This dissertation examines topics related to development, environment and health in developing countries using empirical methods. In the first chapter, I study how developing countries can increase enforcement to reduce subsidy leakage in public programs, by investing in the state capacity to target program beneficiaries. This chapter further attempts to understand how the formal sector and black market respond to a policy that reduces diversion of a subsidized commodity. I explore these questions using the case of a Unique ID-based direct fuel subsidy transfer policy in India. Second chapter focuses on the health and wealth trade off near mineral mining operations in developing countries. Using extensive data on mining, health outcomes and assets from 44 developing countries, this study quantifies the wealth gain and adverse health impact of mineral mining. With a number of empirical strategies, this study shows that, despite high wealth gains, how heavy metal mining significantly increases the level of anemia in women and stunting in children living near mines. In the third chapter, I estimate demand for a water quality diagnostic product -- arsenic testing, when it is offered at a price. I further look into various aspects related to selection, learning and households behavioral response to the information. This study is based on a field experiment in Bihar, India.

Background: In the country of Bangladesh, arsenic (As) exposure and high plasma homocysteine (hyperhomocysteinemia; HHcys) are widely prevalent. An estimated 35-77 million people in Bangladesh are exposed to As above the World Health Organization standard of 10 μg/L, while a cross-sectional study by our group estimated that 63% of men and 26% of women had HHcys. Both As exposure and HHcys are associated with adverse health outcomes. Arsenic exposure is an established cause of skin, lung, and bladder cancer, and cardiovascular disease, while HHcys is a strongly associated with increased risk for cardiovascular disease. Chronic kidney disease is emerging as an As-linked disease outcome. Potential mechanisms for adverse health effects induced by As (e.g. nephrotoxicity) include oxidative stress and inflammation. Inorganic As is metabolized through a series of methylation and reduction reactions which facilitate As excretion in urine; arsenite (AsIII), the primary form of As in Bangladesh drinking water, is converted to monomethylarsonic acid (MMAV), monomethylarsonous acid (MMAIII), and dimethylarsinic acid (DMAV). The methyl donor for these methylation reactions is S-adenosylmethionine (SAM). Because the availability of SAM is modulated by various nutritional parameters, nutritional interventions have the potential to enhance As methylation. Supplementation with folic acid (FA), which increases liver SAM, has been shown by our group to enhance As methylation and lower blood As in folate-deficient Bangladeshi adults. The endogenous synthesis of creatine from guanidinoacetate (GAA) consumes a large proportion of SAM, and creatine supplementation in the diet can downregulate endogenous creatine synthesis by inhibiting GAA production. In this way, creatine supplementation has the potential to spare SAM, enhance As methylation, and also lower homocysteine (Hcys), a by-product of SAM-dependent methylation. The potential for dietary creatine to enhance As methylation may explain the frequently observed associations of urinary creatinine with a decreased proportion of inorganic As in urine out of total urinary As (u%InAs), and an increased proportion of DMA in urine out of total urinary As (u%DMA) in epidemiological studies. Alternatively, it is possible that these associations are due to confounding by renal function, which could influence both As and creatinine excretion. Objectives: Our objectives were to determine (1) whether folic acid and creatine lower blood As in a mixed folate-deficient and replete population, (2) whether creatine lowers plasma total homocysteine (tHcys), (3) whether As exposure is associated with increased inflammation and decreased estimated glomerular filtration rate (eGFR), and whether these effects are greater in those with a more oxidized plasma glutathione redox potential (EhGSH), and (4) whether As metabolite proportions in urine and blood are associated with eGFR, and whether these associations may explain the relationship between As metabolite proportions and urinary creatinine. Methods: We addressed these objectives in five epidemiologic investigations of As-exposed Bangladeshi adults, employing data from a randomized placebo-controlled trial (the Folic Acid and Creatine Trial (FACT)) and two cross-sectional studies (the Nutritional Influences on Arsenic Toxicity (NIAT) study, and the Folate and Oxidative Stress (FOX) study). In the 24-week FACT study, participants were randomized to receive either placebo, 400 μg/day FA (FA400), 800 μg/day FA (FA800), 3 g/day creatine (Cr), or 3 g/day creatine + 400 μg/day FA (Cr+FA400). At week 12, half of the participants in the FA400 and FA800 groups were switched to placebo, while the other half continued their assigned supplements. Additionally, at week 12 participants