Diabetic cardiomyopathy is one of the causes of mortality and morbidity associated with diabetes. Diabetes is a disorder characterised by chronic hyperglycaemia and cardiovascular complications. The relationship between these integrally linked conditions has long been recognised, and for a significant portion of individuals the two conditions co-exist as part of metabolic syndrome. The presence of diabetes increases the risk of heart failure up to fivefold and three-fold in women and men, respectively, when compared to individuals without diabetes. While there has been a significant declining trend in cardiovascular mortality and morbidity in the general population over the past two decades, unfortunately such trends have not been seen among diabetic patients. As a result, this has persuaded many health professionals to re-evaluate their current treatment and pharmacological regimens. It is a well established fact that oxidative stress is a contributory mechanism in many agerelated disorders including T2DM, especially in those with poor glycaemic control. Thus far, clinical trials with antioxidant or carbonyl-trapping agents have produced mixed results, suggesting that the mechanisms underlying this disorder may be more complex than previously thought. Although altered systemic regulation of trace metals in diabetes has been previously investigated, it is still unclear whether changed trace metal metabolism would cause heart disease in common forms of diabetes and whether metal chelation can reverse this condition. Our hypothesis is that the accumulation of redox-active trace metals including Cu and Fe in cardiac muscle may, at least in part, result in cardiomyopathy through the generation of excess reactive oxygen species. We believed that the administration of a specific metal chelator should ameliorate this process by increasing the excretion of free systemic Cu and Fe, consequently limiting the production of superoxide oxygen free radicals and arresting the process of diabetic cardiomyopathy. Data from pre-clinical studies conducted in our laboratory using diabetic animal model with diabetes-induced abnormal Cu metabolism have been remarkably consistent in demonstrating that oral dosing with triethylenetetramine (TETA) can effectively remove systemic Cu via increased urinary Cu excretion, improve cardiomyocyte structure, reverse elevations in left ventricular collagen and β1-integrin, and alleviate heart failure, all in the presence of a consistently high circulating blood glucose profile. Taken together, these findings support the beneficial role of TETA in diabetic animal model and lay the foundation for its potential therapeutic effect in humans with diabetes. This thesis describes a series of randomised, placebo-controlled clinical trials that have investigated the metabolism of Cu and Fe and seven other trace metals in patients with chronic T2DM compared with non-diabetic control subjects. This thesis also examines the mechanism of action of TETA and addresses the hypothesis that a decrease in body systemic Cu pool through chelation therapy may improve cardiac complication in diabetic subjects. Trial 1 is a randomised, double-blind, placebo- and diet-controlled study which measured the 6d balance of Cu and Fe and seven other essential trace metals, in twenty male T2DM and twenty age-matched control subjects in whom we later probed systemic metal balance with oral TETA. Basal urinary output and balance of Cu and Fe was significantly elevated in diabetes, and the two output values correlated strongly (p<0.05). 6d treatment with 2400mg/d dose of TETA (maximum Wilson’s disease dose) has increased the urinary excretion of Cu, which was predicted by basal urinary Cu excretion, thereby causing a positive Cu balance to become negative in diabetes. Regulation of Cu metabolism was shown to be abnormal in diabetes and was selectively modified by TETA, which did not concomitantly modify Fe metabolism. Moreover, TETA did not cause a negative balance in any of the other seven trace metals monitored. These findings are consistent with TETA reversing the accumulation of free systemic Cu in diabetes, which may help to explain its potential therapeutic effects in some diabetic complications. Trial 2 investigated the acute response effect of a single 2400mg dose of TETA on urinary and serum trace metals in the first 10hr and 10~24hr post-dose. The results showed that TETA markedly increased the urinary Cu and Zn excretion in diabetes for the duration of 10hrs with the maximum excretion phase between 4~6hr post-drug (p<0.05). TETA did not change the metabolism of Mg and six other essential trace metals monitored. Trial 3 examined the dose-response effect of TETA, at and below the dose given to patients with the Wilson’s disease over a 7d period, on Cu and eight other trace metals in a subgroup of seven T2DM and seven control subjects who had completed trial 1. The results of this i i trial showed that there was a linear dose-response relationship over the dose range 300~2400 mg/d on urinary Cu excretion in both T2DM and control subjects. However, there was no significant difference between the two subject groups at any of the four doses tested. In addition, 300mg/d of TETA was effective in mobilizing Cu in both T2DM and healthy control subjects. Trial 4 described the full work-up of a sensitive LC-MS methodology to identify and quantify TETA and its metabolite(s) in human urine. Using the LC-MS, TETA metabolism and excretion was investigated by analysing the urine of seven T2DM and seven control subjects who received escalating doses of TETA (samples obtained from trial 3). I have successfully identified and characterised two major metabolites of TETA in the urine of both T2DM and control subjects, N1-monoacetytriethylenetetramine (MAT) and diacetytriethylenetetramine (DAT), the latter which has not been previously reported. The results from urinary TETA excretion analyses also showed that T2DM may metabolise TETA more extensively than control subjects, which in turn is associated with its higher uptake or bioavailability. Urinary Zn excretion was mainly linked with urinary TETA and MAT in T2DM and healthy controls, respectively, whereas urinary Cu excretion was associated with urinary TETA excretion in healthy controls and urinary TETA+MAT excretion in T2DM subjects. These results suggest that MAT may also be involved in the mechanism by which TETA extracts systemic free Cu in diabetes. The identification of the two major metabolites of TETA and the development of a robust analytical LC-MS methodology reported in this study is an important step to further investigate the pharmacological actions of TETA in diabetic individuals. Collectively, the results presented in this thesis and in association with previous animal and clinical studies from our laboratory have provided consistent supporting evidences for the use of TETA clinically as a safe and effective therapy to prevent the genesis of some diabetic complications, in conjunction with conventional complication modifying therapies.

