos Policíclicos Aromáticos (HPA). Operações de dragagem para manutenção das atividades portuárias são necessárias e consequentemente durante este processo pode ocorrer a ressuspensão de contaminantes presentes nesses sedimentos, tornando-os disponíveis novamente na coluna d\'água. Desta forma é interessante ter uma estratégia eficiente e aplicável no monitoramento da qualidade dessas águas. O Blue rayon (BR) é um adsorvente seletivo para compostos policíclicos com três ou mais anéis fundidos em sua molécula e tem sido utilizado com sucesso no monitoramento de HPA e atividade mutagênica em ambientes aquáticos. Este trabalho teve como objetivo padronizar o uso da técnica de Blue rayon in situ ancorado, onde as fibras são fixas a uma distância padronizada dos sedimentos, associada ao teste de Salmonella/microssoma em microssuspensão a ser aplicada no monitoramento das águas desse estuário. Foram selecionados três pontos de amostragem com diferentes características e sedimentos com variados níveis de contaminação. As duas campanhas iniciais foram realizadas com o objetivo de avaliar a eficiência do BR e de escolher a linhagem de Salmonella mais sensível aos compostos mutagênicos possivelmente presentes nos extratos obtidos bem como verificar a presença de HPA. As cinco campanhas posteriores foram realizadas para verificar o comportamento e a eficiência da estratégia previamente definida no monitoramento das águas desse estuário utilizando experimentos de dose resposta. Os resultados obtidos nas duas primeiras campanhas mostraram que as águas do ponto 1, que contém os sedimentos mais contaminados e recebe os efluentes da COSIPA, apresentam maior contaminação por HPA e atividade genotóxica mais elevada que o ponto 2. Também foi possível determinar que a linhagem de Salmonella YG1041 foi a mais sensível para detectar atividade mutagênica tanto no ponto 1 quanto no ponto 2. Nas cinco campanhas subsequentes as maiores potências mutagênicas foram também observadas no ponto 1 com valores máximos de 5.100 e 36.000 revertentes/g de BR para a linhagem YG1041 na ausência e na presença de ativação metabólica (S9) respectivamente. Nos pontos 2 e 3 as potências observadas foram similares entre si, com valores em torno de 1.000 revertentes/g de BR. Com base nos resultados obtidos nas duas etapas deste trabalho pode-se concluir que a o Blue rayon utilizado in situ a uma distância padronizada dos sedimento associado ao teste de Salmonella/microssoma em microssuspensão com a linhagem YG1041 na presença e na ausência de ativação metabólica (S9) é uma ferramenta que pode ser aplicada no monitoramento da qualidade do estuário de Santos. / Santos estuary is the major Latin American harbor and one of the largest industrial complex of Brazil. In the 1970s, it was considered one of the major examples of coastal degradation. Due to enforcement actions the quality of the environment has improved in the last years in relation to the chemical parameters and toxicity but unfortunately the sediment is still contaminated with toxic and genotoxic compounds especially Polycyclic Aromatic Hydrocarbons (PAHs). For the maintenance of the port activities sediment dredging is needed and during this process contaminants resuspension can occur, leading to the contamination of the water column. Therefore it is interesting to have an efficient strategy that can be used for the water quality monitoring of this area. The Blue rayon is a selective adsorbent to polycyclic compounds containing three or more fused rings and has been successfully used in the monitoring of PAHs and mutagenic activity in aquatic environments. The objective of this work was to evaluate a modified blue rayon hanging technique, denominated in this work \"Blue rayon anchored technique\", where the fibers are placed at a fixed distance from the sediment, associated with the Salmonella/microsome microsuspension assay in order to monitor the water quality of Santos estuary. Three sites with different sources and sediment contamination levels were selected in this study. Two initial samplings were performed in order to evaluate the efficiency of the BR modified technique and find the most sensitive strain of Salmonella typhimurium to the mutagens possibly present in the those waters as well as verify the presence of PAHs. Five subsequent samplings were performed to verify the performance and efficiency of the defined strategy in the estuary water quality monitoring using dose response experiments. In the two initial samplings, the water from the site containing the most contaminated sediment and under influence of COSIPA (site 1) presented higher mutagenic activity and higher levels of PAHs. It was also possible to verify the highest sensitivity of the YG1041 strain in the detection of the mutagenic activity in both sites analyzed. In the subsequent five samplings, higher mutagenic potencies were again observed for site 1, reaching 5,100 and 36,000 revertants per gram of BR for the YG1 041 strain in the absence and presence of S9 respectively. Sites 2 and: presented similar potencies, around 1000 revertants per gram of BR. Based on the obtained results we can conclude that the Blue rayon anchored technique associated with the Salmonella/microsome microsuspension assay with the YG1041 strain in the presence and absence of S9 is an suitable tool to monito Santos estuarine waters.