in the Cr and Cr+FA400 groups were switched to placebo. In Chapter 4 (FACT), we examined whether FA400, FA800, Cr, or Cr+FA00 lowered blood As to a greater extent than placebo over the first 12 weeks of the trial, and whether a rebound in blood As occurred from week 12 to 24 related to cessation of FA supplementation. In Chapter 5 (FACT), we examined whether Cr or Cr+FA400 lowered plasma tHcys to a greater extent than placebo or FA400 alone, respectively, over the first 12 weeks of the trial. In Chapter 6 (NIAT), we examined the associations of water and urinary As with eGFR, and whether eGFR confounded the associations between urinary creatinine and the urinary %As metabolites; we also explored the associations of eGFR with the urinary %As metabolites. In Chapter 7 (FOX), we examined the associations of eGFR with the urinary and blood %As metabolites; we also examined whether the relationship between blood and urinary %As metabolites was decreased among those with reduced renal function. In Chapter 8 (FOX), we examined the associations of water, blood, and urinary As with markers of inflammation (C-reactive protein (CRP) and α-1 acid glycoprotein (AGP)), and eGFR, and investigated whether these associations were modified by the plasma EhGSH. Results: FA800 lowered blood As to a significantly greater extent than placebo over the 24 weeks of the FACT study, with no rebound in blood As related to cessation of FA supplementation. FA400, Cr, and Cr+FA400 did not lower blood As to a greater extent than placebo (Chapter 4). Cr and Cr+FA400 did not lower plasma tHcys to a greater extent than placebo or FA400 alone, respectively. However, in the Cr+FA400 group we observed a significant correlation between a decrease in plasma GAA over time and a decrease in plasma tHcys over time (Chapter 5). Total urinary As was marginally associated with a decrease in eGFR in the NIAT study, though water As was not. Additionally in the NIAT study, while eGFR did not confound the relationship between urinary creatinine and urinary %As metabolites, we observed a positive association between eGFR and u%InAs, and a negative association between eGFR and u%DMA (Chapter 6). Likewise in the FOX study, eGFR was positively associated with u%InAs and negatively associated with u%DMA; the associations of eGFR with the blood %As metabolites were in the same direction, although not statistically significant. We additionally observed that for a given increase in blood %InAs, the increase in urinary %InAs tended to be smaller in those with reduced renal function, compared to those with normal renal function (Chaper 7). In the FOX study we also observed the total blood As and urinary As were marginally associated with decreased eGFR, while water As was not. Water As, urinary As, and blood As were significantly positively associated with plasma CRP in those with low plasma GSH or a more oxidized plasma EhGSH (Chapter 8). Conclusions: Strategies to reduce risk for As-induced diseases are sorely needed, particularly due to barriers to As exposure removal and/or persistent elevated risk from past As exposure. Several susceptibility factors which can potentially be intervened upon have been discussed in this dissertation, namely folate nutritional status, redox status, and renal capacity to excrete As. Our finding that folic acid supplementation (800 μg/day) lowered blood As to a greater extent than placebo in a randomized trial indicates that improving the folate status of the general Bangladeshi population may reduce the body burden of As. Folate fortification of food in Bangladesh, in addition to potentially reducing risk for As-induced diseases, would have the additional benefit of substantially lowering the prevalence of HHcys. Our finding in a cross-sectional study that individuals with a more oxidized plasma glutathione redox potential were susceptible to As-induced inflammation may indicate that improving redox status can protect against As-induced inflammation. Randomized trials are needed to confirm a protective effect of antioxidants; upon confirmation, antioxidant dietary recommendations for As-exposed populations could potentially be implemented. Finally, our cross-sectional finding of a positive association between eGFR and urinary %InAs, and that eGFR modified the relationship between blood and urinary %InAs, suggests that InAs excretion may be impaired among individuals with reduced renal function. A decreased renal capacity to excrete InAs may lead to accumulation of InAs in tissues, and related health effects. Potential interventions related to renal function include treatment of risk factors for chronic kidney disease (e.g. blood pressure, blood glucose) in order to prevent onset of renal function deterioration, or to screen for chronic kidney disease in order to identify susceptible individuals and conduct directed interventions. Of these three susceptibility factors, the strongest evidence exists for the potential of folic acid to lower blood As. In Bangladesh, where As exposure and HHcys are widely prevalent, folate fortification should be considered a viable option for reducing risk for As- and Hcys-related diseases.