Diabetic cardiomyopathy is one of the causes of mortality and morbidity associated with diabetes. Diabetes is a disorder characterised by chronic hyperglycaemia and cardiovascular complications. The relationship between these integrally linked conditions has long been recognised, and for a significant portion of individuals the two conditions co-exist as part of metabolic syndrome. The presence of diabetes increases the risk of heart failure up to fivefold and three-fold in women and men, respectively, when compared to individuals without diabetes. While there has been a significant declining trend in cardiovascular mortality and morbidity in the general population over the past two decades, unfortunately such trends have not been seen among diabetic patients. As a result, this has persuaded many health professionals to re-evaluate their current treatment and pharmacological regimens. It is a well established fact that oxidative stress is a contributory mechanism in many agerelated disorders including T2DM, especially in those with poor glycaemic control. Thus far, clinical trials with antioxidant or carbonyl-trapping agents have produced mixed results, suggesting that the mechanisms underlying this disorder may be more complex than previously thought. Although altered systemic regulation of trace metals in diabetes has been previously investigated, it is still unclear whether changed trace metal metabolism would cause heart disease in common forms of diabetes and whether metal chelation can reverse this condition. Our hypothesis is that the accumulation of redox-active trace metals including Cu and Fe in cardiac muscle may, at least in part, result in cardiomyopathy through the generation of excess reactive oxygen species. We believed that the administration of a specific metal chelator should ameliorate this process by increasing the excretion of free systemic Cu and Fe, consequently limiting the production of superoxide oxygen free radicals and arresting the process of diabetic cardiomyopathy. Data from pre-clinical studies conducted in our laboratory using diabetic animal model with diabetes-induced abnormal Cu metabolism have been remarkably consistent in demonstrating that oral dosing with triethylenetetramine (TETA) can effectively remove systemic Cu via increased urinary Cu excretion, improve cardiomyocyte structure, reverse elevations in left ventricular collagen and β1-integrin, and alleviate heart failure, all in the presence of a consistently high circulating blood glucose profile. Taken together, these findings support the beneficial role of TETA in diabetic animal model and lay the foundation for its potential therapeutic effect in humans with diabetes. This thesis describes a series of randomised, placebo-controlled clinical trials that have investigated the metabolism of Cu and Fe and seven other trace metals in patients with chronic T2DM compared with non-diabetic control subjects. This thesis also examines the mechanism of action of TETA and addresses the hypothesis that a decrease in body systemic Cu pool through chelation therapy may improve cardiac complication in diabetic subjects. Trial 1 is a randomised, double-blind, placebo- and diet-controlled study which measured the 6d balance of Cu and Fe and seven other essential trace metals, in twenty male T2DM and twenty age-matched control subjects in whom we later probed systemic metal balance with oral TETA. Basal urinary output and balance of Cu and Fe was significantly elevated in diabetes, and the two output values correlated strongly (p<0.05). 6d treatment with 2400mg/d dose of TETA (maximum Wilson’s disease dose) has increased the urinary excretion of Cu, which was predicted by basal urinary Cu excretion, thereby causing a positive Cu balance to become negative in diabetes. Regulation of Cu metabolism was shown to be abnormal in diabetes and was selectively modified by TETA, which did not concomitantly modify Fe metabolism. Moreover, TETA did not cause a negative balance in any of the other seven trace metals monitored. These findings are consistent with TETA reversing the accumulation of free systemic Cu in diabetes, which may help to explain its potential therapeutic effects in some diabetic complications. Trial 2 investigated the acute response effect of a single 2400mg dose of TETA on urinary and serum trace metals in the first 10hr and 10~24hr post-dose. The results showed that TETA markedly increased the urinary Cu and Zn excretion in diabetes for the duration of 10hrs with the maximum excretion phase between 4~6hr post-drug (p<0.05). TETA did not change the metabolism of Mg and six other essential trace metals monitored. Trial 3 examined the dose-response effect of TETA, at and below the dose given to patients with the Wilson’s disease over a 7d period, on Cu and eight other trace metals in a subgroup of seven T2DM and seven control subjects who had completed trial 1. The results of this i i trial showed that there was a linear dose-response relationship over the dose range 300~2400 mg/d on urinary Cu excretion in both T2DM and control subjects. However, there was no significant difference between the two subject groups at any of the four doses tested. In addition, 300mg/d of TETA was effective in mobilizing Cu in both T2DM and healthy control subjects. Trial 4 described the full work-up of a sensitive LC-MS methodology to identify and quantify TETA and its metabolite(s) in human urine. Using the LC-MS, TETA metabolism and excretion was investigated by analysing the urine of seven T2DM and seven control subjects who received escalating doses of TETA (samples obtained from trial 3). I have successfully identified and characterised two major metabolites of TETA in the urine of both T2DM and control subjects, N1-monoacetytriethylenetetramine (MAT) and diacetytriethylenetetramine (DAT), the latter which has not been previously reported. The results from urinary TETA excretion analyses also showed that T2DM may metabolise TETA more extensively than control subjects, which in turn is associated with its higher uptake or bioavailability. Urinary Zn excretion was mainly linked with urinary TETA and MAT in T2DM and healthy controls, respectively, whereas urinary Cu excretion was associated with urinary TETA excretion in healthy controls and urinary TETA+MAT excretion in T2DM subjects. These results suggest that MAT may also be involved in the mechanism by which TETA extracts systemic free Cu in diabetes. The identification of the two major metabolites of TETA and the development of a robust analytical LC-MS methodology reported in this study is an important step to further investigate the pharmacological actions of TETA in diabetic individuals. Collectively, the results presented in this thesis and in association with previous animal and clinical studies from our laboratory have provided consistent supporting evidences for the use of TETA clinically as a safe and effective therapy to prevent the genesis of some diabetic complications, in conjunction with conventional complication modifying therapies.

Diabetic cardiomyopathy is one of the causes of mortality and morbidity associated with diabetes. Diabetes is a disorder characterised by chronic hyperglycaemia and cardiovascular complications. The relationship between these integrally linked conditions has long been recognised, and for a significant portion of individuals the two conditions co-exist as part of metabolic syndrome. The presence of diabetes increases the risk of heart failure up to fivefold and three-fold in women and men, respectively, when compared to individuals without diabetes. While there has been a significant declining trend in cardiovascular mortality and morbidity in the general population over the past two decades, unfortunately such trends have not been seen among diabetic patients. As a result, this has persuaded many health professionals to re-evaluate their current treatment and pharmacological regimens. It is a well established fact that oxidative stress is a contributory mechanism in many agerelated disorders including T2DM, especially in those with poor glycaemic control. Thus far, clinical trials with antioxidant or carbonyl-trapping agents have produced mixed results, suggesting that the mechanisms underlying this disorder may be more complex than previously thought. Although altered systemic regulation of trace metals in diabetes has been previously investigated, it is still unclear whether changed trace metal metabolism would cause heart disease in common forms of diabetes and whether metal chelation can reverse this condition. Our hypothesis is that the accumulation of redox-active trace metals including Cu and Fe in cardiac muscle may, at least in part, result in cardiomyopathy through the generation of excess reactive oxygen species. We believed that the administration of a specific metal chelator should ameliorate this process by increasing the excretion of free systemic Cu and Fe, consequently limiting the production of superoxide oxygen free radicals and arresting the process of diabetic cardiomyopathy. Data from pre-clinical studies conducted in our laboratory using diabetic animal model with diabetes-induced abnormal Cu metabolism have been remarkably consistent in demonstrating that oral dosing with triethylenetetramine (TETA) can effectively remove systemic Cu via increased urinary Cu excretion, improve cardiomyocyte structure, reverse elevations in left ventricular collagen and β1-integrin, and alleviate heart failure, all in the presence of a consistently high circulating blood glucose profile. Taken together, these findings support the beneficial role of TETA in diabetic animal model and lay the foundation for its potential therapeutic effect in humans with diabetes. This thesis describes a series of randomised, placebo-controlled clinical trials that have investigated the metabolism of Cu and Fe and seven other trace metals in patients with chronic T2DM compared with non-diabetic control subjects. This thesis also examines the mechanism of action of TETA and addresses the hypothesis that a decrease in body systemic Cu pool through chelation therapy may improve cardiac complication in diabetic subjects. Trial 1 is a randomised, double-blind, placebo- and diet-controlled study which measured the 6d balance of Cu and Fe and seven other essential trace metals, in twenty male T2DM and twenty age-matched control subjects in whom we later probed systemic metal balance with oral TETA. Basal urinary output and balance of Cu and Fe was significantly elevated in diabetes, and the two output values correlated strongly (p<0.05). 