Análise proteômica da matriz do esmalte nos estágios de secreção e maturação em camundongos susceptíveis ou resistentes à fluorose dentária, expostos cronicamente ao fluoreto através da água de beber. Os mecanismos pelos quais a ingestão excessiva de fluoreto (F) durante a amelogênese levam à fluorose dentária ainda não são precisamente conhecidos. Tem sido demonstrado que determinadas linhagens de camundongos são mais susceptíveis que outras à fluorose dentária, o que faz destas linhagens o modelo ideal para se estudarem os fenômenos moleculares envolvidos nesta patologia. No presente estudo, foi empregada uma abordagem proteômica para avaliar alterações na expressão de proteínas da matriz do esmalte dentário nos estágios de secreção e maturação, em duas linhagens de camundongos com diferentes susceptibilidades à fluorose (A/J, susceptível e 129P3/J, resistente). Camundongos de ambos os gêneros, representantes das linhagens 129P3/J (n=200) e A/J (n=200) foram distribuídos em dois grupos para cada linhagem, que receberam ração com baixa concentração de F e água de beber contendo 0 (controle) ou 50 mg/L F por 6 semanas. A concentração de F foi analisada no plasma e no esmalte dos incisivos. Para a análise proteômica, foi realizada a raspagem da matriz do esmalte dos incisivos, nos estágios de secreção e maturação. Para a extração das proteínas do esmalte, foram pesados 15 mg de pó da matriz do esmalte, aos quais foi adicionado 1 mL de tampão de lise contendo uréia 7 M, tiouréia 2 M, CHAPS 4 %, DTT 1 %, anfólitos carreadores 0,5 % pH 3-10 e um coquetel de inibidores de proteases. As proteínas do esmalte extraídas para cada grupo foram separadas pela técnica de eletroforese bidimensional e posteriormente submetidas a LC-ESI-MS/MS. A concentração média (±DP) de F encontrada no plasma dos camundongos foi de 0,023±0,010 e 0,019±0,007 mg/L para os animais do grupo controle, das linhagens A/J e 129P3/J, respectivamente, e de 0,151±0,043 e de 0,252±0,060 mg/L de F para os animais das linhagens A/J e 129P3/J, respectivamente, tratados com água contendo 50 mg/L de F. A ANOVA a 2 critérios revelou que houve diferença significativa entre os tratamentos (F= 658,0, p<0,0001), mas não entre as linhagens (F=3,3 p=0,075), tendo havido interação significativa entre estes critérios (F=16,50, p=0,0002). Já a concentração média (±DP) de F incorporado no esmalte dos incisivos dos camundongos foi 471,4±215,8 mg/kg e 151,7±58,8 mg/kg para os animais do grupo controle das linhagens 129P3/J e A/J, respectivamente, e 2711,2±1019,2 mg/kg, 1756,9±921,6 mg/kg para os animais das linhagens 129P3/J e A/J, respectivamente, tratados com água contendo 50 mg/L de F. A ANOVA a 2 critérios encontrou diferença significativa entre as linhagens (F=11,36, p=0,0016) e entre os tratamentos (F=103,50, p<0,0001), sem interação significativa entre ambos (F=2,82, p=0,1004). Os resultados proteômicos mostraram redução na abundância de proteínas no estágio de maturação, quando comparado com o de secreção. Foi observado que o tratamento com F aumentou consideravelmente o número de spots proteicos detectados em ambos os estágios, sendo que este aumento foi maior para os animais da linhagem A/J, indicando uma tentativa de se combater os efeitos deletérios do F e reforçando a maior susceptibilidade aos seus efeitos desta linhagem. A identificação das proteínas com expressão diferencial revelou que tanto a linhagem quanto o tratamento com F levaram à expressão diferencial de proteínas pertencentes a todas as categorias funcionais. / The mechanisms by which excessive ingestion of fluoride (F) during amelogenesis leads to fluorosis are still not precisely known. It has been shown that certain strains of mice are more susceptible to dental fluorosis than others, which turns these strains the ideal model for studying the molecular phenomena involved in this pathology. In the present study, we employed a proteomic approach to identify and evaluate changes in protein expression of secretory and maturation-stage enamel matrix in two strains of mice with different susceptibilities to dental fluorosis (A/J, susceptible and 129P3/J, resistant). Mice of both genders, from 129P3/J (n=200) and A/J (n=200) strains were divided into two groups for each strain. They received a low-F diet and drinking water containing 0 (control) or 50 mg/L F for 6 weeks. The F concentration was analyzed in plasma and enamel incisors. For proteomic analysis, the enamel matrix of secretory and maturation stages (incisors) was scrapped. For the extraction of enamel proteins, 1 ml of lysis buffer containing 7 M urea, 2 M thiourea, 4% CHAPS, 1% DTT, 0.5% ampholytes carriers pH 3-10 and a cocktail of protease inhibitors was added to 15 mg of enamel matrix powder. The enamel proteins extracted for each group were separated by two-dimensional electrophoresis and subsequently subjected to LC-ESIMS/ MS. The mean (± SD) F concentrations found in plasma were 0.023 ± 0.010 and 0.019 ±0.007 mg/L for the control group, A/J and 129P3/J strains, respectively; and 0.151 ± 0.043 and 0.252 ± 0.060 mg/L F for A/J and 129P3/J mice, respectively, treated with water containing 50 mg/L F. Two-way ANOVA revealed significant differences between treatments (F = 658.0, p <0.0001), but not between strains (F = 3.3 p = 0.075), with was significant interaction between these criteria (F = 16.50, p = 0.0002). The mean (± SD) F concentrations in the enamel of the incisors were 471.4 ± 215.8 mg/kg and 151.7 ± 58.8 mg/kg for the control group of 129P3/J and A/J strains, respectively; and 2711.2 ± 1019.2 mg/kg and 1756.9 ± 921.6 mg/kg for 129P3/J and A/J mice, respectively, treated with water containing 50 mg/L F. Two-way ANOVA detected significant differences between the strains (F=11.36, p=0.0016) and between treatments (F=103.50, p <0.0001), without significant interaction between these criteria (F=2.82, p=0.1004). The proteomic results revealed a reduction in the abundance of proteins in the maturation stage, as compared with the secretory stage. Treatment with F greatly increased the number of protein spots detected in both stages. This increase was greater for A/J mice, indicating an attempt to fight the deleterious effects of F and, thus, reinforcing the susceptibility of this strain to the effects of F. The identification of differentially expressed proteins revealed that both the strain and the treatment with F led to differential expression of proteins belonging to all functional categories.