6d treatment with 2400mg/d dose of TETA (maximum Wilson’s disease dose) has increased the urinary excretion of Cu, which was predicted by basal urinary Cu excretion, thereby causing a positive Cu balance to become negative in diabetes. Regulation of Cu metabolism was shown to be abnormal in diabetes and was selectively modified by TETA, which did not concomitantly modify Fe metabolism. Moreover, TETA did not cause a negative balance in any of the other seven trace metals monitored. These findings are consistent with TETA reversing the accumulation of free systemic Cu in diabetes, which may help to explain its potential therapeutic effects in some diabetic complications. Trial 2 investigated the acute response effect of a single 2400mg dose of TETA on urinary and serum trace metals in the first 10hr and 10~24hr post-dose. The results showed that TETA markedly increased the urinary Cu and Zn excretion in diabetes for the duration of 10hrs with the maximum excretion phase between 4~6hr post-drug (p<0.05). TETA did not change the metabolism of Mg and six other essential trace metals monitored. Trial 3 examined the dose-response effect of TETA, at and below the dose given to patients with the Wilson’s disease over a 7d period, on Cu and eight other trace metals in a subgroup of seven T2DM and seven control subjects who had completed trial 1. The results of this i i trial showed that there was a linear dose-response relationship over the dose range 300~2400 mg/d on urinary Cu excretion in both T2DM and control subjects. However, there was no significant difference between the two subject groups at any of the four doses tested. In addition, 300mg/d of TETA was effective in mobilizing Cu in both T2DM and healthy control subjects. Trial 4 described the full work-up of a sensitive LC-MS methodology to identify and quantify TETA and its metabolite(s) in human urine. Using the LC-MS, TETA metabolism and excretion was investigated by analysing the urine of seven T2DM and seven control subjects who received escalating doses of TETA (samples obtained from trial 3). I have successfully identified and characterised two major metabolites of TETA in the urine of both T2DM and control subjects, N1-monoacetytriethylenetetramine (MAT) and diacetytriethylenetetramine (DAT), the latter which has not been previously reported. The results from urinary TETA excretion analyses also showed that T2DM may metabolise TETA more extensively than control subjects, which in turn is associated with its higher uptake or bioavailability. Urinary Zn excretion was mainly linked with urinary TETA and MAT in T2DM and healthy controls, respectively, whereas urinary Cu excretion was associated with urinary TETA excretion in healthy controls and urinary TETA+MAT excretion in T2DM subjects. These results suggest that MAT may also be involved in the mechanism by which TETA extracts systemic free Cu in diabetes. The identification of the two major metabolites of TETA and the development of a robust analytical LC-MS methodology reported in this study is an important step to further investigate the pharmacological actions of TETA in diabetic individuals. Collectively, the results presented in this thesis and in association with previous animal and clinical studies from our laboratory have provided consistent supporting evidences for the use of TETA clinically as a safe and effective therapy to prevent the genesis of some diabetic complications, in conjunction with conventional complication modifying therapies.

Les sédiments de surface du Golfe du Morbihan et de la Baie de Quiberon ont été analysés afin d’évaluer les éléments traces métalliques (ETMs), leur comportement, les processus qui contrôlent leur distribution spatiale, leur spéciation, leur réactivité et leur biodisponibilité. Les potentielles sources métalliques ont été recherchées à partir de l’analyse des sédiments des ports à proximité et des sédiments du bassin versant. Les analyses ont été faites sur la fraction inférieure à 63 µm des sédiments collectés en Avril 2013. Les concentrations totales et la spéciation des ETMs ont été obtenues à partir des attaques totales et sélectives, respectivement. L’enrichissement en Zn, Cu, Cd et Pb a été mis en évidence dans les sédiments de surface du Golfe du Morbihan. De même, la labilité et la biodisponibilité du Pb ont été montrées dans les sédiments de la Baie de Quiberon. Le comportement des ETMs dans les sédiments de la côte morbihannaise est principalement contrôlé par le gradient terre/mer. Cependant, les ports et les rivières constituent des sources d’ETMs, principalement de Cu et Zn. / Surface sediments in the Gulf of Morbihan and the Bay of Quiberon were analyzed in order to characterize the trace metals elements, their behavior, the processes that control their spatial distribution, their speciation, reactivity and bioavailability. Potential sources of metals were looked for, based on the analysis of nearby harbors and river basin’s sediments. The analyses were done on the fraction below 63 µm of the sediments collected in April 2013. MTEs total concentration and speciation were obtained from total and selective attacks, respectively.The enrichment of Zn, Cu, Cd et Pb was identified in the surface sediments of the Gulf of Morbihan. Pb lability and bioavailability were shown in the sediments of the Bay of Quiberon. The MTEs behavior of the Morbihan’s coast is mostly controlled by the land-sea gradient. However, harbors and rivers form sources of ETMs, principally of Cu and Zn.

Rising carbon dioxide (CO2) concentrations in the atmosphere will increase the average pCO2 level in the world oceans, which will have a knock-on effect on the marine ecosystem. Coastal seagrass communities one of the most productive marine ecosystems are predicted to benefit from the increase in CO2 levels, but long-term effects of elevated CO2 on seagrass communities are less understood. Population reconstruction techniques was used to investigate the population dynamics of Cymodocea nodosa meadows, exposed to long term elevated CO2 at volcanic seeps off Greece and Italy. Effect of elevated CO2 was noticed on the growth, morphometry, density, biomass and age structure at CO2 seeps. Above to below ground biomass ratio of C. nodosa were higher at CO2 seeps than at reference sites. The plastochrome interval were similar at all CO2 seeps. The shoot age and shoot longevity of plants were lower at seeps than reference sites. The present recruitment (sampled year) of the seagrass were higher than long-term average recruitment of the communities near the seeps. Carbon to nitrogen ratios (%DW) of C. nodosa were higher in leaves at seeps. Annual leaf production was higher near the seeps. This study suggests increased production of C. nodosa under elevated CO2 levels, but other co-factors such as nutrients, trace metal toxicity must also be taken into consideration while predicting effects of future CO2 concentrations. Volcanic CO2 seeps are now being used as natural analogues for ocean acidification studies although these areas can be affected by trace element input and may alter ecosystem responses to gradient in carbonate chemistry. Here Fe and a range of trace elements (Cd, Co, Cu, Hg, Mn, Pb, Ni and Zn) were analysed from sediments and from the roots, rhizomes and leaves of seagrass at six CO2 seeps and reference sites off Greece and Italy. There were higher metal levels in sediment and seagrasses at all CO2 seeps than reference sites. Sediment Quality Guideline Quotient, a commonly used pollution index, indicated that some of the metals (Cd, Cu, Hg, Ni) were in high enough concentrations to have adverse biological effects, such as Cu at Ischia site and Hg at Vulcano. Higher accumulation of elements from sediments in roots and leaves at CO2 seeps were found from Bio Sediment Accumulation Factor index. There were higher levels of Cu, Fe, Mn and Zn in leaves and rhizomes for P. oceanica and higher levels of Cd, Co, Cu, Fe and Zn in C. nodosa compartments at CO2 seeps. Fe and Mn were found with positive correlation within sediment-roots and sediment-rhizomes, whereas Cd, Co and Pb were found with positive correlation in compartments of C. nodosa. In P. oceanica positive correlation were only observed for Cd within sediment-roots and plant compartments. Low pH and ocean acidification increased the concentration of elements at CO2 seeps than reference sites. Thus, caution is needed, when using volcanic seep systems as analogue for the effects of rising CO2, as metals can reach levels that are toxic to seagrass, masking any potential benefits of increased levels of carbon dioxide for seagrass productivity. Net community production (NCP) and community respiration (CR) were measured under air exposed and CO2 enriched conditions for intertidal Z. noltei meadows and unvegetated sediment communities during emersion in summer and winter seasons. Community production and respiration were measured in-situ using benthic chambers. CO2 flux under air and CO2 enriched conditions were measured over a series of short term incubations (30min) using an infra-red gas analyser. Incident photosynthetic active radiation (PAR) was recorded during the incubations covering the daily and seasonal variation. Linear regression model was used to test the effects of irradiance on net community production. NCP of Z. noltei community were higher under CO2 enriched conditions than air exposed conditions in both summer and winter seasons. There was no effect of CO2 on the CR rate of Z. noltei community in summer season. NCP of sediment community were higher in summer season and winter season under CO2 enriched conditions. Sediment CR rates were higher in winter than summer season. The light compensation point of Z. noltei and sediment community were lower in both seasons under CO2 enriched conditions. Seasonal budget of community production was higher in Z. noltei than sediment communities. A clear effect of PAR was noticed on the net community production of both communities. Higher PAR intensities resulted in higher NCP under CO2 enriched conditions for both communities. CO2 enrichment will have a positive effect on the intertidal communities during emersion.