<p><a>This dissertation focused on better understanding the fundamental processes that control organic and inorganic contaminant interaction with plastic plumbing pipes. Plastic pipes are increasingly being installed for drinking water plumbing, but their role in affecting drinking water quality has received little study. It is well-known that plastic pipes can sorb and release organic contaminants and be difficult to decontaminate. Several problems were identified in the literature and through discussions with industry: (1) Past guidance issued to communities affected by petroleum contaminated water does not seem to specifically consider plastic plumbing pipe remediation, (2) investigators have also identified heavy metals can accumulate on pipe inner walls, (3) Others have proposed certain heavy metals can catalyze plastic water pipe degradation, (4) No nondestructive cleaning methods were found for removing metal scales from plastic pipes.</a> These topics were a basis for studies conducted because lack of information inhibits greater protection of public health, safety, and welfare.</p> This dissertation involved the application of knowledge and techniques from the environmental engineering and science, polymer engineering, and material science disciplines. Chapter 1 focused on the response of copper and plastic pipes (i.e., chlorinated polyvinylchloride (cPVC), high-density polyethylene (HDPE), crosslinked polyethylene (PEX)) exposed to petroleum contaminated drinking water. Bench-scale results revealed that pipe rinsing followed by a single 3 day water stagnation period removed target monoaromatic hydrocarbons (MAH) from copper pipes, but much longer (<u>></u>15 days) time was required for decontaminating cPVC, HDPC, and PEX pipes. Benzene, trimethylbenzene and polynuclear aromatic hydrocarbons, some of which are not typically considered in drinking water contamination investigations, were found desorbed into clean drinking water from pipes. Future plumbing decontamination guidance should consider the conditions necessary for plastic pipe remediation. Chapter 2 describes the influence of drinking water conditions on heavy metal contaminant – low density polyethylene (LDPE) pellet surface interactions. Mixed metal drinking water solutions were applied and contained Cu, Fe, Mn, Pb and Zn at 30 µg/L. LDPE was selected as the model polymer because of its prior use for piping in Europe, use in bench-scale studies by others, and similarity to products used for the manufacture of more complex materials in the USA (HDPE, PEX). As expected, metal loadings were about 5 times greater for aged LDPE pellets suspended in solution compared to new LDPE pellets. This difference was attributed to the aged plastic surfaces having oxygen containing functional groups, increased surface area, and enhanced hydrophilicity. Metal loading was lower at pH >9.5 and in the presence of dissolved organic contaminants. The presence of free chlorine and corrosion inhibitor also decreased metal adsorption onto LDPE pellets. These factors likely enabled metal precipitation thereby not allowing metal species to adsorb to LDPE pellets suspended in water. XPS results showed deposited metals (i.e., Cu, Pb, Zn) primarily consisted of hydroxides and oxides. To further understand heavy metal – plastic pipe interactions, Chapter 3 involved the use of metal and plastic pipe rigs and exhumed PEX plumbing pipes. Exhumed cold and hot water PEX pipes contained a noticeable amount of heavy metals (i.e., most abundant metals were 2049 mg/m² Fe, 400 mg/m² Ca, 438 mg/m² Zn and 150 mg/m² P). Metal release and deposition onto PEX pipe was examined using bench-scale pipe rigs that contained new PEX pipe, brass valves, and copper pipe. Two water matrices (pH 4 and 7.5) and two temperatures (23^oC and 55^oC) were explored. The pH 4 water often accelerated metal leaching from brass valves, and a greater amount of heavy metals deposited on PEX pipes at high water pH and temperature (pH 4 and 55^oC) conditions. Oxygen containing functional groups were detected on PEX pipes connected to a brass valve or a brass valve combined copper pipe, but were not found on PEX pipe only (controls) samples, indicating that certain configurations may facilitate plastic pipe degradation. The last chapter describes the ability of a new lignin derived ligand to remove metal deposits from exhumed PEX plumbing pipes. When the ligand concentration was ≥ 5mM, more than 95% of sorbed metals (i.e., Cu, Fe, Mn, Pb and Zn) were removed. The ligand favored certain metals over others (Cu > Zn > Fe > Mn > Pb) and heavy metal removal mechanisms were proposed. This dissertation provides insights into the role of plastic pipes on drinking water quality. As plastic pipes continue to be installed, it is in the interest of public health, welfare, and safety to understand their role in positively and negatively affecting drinking water safety.

Neste projeto de pesquisa avaliou-se a etapa de filtração no processo de tratamento de água para abastecimento público. Para isto, foi utilizado um sistema de filtração piloto composto por quatro filtros rápidos por gravidade de camada profunda. Os filtros piloto foram alimentados com água decantada da Estação de Tratamento de Água Rio Grande, e operados com taxa de filtração de 500 m3/m2/dia. A concepção dos filtros variou em termos de material filtrante (areia e antracito), diâmetro dos grãos e altura do leito. Os filtros foram avaliados em termos de turbidez, contagem de partículas, evolução de perda de carga e velocidade ascensional de água de lavagem. Na Etapa 1, operando-se filtros de areia e antracito com diferentes diâmetros, o filtro de antracito com 1,3 mm de diâmetro e 120 cm de altura apresentou melhor comportamento no tocante aos parâmetros avaliados. Na etapa 2, comparando-se filtros de areia e de antracito com mesmo diâmetro (1,3 mm) e altura de leito (120 cm), mais uma vez o filtro de antracito foi superior. Acredita-se que os índices físicos justifiquem esse comportamento. Na Etapa 3, conclui-se que o aumento de altura de leito dos filtros de areia (1,3 mm) e antracito (1,3 mm) de 120 cm para 160 cm foi benéfico para ambos os materiais filtrantes em termos de qualidade do efluente, mas muito mais significativo para o antracito, e não se observou alteração de comportamento no tocante à evolução de perda de carga. Com o ensaio de fluidificação e expansão do leito filtrante, conclui-se que, considerando-se o mesmo tempo de duração da lavagem e a mesma expansão do leito, o filtro de antracito possibilitou a utilização de menor velocidade ascensional de água de lavagem, que representa grande economia com relação aos custos do sistema de lavagem. Assim, em todos os aspectos estudados, o uso de antracito (1,3 mm) como material filtrante para filtros rápidos por gravidade de camada profunda se mostrou mais vantajoso. / This project researched the filtration stage in the water treatment process for public use. The research used a pilot filtration system based on four rapid gravity depth bed filters, with a filtration rate of 500m3/m2/dia. The water used in the experiment came from sedimentation tank of the Rio Grande water treatment facility. During the experimental phase the filters were loaded with different depth, used different filter media (sand and anthracite) and used grain with different effective size. The filters were evaluated in terms of turbidity, particle count, head loss and superficial velocity of backwashing water. In the first part of the study, when analyzing the results of filters loaded to a depth of 120 cm using both sand and anthracite with different size, the anthracite filter with effective size of 1.3 mm was the one with the best results. In the second part of the study, when comparing anthracite and sand with same the effective size, the anthracite also presented better results. Finally when increasing the depth of the filter, both sand and anthracite filters showed improved performance in terms of effluent quality, but anthracite filters kept outperforming sand filters. In both case, there were no evidences of changing in the head loss development. When performing fluidization and expansion experiments, considering the same backwashing cycle time and expansion of filter media, the anthracite filter allowed lower superficial velocity which represents relevant economies in the washing system costs. Therefore the use of anthracite (1.3mm) as a filter medium for rapid gravity depth bed filters is recommended.

Novas tecnologias para o tratamento de água potável vêm sendo empregadas na medida em que a utilização de sais de alumínio tem apresentado correlação com doenças de envelhecimento mental nos seres humanos. Os coagulantes orgânicos de origem vegetal podem substituir de forma satisfatória estes sais no tratamento convencional de água potável. A utilização de processos combinados utilizando membranas de ultrafiltração com coagulação é uma alternativa aos métodos convencionais de potabilização. Com este cenário, o presente trabalho tem como objetivo comparar o desempenho operacional de uma planta piloto de ultrafiltração com membranas submersas para produção de água potável a partir do Lago Guaíba, utilizando o coagulante convencional poli (cloreto de alumínio) (PAC) e um coagulante orgânico oriundo da casca da Acácia Negra (Acacia maernsii) Tanfloc SG, com a análise da morfologia, massa molar de corte e permeabilidade hidráulica da membrana e com análises da água bruta e filtrada. As membranas de fibra oca de Poliéter Sulfona (PES) com massa molar de corte de 50 kDa, permearam sob pressão fixa de -500 mbar, com ação de borbulhamento em testes de 140 horas para avaliação da performance e testes de 10 horas para avaliação da qualidade de permeado. Os resultados indicaram semelhança no desempenho operacional dos dois coagulantes quanto à redução da permeância hidráulica relativa, e a qualidade do permeado indicou que mesmo com a ausência de flocos no tanque de alimentação, não houve passagem significativa de coagulante para o permeado. Os parâmetros de potabilidade indicaram o enquadramento da água produzida nos padrões organolépticos na atual Portaria 2914/2011 do Ministério da Saúde. / New technologies to water treatment have been applied as the aluminum salts commonly used have shown correlations with mental diseases in human beings. The organic coagulants from natural sources can satisfactorily replace those inorganic salts in drinking water treatment. The hybrid processes join ultrafiltration membranes with coagulation are alternatives to the standard potabilization. The present study compares the operational behavior of a submersed ultrafiltration (UF) pilot plant producing drinking water from Guaíba Lake, using poli (aluminum chloride) (PAC) and an organic coagulant extracted from Acacia maernsii Tanfloc SG. The membrane and the permeate were investigated. The polyether sulfone hollow fiber membranes filtered with a -500 mbar constant vacuum and air bubbles through 140 hours for performance test and for 10 hour for permeate quality verification. The results showed similarity of the relative hydraulic permeability of the two coagulants, and even with the absence of visible flocs in the membrane tank, there were no significant coagulant carryover through the membrane. The analytical data pointed that the water produced with both coagulants had concentration bellow the Brazilian organoleptic standards, according to the Portaria 2914/2011 of the Health Ministry.

Este trabalho apresenta a aplicação da Cromatografia Líquida de Ultra Performance acoplada à espectrometria de massas (UPLC-MS/MS) como uma técnica analítica em potencial para a determinação de contaminantes orgânicos em amostras de água para consumo humano. A técnica foi aplicada no desenvolvimento de um método analítico para a determinação de 28 praguicidas listados na Portaria 2914/11 como indicadores da qualidade de águas para o consumo humano. O método analítico apresentou limite de quantificação (LQ) (entre 0,2 e 50 g L-1, considerando todas as substâncias investigadas) capaz de monitorar as substâncias de interesse em concentrações inferiores aos limites máximos permitidos pela legislação, com taxas de recuperação superiores a 80% e coeficiente de variação (CV) menor do que 15% no nível de &#181;g L-1. A filtração da amostra, empregando filtros de seringa de 0,22µm de diâmetro de poro, foi empregada como etapa de preparo de amostra, não sendo necessário o emprego de métodos de extração e concentração da amostra previamente à análise. O método analítico proposto foi aplicado em duas amostras de água potável coletadas na cidade de Paulínia-SP; entretanto, os praguicidas investigados não foram detectados em ambas as amostras analisadas. Adições de padrão foram realizadas sobre as amostras no nível de concentração do Valor Máximo Permitido (VMP) e três vezes o VMP pela Portaria 2914/11. Valores de recuperação entre 80 e 120% foram obtidos, demostrando a aplicabilidade e exatidão do método proposto. / This work describes the application of Ultra Performance Liquid Chromatography tandem mass spectrometry (UPLC-MS/MS) for determination of organic contaminants in drinking water. The tecnique was used for the development of an analytical method for the determination of 28 pesticides, listed in the Brazilian Administrative Rule 2914/11, these compounds are considered as quality indicators for drinking waters. The limit of quantification (LQ) of the analytical method was between 0,1 e 5 &#181;g L-1 for all target substances, being able to quantify the target substances at concentrations lower than the maximum levels of contamination (MLC) established by the Rule, with accuracy above 80% and relative standard deviation below 15%, at g L-1 level. The filtration of the sample, using 0.22 µm syringe filters, was applied as sample preparation step. The analytical method based on UPLCMS/MS was used to analyze two drinking water samples collected in Paulínia-SP city. The target pesticides were not detected in any samples. The two samples were then enriched with analytical standards of the pesticides at the MLC and 3 times the MLC levels and analyzed by the proposed method. Recoveries ranged from 80 to 120%, showing the applicability and efficiency of the proposed analytical method.

Este trabalho teve por objetivos estudar a distribuição das concentrações de atividade dos isótopos de rádio de meias-vidas longas, 226Ra e 228Ra, em amostras de águas minerais coletadas no Balneário de Caxambu (MG) e no Balneário de Águas de Lindóia (SP). Foram observadas concentrações de atividade de 228Ra relativamente aumentadas em relação às de 226Ra nas águas minerais estudadas no Balneário de Caxambu. As concentrações elevadas de carbonatos e bicarbonatos destas águas podem resultar em um conseqüente aumento da solubilidade dos isótopos de Ra e pode ter um papel importante para a distribuição do 228Ra e para as reações de equilíbrio entre as fases sólida e líquida das soluções. No Balneário de Caxambu, as concentrações de atividade médias aritméticas variaram de 83 mBq L-1 a 3599 mBq L-1 e de 60 mBq L-1 a 4481 mBq L-1 para 226Ra e 228Ra, respectivamente. O maior valor de atividade de 226Ra foi observado nas águas da Fonte Venâncio, enquanto que a concentração máxima de 228Ra foi determinada na Fonte Ernestina Guedes. As razões de atividade 228Ra/ 226Ra variaram de 0,079 (Fonte Conde DEau e Princesa Isabel) a 4,2 (Fonte Mairink II). Em Águas de Lindóia as concentrações de atividade médias aritméticas variaram de 4,6 mBq L-1 a 41 mBq L-1 e de 30 mBq L-1 a 54 mBq L-1 para 226Ra e 228Ra, respectivamente. O maior valor de atividade de 226Ra foi observado nas águas da Fonte Engarrafada São Jorge, enquanto que a concentração máxima de 228Ra foi determinada na Fonte Santa Filomena (torneira pública 2). As razões de atividade 228Ra/ 226Ra variaram de 1,2 (Fonte Engarrafada São Jorge) a 9,1 (Fonte Engarrafada Jatobá 1). A exposição de indivíduos do público à radiação natural em virtude do consumo das águas minerais também foi avaliada neste trabalho. As doses efetivas foram estimadas utilizando-se um modelo dosimétrico conservativo, e integrando-se os resultados ao longo de 70 anos de vida de um indivíduo adulto, após a incorporação de 226Ra e 228Ra. Os resultados desta avaliação radiossanitária demonstraram que o nível de referência de dose efetiva comprometida recomendado pela Organização Mundial de Saúde de 0,1 mSv a-1 foi ultrapassado em quase todas as fontes de Caxambu, exceto para a Fonte Viotti, Fonte Dom Pedro e Fonte Dona Leopoldina. Em Águas de Lindóia e Lindóia as maiores doses efetivas comprometidas obtidas foram 8,4 10-3 mSv a-1 para o 226Ra (Fonte engarrafada São Jorge) e 2,6 10-2 mSv a-1 para o 228Ra (Fonte Santa Filomena torneira pública 2). Estes valores são menores que o limite recomendado pela Organização Mundial de Saúde. Doses efetivas comprometidas de até 7,4 x 10-1 mSv a-1 para o 226Ra (Fonte Venâncio, Caxambu) e 2,2 mSv a-1 para o 228Ra (Fonte Ernestina Guedes, Caxambu) foram estimadas no presente trabalho. No caso do 226Ra, este valor representa menos que 31% da dose efetiva média anual atribuída a radioatividade natural. Contudo, no caso do 228Ra, o limite anual de dose efetiva comprometida recomendado pela ICRP (considerando-se todas as fontes de exposição da população mundial à radiação) foi excedido não só na Fonte Ernestina Guedes, mas também na Fonte Beleza. / The aim of this work was to study the long-lived Ra isotopes, 226Ra and 228Ra, natural distribution in mineral and spring waters from Caxambu (MG) and Águas de Lindóia (SP) waterparks. In Caxambu mineral waters it was observed 228Ra acitivity concentrations slightly higher than those of 226Ra. The elevated content of carbonates and bicarbonates of these waters can result in an increased solubility of the both Ra isotopes and may play an important role for the fate of 228Ra and its equilibrium distribution between solid and liquid phases. In Caxambu Thermal Spa, arithmetic mean activities ranged from 83 mBq L-1 to 3599 mBq L-1 and from 60 mBq L-1 to 4481 mBq L-1 for 226Ra and 228Ra, respectively. The highest 226Ra activity was found in Venancio Spring, while the maximum 228Ra activity value was determined in Ernestina Guedes. 228Ra/ 226Ra activity ratios varied from 0.079 (Conde DEau and Princesa Isabel Spring) to 4.2 (Mairink II Spring). In Águas de Lindóia, arithmetic mean activities ranged from 4.6 mBq L-1 to 41 mBq L-1 and from 30 mBq L-1 to 54 mBq L-1 for 226Ra and 228Ra, respectively. The maximum 226Ra activity concentration was found in the bottled mineral water São Jorge, while the higher 228Ra activity concentration was determined in Santa Filomena Spring (public station 2). 228Ra/ 226Ra activity ratios varied from 1.2 (bottled mineral water São Jorge) to 9.1 (bottled mineral water Jatobá 1). This work also performed the dose assessment due to the ingestion of 226Ra and 228Ra in Caxambu and Águas de Lindóia mineral and spring waters. The committed effective doses were estimated by using a conservative dosimetric model and taking into account the results over a lifetime (70 years) following intake of both long-lived Ra isotopes. The results from this radiological evaluation showed that the guindance committed effective dose level of 0.1 mSv y-1 recommended by World Health Organization was exceeded in almost all samples studied in Caxambu, except for Viotti Spring, Dom Pedro Spring and Dona Leopoldina Spring. In Águas de Lindóia and Lindóia, the highest committed effective doses estimated were 8.4 10-3 mSv y-1 for the intake of 226Ra (bottled mineral water São Jorge) and 2.6 10-2 mSv y-1 for 226Ra (Santa Filomena spring station 2). Both values are below the limit recommended by World Health Organization. The maximum commited effective doses per year obtained in this work were 7.4 10-1 mSv y-1 for 226Ra (Venancio Spring) and 2.2 mSv y-1 for 228Ra (Ernestina Guedes Spring). Considering the case of 226Ra intake via mineral water, the dose obtained represents less than 31 % of the average effective dose attributable annually from natural background radiation. However, in the case of 228Ra the annual committed effective dose limit recommended by ICRP (considering all sources of radiation exposure for the world population) was exceeded not only in Ernestina Guedes Spring, but also in Beleza Spring.

A represa Billings é o maior manancial superficial do Estado de São Paulo cuja importância está ligada ao abastecimento público, à geração de energia, à pesca, à recreação e ao lazer para a cidade de São Paulo e os municípios da sua região metropolitana. Nos últimos anos essa região vem sofrendo grande impacto ambiental. Apesar de ser uma APA (Área de Proteção Ambiental), há no entorno da represa, vários tipos de assentamentos cujas famílias utilizam para o seu consumo a água proveniente de poços situados, muitas vezes, a poucos metros da represa, já que inexiste o acesso à rede de saneamento básico (tratamento de água e esgoto em rede pública). De acordo com relatórios de entidades governamentais, observa-se que a espécie química alumínio está presente nas águas da represa em valores acima do permitido, o que gera preocupações relacionadas à contaminação do meio ambiente e à saúde da população; por outro lado, há poucas informações sobre a qualidade das águas subterrâneas da região. Considerando-se essa deficiência de informações, este trabalho teve como objetivo investigar a possível contaminação de poços, partindo da aplicação de um programa criado o PAMQUÁ ® - que auxiliou e direcionou à tomada de decisão a um determinado contaminante de risco à saúde humana encontrado na água e como o uso da radiação ionizante pôde ser aplicada no beneficiamento de diagnóstico químico e em solução para tratamento específico. Dessa forma, pôde-se ter o respaldo de que a espécie química alumínio é o principal contaminante daquelas águas superficiais. Como os íons alumínio são susceptíveis à complexação por substâncias orgânicas, o processo de irradiação ionizante como etapa de pré-tratamento para a determinação analítica foi um processo inovador e que foi aplicado em dois tipos de amostra: 1) amostras de água padronizadas contendo ácido húmico, que é o tipo de matéria orgânica que ocorre com frequência em águas subterrâneas e 2) amostras de água coletadas dos poços da região estudada. O processo de irradiação permitiu a redução do teor de matéria orgânica e a mineralização dessas amostras, contribuindo com dados inéditos sobre o teor de alumínio. Finalmente, foi desenvolvido um novo material - uma membrana polimérica seletiva modificada por radiação que propõe a remediação do alumínio na água. / The Billings dam is the largest source of water in São Paulo state, whose its importance to São Paulo city and its metropolitan region is closely linked to the public water supply, power generation, fisheries, recreation and leisure. In recent years, the dam region has suffered high environmental impact. Although it is an EPA (Environmental Protection Area), there are in dam surroundings several types of settlements, whose families use water from wells often located a few meters from the dam, once does not have their access to the sanitation (public water and sewage treatment). In accordance to the reports of governmental entities, the aluminum is present in the dam water and its concentration exceeds the permissible values, which raises concerns related to contamination of the environment and the health of the population; by the other side, no information exists about the ground water quality in this region. Considering this deficit of information, the main goal of this work was the investigation of ground water of a potential contamination, based on a new program PAMQUÁ ® - which supported and drove the decision making of a specific contaminant with risk to human health found in water and how the use of ionizing radiation can be applied for processing of chemical diagnose and for specific treatment solution. By this way, it was possible to have support that the chemical specie of aluminum is the main contaminant of that surface water. As aluminum ions are susceptible to organic matter complexation, the ionizing irradiation process applied as pre-treatment step in an analytical determination was an innovative procedure and it covered two kinds of sample: 1) standard water samples containing humic acid, that is the more common type of organic matter in ground water and 2) natural water samples from wells of studied region. The irradiation process allowed the decreasing of the organic matter levels and the mineralization of these water samples contributing with unpublished data about the contents of aluminum. Finally, a new material was developed a selective polymeric membrane modified by radiation that suggests the aluminum mitigation in water.

Advanced monitoring of water quality in order to perform a real-time hazard analysis prior to Water Treatment Works (WTW) is more of a necessity nowadays, both to give warning of any contamination and also to avoid downtime of the WTW. Downtimes could be a major contributor to risk. Any serious accident will cause a significant loss in customer and investor confidence. This has challenged the industry to become more efficient, integrated and attractive, with benefits for its workforce and society as a whole. The reality is that water companies are not yet prepared to invest heavily in trials, before another company announces its success in implementing a new monitoring strategy. This has slowed down the development of the water industry. This research has taken the theoretical idea that the use of advanced online monitoring technique in the water industry would be beneficial and a step further; demonstrating by means of a state-of-the-art assessment, usability trials, case studies and demonstration that the barriers to mainstream adoption can be overcome. The findings of this work have been presented in four peer-reviewed papers. The research undertaken has shown that Turbidity levels in rivers can be measured from the rivers' mean flow rate, using either Doppler Ultrasound device for real-time readings or based on past performance history. In both cases, the Turbidity level can also help estimate both the Colour and Conductivity levels of the subject river. Recalibration of the equations used is a prerequisite as each individual river has its own unique "finger print".