Dissertação(mestrado) - Universidade Federal do Rio Grande, Programa de Pós-Graduação em Oceanografia Física, Química e Geológica, Instituto de Oceanografia, 2006. / Submitted by Cristiane Silva (cristiane_gomides@hotmail.com) on 2013-02-11T18:24:39Z No. of bitstreams: 1 2006_fabiana_barbosa.pdf: 1776412 bytes, checksum: 1983355c08ebff62770a80ecc0896046 (MD5) / Approved for entry into archive by Bruna Vieira(bruninha_vieira@ibest.com.br) on 2013-06-11T21:35:03Z (GMT) No. of bitstreams: 1 2006_fabiana_barbosa.pdf: 1776412 bytes, checksum: 1983355c08ebff62770a80ecc0896046 (MD5) / Made available in DSpace on 2013-06-11T21:35:03Z (GMT). No. of bitstreams: 1 2006_fabiana_barbosa.pdf: 1776412 bytes, checksum: 1983355c08ebff62770a80ecc0896046 (MD5) Previous issue date: 2006 / Os estuários são áreas preferidas para a ocupação e urbanização devido a sua localização e importância sócio-econômica. Este tipo de ambiente é vulnerável ao lançamento de inúmeros compostos orgânicos e inorgânicos através de efluentes domésticos e industriais. O Canal de Acesso ao estuário da Lagoa dos Patos, sofre impactos diretos e indiretos, o que pode levar a uma possível deterioração ambiental. Monitoramentos no canal e suas áreas adjacentes são necessários, para a identificação do estado atual da qualidade ambiental principalmente nas áreas de influências diretas e indiretas das atividades portuárias. O objetivo do presente estudo é avaliar de forma espacial, sazonal e temporal as variações nas concentrações totais de metais traço (cádmio, cobre, chumbo e zinco) e de nutrientes dissolvidos (amônio, nitrato, nitrito e fosfato) em águas superficiais do Canal de Acesso (Canal do Rio Grande) ao estuário da Lagoa dos Patos, particularmente na área portuária da cidade do Rio Grande (Porto Novo, São José do Norte e Super porto). Neste estudo foram utilizados os dados obtidos de 5 relatórios técnicos realizados ao longo do eixo do canal, no período compreendido entre 1988 a 2004. A avaliação das concentrações dos nutrientes dissolvidos e metais traço indicou que ocorrem variações espaciais, sazonais e temporais, dependendo principalmente das condições metereológicas e hidrológicas da região, além das diversas influências antrópicas presentes no estuário da Lagoa dos Patos. De maneira geral, os nutrientes e os metais traço no Canal de Acesso apresentaram concentrações abaixo dos limites recomendados pela FEPAM e CONAMA. As concentrações de metais traço mostraram um decréscimo após o início das operações de dragagem de sedimentos no estuário, indicando a importância deste processo na remoção destes elementos do meio ambiente. / Estuaries are preferential areas for occupation and urbanization due its localization and socio-economic importance. This environment is vulnerable to the introduction of organic and inorganic compounds through domestic and industrials effluent. The access canal of the Patos Lagoon estuary, suffers from direct and indirect impacts, and can lead to a possible ambient deterioration. Monitoring studies in the canal and its adjacent regions is necessary to stablish the current state of the environment quality mainly in areas of direct and indirect influences of port activities. The aim of the present study is to evaluate spatially, seasonally and temporally variations of the total concentrations of trace metals (cadmium, copper, lead and zinc) and dissolved nutrients (ammonium, nitrate, nitrite and phosphate) in superficial waters of the Patos Lagoon estuary, particularly the region influenced by the Rio Grande Harbour (Porto Novo, São José do Norte and Superporto). Data between 1988 and 2004 were obtained from 5 technical reports. The assessment of dissolved nutrients and trace metal concentrations indicated that variations occur according the location, meteorological and hydrological conditions of a region, and antropic influences. Results showed that the nutrients and metals concentrations in the canal are below FEPAM and CONAMA recommended limits. Trace metals concentrations showed a decrease, after the beginning of sediment dredging operations in the estuary, showing the importance of this process in the removal of these elements from the environment.

A contaminação dos ecossistemas aquáticos por metais-traço demanda preocupação já que estes contaminantes podem exercer efeitos tóxicos sobre a biota e aumentar os custos para tratamento da água. Em geral, tais problemas de degradação são decorrentes de uma gestão de recursos hídricos deficiente. Tendo como área de estudo a represa Paiva Casto, reservatório integrante do Sistema Cantareira, maior sistema de abastecimento público da região metropolitana de São Paulo, este trabalho teve o intuito de: investigar o histórico da contaminação por metais-traço (Cd, Cr, Cu, Ni, Pb, Zn, Mn, Al) por meio da geocronologia por 210Pb e indicar um valor de referência para estes; identificar a heterogeneidade espacial destes contaminantes; analisar a biodisponibilidade e com base na possibilidade de adequar etapas do sistema de gestão de recursos hídricos europeu, a Diretiva Quadro da Água (DQA) discutir a qualidade química dos sedimentos da represa em estudo. Foram efetuadas duas coletas em campo, destinadas à avaliação do histórico da contaminação ambiental por metais-traço e à análise da biodisponibilidade por meio da técnica de sulfetos volatilizáveis por acidificação (SVA) e metais simultaneamente extraídos (MES). O histórico da contaminação por metais-traço abrangeu um período de 100 anos e indicou que os maiores impactos na região, em relação a estes contaminantes, ocorreu em período anterior ao início de operação da represa Paiva Castro, com exceção do Cu. Para o Cu, em sedimentos superficiais, os teores excederam até três vezes e meia o VR. Este resultado é provável consequência da aplicação de sulfato de cobre para o controle de florações de algas. Os dados para os VR divergiram daqueles estabelecidos para a crosta terrestre, porém foram semelhantes aos encontrados para a bacia do Alto Tietê, com exceção dos metais Cr e Pb. A análise de (SVA/MES) indicou que os metais não estavam biodisponíveis. Dentre as áreas amostradas, a região da barragem apresentou ao longo do tempo as maiores taxas de acumulação para metais-traço em contraposição à área de captação das águas para abastecimento público. Em relação a DQA, constatou-se que existe capacidade científica para avançar na incorporação de novos instrumentos na gestão, principalmente no Estado de São Paulo, entretanto, é preciso que haja sistemas de saneamento e monitoramento adequados e especialmente decisão política e rigor na aplicação destes novos instrumentos, caso contrário a incorporação da DQA é inviável. Aplicando algumas das normas da DQA na avaliação da qualidade química dos sedimentos da represa Paiva Castro constatou-se que a qualidade geral para este manancial é boa. Apesar disto é necessário que as políticas públicas sejam de fato aplicadas contra a degradação deste importante manancial, caso contrário a boa qualidade deste reservatório estará em risco / Contamination of aquatic ecosystems by trace metals demand concern since these contaminants may cause toxic effects on biota and increase costs for water treatment. In general, such degradation problems are due to a poor water management. A study was conducted at Paiva Castro reservoir, one of the reservoirs of the Cantareira System, largest public water supply system in the metropolitan region of São Paulo, this study aimed to: investigate the history of the accumulation of trace-metals (Cd, Cr, Cu, Ni, Pb, Zn, Mn, Al), through geochronology by 210Pb; establish background values (BV); analyze spatial heterogeneity; bioavailability and based on the possibility of adjusting some instruments of the European water resources management system, the Water Framework Directive (WFD), discuss the chemical quality of Paiva Castro\'s sediments. Two collections were performed, to assess the historical environmental contamination by trace-metals and to analyze the bioavailability using the technique of sulfides volatilizable by acidification (AVS) and simultaneously extracted metals (SEM). The history of contamination by trace- metals covered a period of 100 years and indicated that the greatest impacts in the region occurred in periods prior to the reservoir operation, with the exception of Cu. For Cu, in surface sediments, the levels exceeded three times and a half the BV. This result is probable consequence of copper sulphate application for controlling algal blooms. Data for BV were different from those found in the earth\'s crust, but similar to those found for the Alto Tietê basin, except for Cr and Pb metals. Analysis (AVS/ SEM) indicated that metals were not bioavailable. Among the sampled areas, the region of the dam, showed the highest rates of accumulation for trace- metals in contrast to the catchment area for public water supply. Regarding WFD, it was observed that there is scientific capacity to incorporate new instruments in the management, mainly in São Paulo, however, there must be adequate sanitation and monitoring systems and especially political decision and rigor in the application of these new tools, otherwise the incorporation of the WFD is unviable. Applying some of the WFD instruments in assessing the chemical quality of Paiva Castro\'s sediments, it was found that the quality of this ecosystem is good. Nevertheless, it is necessary that public policies are actually applied against the degradation of this important ecosystem; otherwise, reservoir\'s \'good quality\' will be at risk

Abstract The mineralogy and geochemistry of the fine and clay fractions of till in different moraine types and in different bedrock areas in northern Finland have been studied. A total of 250 till samples from 140 test pits were studied mineralogically and geochemically. X-ray diffraction, differential thermal and thermogravimetric analyses, transmission electron microscopy, X-ray fluorescence and atomic absorption spectrometry were used as analytical methods. In the clay fraction of till quartz, plagioclase, microcline and amphibole are the primary minerals occurring. The clay minerals proper include vermiculite, chlorite, illite, swelling-lattice vermiculite and mixed-layer clay minerals. Kaolinite occurs most abundantly in the clay fractions of till in the Kittilä, Jerisjärvi, Kaaresuvanto and Pulju areas. In the clay fraction of Kittilä and Jerisjärvi illite is dioctahedral type, but in their of other study areas both di- and trioctahedral types occur. Kaolinite and dioctahedral illite are evidence of the mixing of the weathered bedrock material into the till matrix. In the fine fraction of till most abundant minerals are primary minerals and clayminerals are in a minor role. In the clay fraction of till the content of primary minerals are at higher and secondary minerals are at lower level in the Granitic and Archaean gneiss areas than in the Greenstone Belt, Svecokarelian schists and gneiss and Granulite areas. Amphibole, microcline and plagioclase occur in very low amounts or are totally destroyed by chemical weathering in the clay fraction of the till in the Kittilä area. The mineral composition of fine and clay fractions in the tills of northern Inari gives an indication that there occur much more mafic volcanites than is known today. The mineralogical compositions of fine fraction of the tills correlates quite well with the underlying bedrock in all study areas, but clay fraction does not. Geochemical results are in accordance with the mineralogical composition of both fractions. In the fine fraction of the till Si, Ca and Na contents are higher than in the clay fraction. Clay fraction is enriched in Al, Fe, Mg, K and trace elements as compared to the fine fraction. Present study material points out that the distribution of chemical elements in the clay fraction of the till does not correlate with the composition of the underlying bedrock, but fine fraction does so with a few exceptions. The chemical composition of till in Kaaresuvanto and Inari does not fully correspond to the composition of the underlying bedrock as known today. In northern Inari and Kittilä the results give an indication that there are more mafic volcanites and/or sulphide mineralizations occurring in these areas than is known at the present time. The most important factors controlling the mineralogical and geochemical composition of the fine and clay fractions of the tills in northern Finland are the composition of the bedrock and the possible occurrence of an old weathering crust. The final grain size composition of the tills and consequently the quantitative proportions of the different minerals are often related to the last glacial quarrying and sorting processes; therefore the mineralogical composition of the tills is to a certain extent bound also to the respective moraine type.

The purpose of this study is to evaluate the relative advantages and disadvantages of two approaches for estimating oral bioaccessibility using a physiologically-based extraction technique (PBET): a simple gastric phase simulation and a two-phase gastrointestinal simulation. Bioaccessibility estimates of six metals prevalent in Canadian contaminated sites (zinc, lead, cadmium, copper, nickel, and chromium) were compared using the gastric phase simulation alone and the complete gastrointestinal simulation. Samples included vacuum dust samples from 33 homes, certified dust and soil reference materials, and a house dust control sample. Bioaccessibility measurements using the gastric phase simulation were greater than or equal to measurements obtained using the gastrointestinal simulation for the six studied metals. This research found that for the six studied metals, a simple simulation of the gastric phase provides the most conservative and cost-effective approach for estimating oral bioaccessibility of ingested metals.

Samples were taken from 72 high-rise apartment suites (6 suites in 12 individual high-rise towers) and 60 single-family houses located within the Greater Vancouver Regional District. The influence of the following factors on trace metal concentrations in 1-L first-flush drinking water samples and running hot water samples was investigated: building height, location, plumbing age, type of plumbing and type of building. Results of this survey show that with the exception of building height, all factors had a correlation with one or more of the trace metals investigated. The trace metals examined were lead, copper, iron and zinc. Lead was influenced primarily by building type, copper by plumbing age and type of plumbing and iron by location. Elevated lead levels were associated with high-rise samples. New copper plumbing systems resulted in high copper levels. Highest iron levels in the drinking water were measured in the East location. Zinc did not show a distinct correlation with any of the factors investigated. Brass faucets were the primary source of zinc in tap water. They also contributed substantially to the lead detected in the 1-L first-flush sample. Metal concentrations measured in high-rise and house samples were compared with U.S. Environmental Protection Agency's (USEPA) maximum contaminant levels (MCLs) and the proposed no-action level for lead1. In high-rise samples, the 0.01 mg/L "no-action" proposed for lead was exceeded in 43% of the samples and 62% of the samples exceeded the current 1.0 mg/L MCL standard for copper. In single-family house samples, these values were 1 Compliance with the proposed 0.01 mg/L no action limit for lead is based on a sample average. Individual samples may exceed this value and still be in compliance. 47% and 73%, respectively. The average lead concentration for all high-rise samples was 0.020 mg/L and 0.013 mg/L for house samples. Regulatory levels stated above would still be exceeded in 6% of the cases for lead and 9% of the cases for copper, even after prolonged flushing of the tap in a high-rise building. In all cases associated with single-family houses, flushing the cold water tap for 5 minutes was successful in achieving compliance levels. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate