Uma das principais consequências dos processos de mineração e beneficiamento do carvão é a elevada produção de rejeitos. Esses materiais retornam às cavas de mineração ocasionando efeitos negativos ao meio ambiente, como a drenagem ácida de mina. Uma alternativa em potencial para esses rejeitos é aplica-los no tratamento de efluentes líquidos como sólidos sorventes. Dentre os principais poluentes aquosos destacam-se os metais pesados e, entre eles, o cromo hexavalente, devido aos seus efeitos carcinogênicos e mutagênicos, sendo altamente prejudicial aos organismos vivos. Neste contexto, o presente trabalho tem como objetivo utilizar o rejeito do beneficiamento do carvão de Moatize (Moçambique) como sólido sorvente para a remoção de cromo hexavalente de águas contaminadas. O sólido foi utilizado em duas granulometrias diferentes: no intervalo entre 0,7 e 1,5 mm (R1) e menor que 0,074 mm (R2). As amostras foram caracterizadas segundo sua massa específica, densidade aparente, área superficial (BET), volume de poros e diâmetro de poros (BJH), ponto de carga zero, composição química (FRX) e mineralógica (DRX). Ensaios experimentais foram realizados a fim de determinar as melhores condições de sorção, onde foram avaliados o efeito do pH, do tempo de residência e da concentração de sorvente As melhores condições encontradas para o sólido R1 foram: pH 2, 10 h de ensaio e concentração de sorvente de 8 g L-1, onde foi obtido 98,6% de remoção de Cr(VI). A maior remoção para o sólido R2 foi de 98,8%, obtida utilizando-se: pH 2, 50 min de ensaio e concentração de sorvente de 10 g L-1. Comparando com o limite previsto pela legislação brasileira CONAMA 430 para despejos industriais as concentrações finais de cromo hexavalente em solução ficaram abaixo do valor máximo estabelecido (0,1 mg L-1). A partir destas condições encontradas, foram construídas isotermas de equilíbrio e os modelos de Langmuir, Freundlich e Sips foram ajustados aos dados experimentais. Para o sólido R1, os modelos de Langmuir e Sips demostraram um bom ajuste, apresentando valores de R2 de 0,897 e 0,907 respectivamente. Já para o sólido R2, o modelo de Sips foi o que melhor representou os dados experimentais, com um R2 de 0,954. Os resultados encontrados indicam que o rejeito de carvão de Moatize pode ser utilizado para o tratamento de águas contaminadas com cromo hexavalente. / One of the main consequences of coal mining and beneficiation process is the large production of waste and by-products. These materials return to the mines generating significant negative impacts to the environment. One of the possible applications for the coal wastes is in the wastewater treatments, where it can be used as a sorbent. Amongst the main water pollutants, heavy metals stand out, especially hexavalent chromium, due to its carcinogenic and mutagenic effects, being highly prejudicial to the living organisms. In this context, the objective of this study is to use coal beneficiation waste from Moatize (Mozambique) as a sorbent to remove hexavalent chromium from aqueous solution. Coal waste was utilized in two different particle sizes: between 0.7 and 1.5 mm and smaller than 0.074 mm. These solids were characterized for their specific weight, bulk density, superficial area (BET), pore volume and diameter (BJH), point of zero charge, chemical composition (XRF) and mineral composition (XRD). Experiments were conducted to determinate the best sorption conditions, were the operating parameters investigated were: solution pH, contact time and sorbent concentration The best conditions for Cr(VI) sorption onto R1 were: pH 2, 10 h and 8 g L-1 of sorbent concentration, were 98.6% removal was obtained. Cr(VI) maximum removal onto R2 of 98.8% was achieved at pH 2, 50 min and 10 g L-1 of sorbent concentration. Comparing with the limit permitted by Brazilian legislation, CONAMA 430, for industrial wastewaters, the final Cr(VI) concentration in water were below the maximum established by law (0.1 mg L-1). From these results, equilibrium isotherms were build and the mathematical models of Langmuir, Freundlich and Sips were fitted to the experimental data. For the R1 sorbent, Langmuir and Sips models fitted better the experiments, with R2 values of 0.897 and 0.907, respectively. Sips model described better the experimental data when the R2 sorbent was used, with a R2 of 0.954. Results showed that Moatize’s coal waste can be utilized for hexavalent chromium wastewater treatment.

O glifosato é um dos herbicidas mais consumidos no Brasil e com perspectivas de aumento deste consumo, diante da expansão do plantio direto e do plantio de culturas geneticamente modificadas com resistência a esse herbicida. Porém, pesquisas com esta molécula são ainda incipientes em solos de clima tropical. Nesse contexto, esta pesquisa objetivou gerar dados para uma melhor compreensão do comportamento ambiental desta molécula. Com este intuito, foram realizados ensaios laboratoriais com um Latossolo Vermelho (LE) e um Neossolo Quartzarênico (RQ) que permitiram o desenvolvimento dos capítulos descritos. Os ensaios foram realizados no laboratório de Ecotoxicologia do Centro de Energia Nuclear na Agricultura (CENA/USP), com glifosato radiomarcado no carbono fosfonometil. Na parte inicial da tese, foi realizada uma breve revisão do comportamento ambiental do glifosato. No segundo capítulo, procurou-se determinar os principais constituintes dos solos responsáveis pela sorção do herbicida. Para isso, foram realizadas extrações seqüenciais dos principais componentes dos solos, com métodos adequados, e em seguida, realizados os ensaios de sorção e dessorção nas amostras. No terceiro capítulo, foi estudado o efeito da calagem, prática comum na agricultura brasileira, nos processos de retenção e mineralização do glifosato, além de avaliar o efeito da calagem e do glifosato na atividade microbiana dos solos estudados. No quarto capítulo foi avaliado a remobilização dos resíduos ligados de 14C-glifosato nos solos, na presença ou não de calagem. Os dados obtidos permitiram verificar que, dentre as frações avaliadas no segundo capítulo, os óxidos de ferro foram os principais responsáveis pela sorção do glifosato nos dois solos estudados e a dessorção do herbicida foi baixa em todas as condições. Nos resultados obtidos com os ensaios do terceiro capítulo, foi possível observar que a calagem não influenciou significativamente a sorção e a dessorção do glifosato, tanto no LE quanto no RQ. A atividade da microbiota de ambos os solos foi afetada pela calagem e pelo glifosato. Com relação ao ensaio de mineralização, a calagem aumentou significativamente a mineralização do glifosato no LE e no RQ. Este mesmo efeito da calagem foi observado na remobilização dos resíduos ligados deste herbicida nos solos. Em todos os ensaios foi possível observar a elevada capacidade que o glifosato possui em formar resíduo ligado nos solos, sendo a principal fração formada deste herbicida. Diante dos resultados obtidos foi possível notar a necessidade de mais pesquisas sobre o comportamento do glifosato em solos de clima tropical, sob diferentes condições. / Nowadays, glyphosate is one of the most used herbicides in the Brazilian agriculture being expected an increase in its employment due to both the expansion of no-tillage cropped areas and the cultivation of transgenic plants resistant to this molecule. Considering that research related to glyphosate behaviour in tropical soils remains incipient, the present study aimed at to get more detailed information on the dynamics of this molecule in two different Brazilian soils. Laboratory experiments were carried out with both a Red Latosol (LE) and a Quartzarenic Neosol (RQ) at the Ecotoxicology Laboratory from Nuclear Energy in Agriculture Center (CENA/USP) by using 14C-glyphosate (C labelled at phosphonomethyl group). In the first part of the thesis, it is presented a brief review of the environmental behaviour of glyphosate. The second chapter describes an experiment carried out to identify the main soil component responsible for the glyphosate sorption. To attend this, the sequential removals of organic matter, iron oxides and gibbsite was done being each one followed by glyphosate sorption and desorption batch experiments. In the third chapter it was studied the soil liming effects on both retention and mineralization of glyphosate and also the mutual effect of liming and glyphosate on the soil microbial activity. In the fourth chapter it was evaluated the remobilization of glyphosate bound residues in soil with or without liming. The results presented in the second chapter indicated that the iron oxides are the main components responsible for the glyphosate sorption in both studied soils and that the desorption was low in all studied conditions. The results of the third chapter showed that liming influences neither glyphosate sorption nor its desorption in the two soils and that its mineralization increased in both of them due to the lime application. Similar effects were observed in the fourth chapter, where, for all experiments, liming increased the remobilization of bound residues of glyphosate.

Este trabalho teve como objetivo avaliar a tolerância e a capacidade de fitorremediação de crotalária (Crotalaria spectabilis), sorgo (Sorghum bicolor), nabo forrageiro (Raphanus sativus), amendoim (Arachis hypogaea) e alfafa (Mendicago sativa) a solos contaminados por tebuthiuron. Para determinar a tolerância das plantas ao herbicida estas foram submetidas a 5 diferentes doses (300, 600, 1200, 2400 e 4800 gramas de ingrediente ativo por hectare gi.a. ha-1) e comparadas com uma testemunha que não recebeu aplicação do herbicida. Crotalária, Nabo forrageiro e alfafa se mostraram sensíveis ao herbicida, mesmo na menor dose de aplicação, enquanto sorgo se mostrou tolerante ao herbicida até a dose de 600 gi.a. ha-1 tendo apresentado fitointoxicação de 80% na dose de 1200 gi.a. ha-1 e amendoim foi tolerante até a dose de 4800 gi.a. ha-1 para a qual apresentou apenas 40% de fitointoxicação. Plantas de amendoim e sorgo foram submetidas a dose de contaminação de 600 gi.a. ha-1 aplicada por meio de uma solução de trabalho contendo 17,47kBq (Quilobecquerels) de 14C-tebuthiuron. As duas plantas foram capazes de remediar o solo, no entanto amendoim se mostrou mais eficiente reduzindo a contaminação em 75,8% enquanto sorgo retirou do solo 44,49% do herbicida contaminante / This study aimed to evaluate the tolerance and phytoremediation capacity of sunn hemp (Crotalaria spectabilis), sorghum (Sorghum bicolor), turnip (Raphanus sativus), peanuts (Arachis hypogaea) and alfalfa (Mendicago sativa) in tebuthiuron contaminated soil. To determine the tolerance to the herbicide, plants were subjected to five different doses (300, 600, 1200, 2400 and 4800 grams of active ingredient per hectare gi.a. ha-1) and compared with a control that had no herbicide application. Sunn hemp, turnip forage and alfalfa were sensitive to the herbicide, even at the lowest application dose, while sorghum showed tolerance to the herbicide at 600 gi.a. ha-1 dose, having 80% phytointoxication presented at dose 1200 gi.a. ha-1 and peanut was tolerant at dose 4800 gi.a. ha-1 for which it showed only 40% of phytointoxication. Peanut and sorghum plants were subjected to a contamination dose 600 gi.a. ha-1 applied in a work solution containing 17.47kBq (Kilobecquerels) of 14C-tebuthiuron. The two plants were able to remediate the soil, however peanut was more efficient reducing contamination by 75.8% while sorghum removed 44.49% of the soil contaminant herbicide

Teores anômalos de cromo hexavalente vêm sendo detectados na água subterrânea de vários municípios da região noroeste do Estado de São Paulo, sendo que em Urânia foram observadas as maiores concentrações do elemento, afetando as condições do consumo e uso humano. Estudos prévios realizados indicaram que a origem do cromo na água subterrânea é natural e proveniente de minerais com cromo no aqüífero profundo. Este projeto teve como principais objetivos: (1) a caracterização química e mineralógica da fase sólida do aqüífero profundo, realizada em testemunhos de duas sondagens profundas; (2) a caracterização da estratificação das concentrações de cromo na água subterrânea, com base na coleta e análise de amostras de água provenientes de poços de monitoramento instalados em diferentes profundidades do aqüífero; (3) a identificação dos processos hidrogeoquímicos que justificam a passagem do cromo da fase sólida para a água. Para tanto, foram realizadas análises químicas e mineralógicas por WDS, microssonda eletrônica e CTC, diversos métodos de análise química da água subterrânea, utilizados programas como o AquaChem e PHREEQc para trabalhamento do banco de dados e modelagens, além de uma grande variedade de experimentos de laboratório. As análises químicas por WDS e microssonda eletrônica indicaram concentrações de cromo de até 12.600 ppm em cristais de diopsídio, e de 650 ppm em capas de argilomineral. O material sólido apresenta uma capacidade de troca de cátions da ordem de 30 meq/100g, com ordem de abundância dos cátions Ca>>Mg>>K>Na. Na porção profunda do aqüífero, foi observada uma anomalia de sódio adsorvido, influenciando na composição química da água. As características hidroquímicas do aqüífero indicaram a ocorrência de estratificações de águas com diferentes perfis hidroquímicos. As águas são, no geral, do tipo bicarbonatadas cálcicas, porém com uma elevação do conteúdo de sódio na base do aqüífero. O cromo foi identificado na água predominantemente na forma hexavalente, com concentrações que atingiram 0,139 mg/L, acima, portanto do limite de potabilidade (0,05 mg/L). A ocorrência de valores mais elevados de cromo na água parece estar associada a ambientes de elevados pH e Eh, como observado no aqüífero profundo, enquanto que nas zonas rasas, que apresentam valores de pH e Eh neutros, apresentaram baixo conteúdo de cromo. Os principais resultados dos ensaios de laboratório indicaram que há passagem de cromo para água subterrânea, através do ataque aos minerais pesados com pH ácido; os ensaios de batch test realizados apontaram que o material sólido do aqüífero apresenta alguma capacidade de adsorção de Cr6+, chegando a um máximo de 0,12 ppm; o experimento de solubilização indicou a passagem de pequenas concentrações de cromo para a água e que a composição química da água do ensaio é semelhante à água do aqüífero. O modelo mais provável das reações geoquímicas que explicam a passagem do cromo da fase sólida para a água é apresentado a seguir, divido por etapas: (1) o intemperismo dos diopsídios cromíferos deve ser o processo inicial de disponibilização de cromo para a água, resultando na precipitação do cromo como hidróxidos ou sendo adsorvido por hidróxidos de ferro e manganês; (2) ocorrência de uma reação de oxi-redução a partir do cromo trivalente que ocorre nos minerais secundários, disponibilizando o cromo para a água subterrânea, sendo que esta oxidação ocorre a partir da redução de óxidos de manganês presentes como minerais em aqüíferos, liberando Mn2+; (3) O Cr3+ é rapidamente e fortemente imobilizado por adsorção em argilominerais de baixo valor de pHpzc, enquanto que o Cr6+, devido à sua natureza aniônica, é preferencialmente retido em superfícies carregadas positivamente, como os óxidos e hidróxidos de ferro e alumínio (minerais com elevados valores de pHpzc), principalmente em condições hidroquímicas neutras a ácidas; (4) altas concentrações de OH-, de HCO3- e de CO3 2- provavelmente elevam a competição pelos sítios de adsorção de ânions e causam a dessorção dos ânions de Cr6+ para a água do aqüífero. / Anomalous hexavalent chromium contents have been detected in groundwater in many municipalities of the northwestern region of São Paulo state. In the city of Urânia, the highest concentrations of this element have been observed, affecting the conditions for human consumption. Previous studies indicated that the origin of chromium in groundwater is from natural sources and derived from chromium minerals in the deep aquifer. The main objectives of this research are to: (1) characterize chemically and mineralogically the solid phase from the deep aquifer; (2) characterize the stratification of chromium concentrations in groundwater, based on sampling and analysis of groundwater from wells installed in different depths of the aquifer; (3) identify hydrogeochemical processes that justify the passage of chromium from solid phase to groundwater. To achieve these objectives, chemical and mineralogical analysis by WDS, microprobe and CEC were made, diverse chemical analytical methods were used for groundwater, database and modeling were used through AquaChem and PHREEQc programs, besides a great variety of laboratory experiments. Chemical analysis from WDS and microprobe indicated chromium concentrations of up to 12.600 ppm in diopside crystals, and up to 650 ppm in clay mineral coats. The solid material has a Cation Exchange Capacity (CEC) of about 30 meq/100g, with cation abundance order of Ca>>Mg>>K>Na. In the aquifer deep zone, it was observed an adsorbed sodium anomaly, that influences groundwater chemical composition. The aquifer hydrochemical characteristics indicated the occurrence of water stratifications with different hydrochemical profiles. The groundwaters are, in general, calcium bicarbonated, with a elevation of sodium contents in the base of the aquifer. Chromium was identified predominatly in hexavalent state of oxidation, with concentrations of up to 0,139 mg/L, thus above potability standards (0,05 mg/L). The occurrence of higher chromium concentrations in groundwater seems to be related to high pH and Eh environments, whereas shallow zones, that have neutral values of pH and Eh, presented low chromium contents. The main results of laboratory experiments have indicated that there is passage of chromium to groundwater through acid etching in heavy minerals; batch tests have shown that solid phase has some sorption capacity, reaching a maximum of 0,12 ppm; solubilization experiment indicated the passage of low concentrations of chromium to water and that chemical composition from the experiment water is similar to groundwater. The probable model that explain the passage of chromium from solid phase to groundwater is presented hereafter, divided in steps: (1) it is indicated that weathering of chromium diopsides must be the initial process of availability of chromium to water; (2) hexavalent chromium can only occur in groundwater after the occurrence of an oxi-reduction reaction from the trivalent chromium that occurs in minerals. Many authors recognize that this oxidation occurs from the reduction of manganese oxide presented as minerals in the aquifer, releasing Mn2+, that later will be oxidated again; (3) the trivalent chromium is rapidly and strongly immobilized by sorption in clay minerals of low values of pHzpc, whereas the hexavalent chromium, due to its anionic nature, is preferably retained in positively charged surfaces, like iron and aluminium hydroxides (minerals with high values of pHzpc), mainly in neutral to acid hydrochemical conditions; (4) high OH-, HCO3 - and CO3 2- concentrations probably elevate the competition for anion sorption sites and cause the desorption of hexavalent chromium anions to groundwater.

The contamination of sterile pharmaceutical products is a serious event which has in the worst case scenario led to patient death. Operators are the primary source of clean room contamination, with the majority of their detritus being identified as skin squames and their related microorganisms. The ability of operator associated bacterial contamination to disseminate through specialist garments worn in the clean room environment is apparent in the literature. However, despite the fibres of such garments being identified as a suitable substrate for bacteria to adhere to and grow upon, the bacterial bioburden of the surface of clean room operators’ garments is an area which severely lacks in published research. Reported here is the recovery, enumeration and comparison of the levels of bacteria on the surface of reusable antistatic carbon filament polyester clean room garments, using the direct agar contact method, following their laundering with and without terminal gamma sterilisation, immediately following their donning with operators dressing wearing either no gloves, non – sterile gloves or sterile clean room gloves, and following their wear within the clean room environment, with respect to gender. The aforementioned method, with its recovery efficiency shown to be unaffected by agar composition (NA or TSA), recovered bacteria from the surface of garments laundered with and without gamma sterilisation. Such terminal decontamination was shown to reduce the surface bacterial bioburden of the garments, especially at the chest and umbilicus regions, which were shown to harbour higher levels of bacteria than the other sites tested. The direct agar contact method, showing an increase in recovery efficiency following a 48 hour agar incubation period as opposed to a 24 hour period, also recovered bacteria from the surface of clean room garments donned by operators dressing wearing either no gloves, non – sterile gloves and sterile clean room gloves. Bacteria were transferred onto the surface of these garments via the hand borne route, with the chest and oral cavity regions being found to harbour more bacteria than the other sites tested. Overall, glove type was shown to have no effect upon the resultant bacterial bioburden of the surface of the garments, suggesting expensive clean room gloves could be substituted for their cheaper non – sterile equivalents or no gloves during the donning process without subsequently increasing the surface bacterial bioburden of the garment. The direct agar contact method also recovered bacteria from the surface of clean room garments worn by male and female operators, following their working period within a clean room environment. Gender was found to significantly affect the surface bacterial bioburden of the garments, with the surface of those garments worn by male operators being more contaminated than the surface of those worn by their female counterparts. In addition, the donning of a clean room hood was shown to reduce the levels of bacteria at the chest and posterior cervicis regions of suits worn by both genders. Overall, the direct agar contact method was identified as a successful tool to recover, enumerate and estimate the surface bacterial bioburden of reusable antistatic polyester carbon filament clean room garments. Finally, using 16S rRNA gene sequencing, found to be more reliable and accurate at identifying unknown isolates than traditional phenotypic first - stage tests, which were subsequently found to misidentify > 85 % of the isolates tested, a self - selected representative number of isolates recovered from the surface of garments during the laundering and gender comparison studies were predominantly identified as skin commensal species of Staphylococcus and Micrococcus, as well as environmental species of Bacillus. The knowledge contained within this thesis, with respect to clean room operators and their specialist garments, contributes towards improving contamination control standards within clean room facilities.

There is great interest in understanding the contamination of stainless steel by radionuclides across the nuclear fuel cycle. Through study of uptake mechanisms, contaminant localisation and process conditions that affect uptake, decontamination strategies can be tailored to remove built-up radioactive species. This study focusses on understanding stainless steel contamination by inactive lanthanides and radioactive actinide species (U, Np, Pu and Am) in acidic media. Through depth profiling, contamination has been seen to localise on the interface of the oxide layer and the bulk metal (at depths of up to 100 nm) indicating a potentially tenacious contamination mechanism. Furthermore, contaminant was observed at greater depths within the material (up to ~300 nm), suggesting penetration beyond the passive layer in to the bulk of the material. Long term immersion studies (up to 9 months) in 12 M HNO3 have also been undertaken to investigate the effect of surface corrosion on contaminant uptake. After 3 months the surface had undergone intergranular corrosion and grain droppage was observed. Further surface analysis revealed localisation of contaminants within the steel grain boundaries and vacancies. Once again, this may necessitate a more aggressive decontamination strategy. Conditions have been identified that enhance uptake of transuranic contaminants. Highest levels of uptake were seen in polished steel samples immersed in 4 M HNO3. The Np-237, Pu-239 and Am-241 contaminated samples showed surface concentrations of up to 1.2x107, 9.4x105 and 1x109 Bq/m2, respectively. In the case of Np contamination of stainless steel, microfocus X-ray absorption spectroscopy has shown the surface-mediated reduction of Np(V) leading to Np(IV) adsorption.

Discussion: This study aims at expanding the understanding of mental contamination. First, the dirty kiss experiment is independently replicated in a Chinese population. Second, contact contamination and mental contamination are found to be separable and do not interact with each other. This underscores the independence of the two forms of contamination. Third, betrayal is shown to evoke mental contamination. Discussion has been made on the potential link between psychological violation, morality and mental contamination. / Mental contamination, an important phenomenon in OCD, refers to a sense of dirtiness without any contact with objectively dirty contaminant. However, the concept of mental contamination has not been thoroughly researched and there is an impending need for a psychological model to explain the phenomenon. / Method: Participants were assessed on questionnaires after imagining a non-consensual kiss or betrayal. / Objectives: The overall goal of this study is to enhance our understanding about mental contamination. Based on an experimental paradigm developed by Fairbrother, Newth, and Rachman (2005), three experiments are designed. The first experiment aims at replicating the results of the original study in local Chinese women. The second experiment examines the relationship between contact and mental contamination. The third experiment investigates the presence of mental contamination in persons experiencing betrayal. / Results: In Experiment 1, with an imagined non-consensual kiss, feeling of dirtiness, urge to wash and negative emotions were reproduced. In Experiment 2, it illustrated that either kissing a physically dirty looking man or being kissed non-consensually would experience stronger feeling of dirtiness, urge to wash and negative emotions. The last experiment showed that an imagined betrayal, a form of psychological violation, also induced a feeling of dirtiness, washing urge and negative emotions as with an imagined non-consensual kiss. / Three different pools of adult female participants were recruited for each experiment. In Experiment 1, 72 participants were recruited and randomly assigned to either a consensual kiss or a non-consensual kiss condition. In Experiment 2, 122 participants were recruited and randomly assigned to one of the four conditions. In Experiment 3, a total of 64 participants were recruited and randomly assigned to either non-betrayal or betrayal condition. / Kwok, Pui Ling Amy. / Adviser: Patrick Leung. / Source: Dissertation Abstracts International, Volume: 73-01, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 166-177). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract and appendixes 1-3, 5-8 also in Chinese.

The small dinoflagellate Azadinium spinosum produces azaspiracid (AZA) toxins which can contaminate filter feeding shellfish to dangerous levels. Toxin-contaminated shellfish flesh, when consumed by humans, can cause acute intense illness and chronic health issues. Shellfish biotoxins are monitored in Scottish shellfish by Food Standards Scotland (FSS), and the concurrent monitoring of harmful phytoplankton in the water column acts as an important early warning system of future shellfish toxin contaminations. Since A. spinosum is very small (12-16 μm long) it is difficult to identify using a light microscope, therefore molecular techniques have been developed to detect species-specific environmental DNA from phytoplankton samples. In this thesis the application and verification of quantitative real time polymerase chain reaction (qPCR) is discussed in detail and documents its first use in Scottish waters to survey A. spinosum abundance and seasonality. The limit of detection of the method was found to be 2000 ±5600 cells L-1, however it is unclear whether this is adequate for regulatory monitoring because it is not yet understood how cell density in the water column relates to AZA shellfish toxicity. The qPCR probe and primer sequences were also found to be too specific to detect all strains of the A. spinosum species, as new strains have been isolated since their development. This is a significant hindrance to the application of the tool for monitoring which will need to be addressed in the future through the isolation of local A. spinosum strains. Over a year long sampling period, A. spinosum was detected only twice (maximum cell density of 2545 ±5600 cells L-1, August 2014) off the Shetland Islands. The seasonality of the species in Scottish waters could not be assessed with so little data, however other observed harmful species of importance to shellfish regulatory monitoring are discussed; of particular note an unusual bloom of Dinophysis acuta as its association with a temperature front at the mouth of Loch Fyne. This thesis critiques the use of this qPCR technique for A. spinosum detection at high-throughput. The issues which have been highlighted do not prevent its future use by FSS, but highlight specific areas of development which need addressed before national monitoring can occur.

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / O córrego de São Lourenço (Nova Friburgo RJ), situado na principal região agrícola do estado, representa um importante manancial hídrico do município de Nova Friburgo que percorre um vale onde se concentram as principais lavouras responsáveis pela produção de olerícolas do Estado. Esta localidade apresenta expressiva relação de consumo de agrotóxicos por trabalhador (56 kg/trabalhador/ano). Assim, este córrego recebe todos os resíduos provenientes das lavouras situadas em suas margens. As águas desse córrego são usadas após tratamento pela população residente na área metropolitana e, são usadas sem tratamento pela população residente em suas margens. Este estudo tem como objetivo avaliar a contaminação das águas desse córrego por agrotóxicos anticolinesterásicos. Amostras de água foram coletadas mensalmente de abril/07 a fevereiro/08, em seis pontos do Córrego São Lourenço e em um ponto do Córrego das Paixões. Foram utilizadas garrafas previamente rinsadas com metanol e enxaguadas várias vezes com água destilada. A avaliação dos níveis de pesticidas se deu por método enzimático descrito por Cunha Bastos et al (1991) e pela etapa de concentração e extração dos pesticidas em coluna de carvão ativado foi adaptada a partir do método descrito por Kaipper et al. (2001), que possui a vantagem de ser um teste rápido de avaliação inicial e de baixo custo. Como controle negativo foi usado águas coletadas no ponto um, situado em área de floresta, sem terras cultivadas ao redor. Foram geradas 72 amostras, onde 33 apresentaram indícios de contaminação, mas apenas uma atingiu o limite de detecção do método, 5 ppb, em maio/07. Estes resultados, principalmente os obtidos nos pontos localizados na parte final do córrego São Lourenço, sugerem, além da utilização recente de agrotóxicos, a importância de fatores climatológicos e do regime do uso de tais compostos possivelmente interferindo na detecção dos resíduos em questão / The São Lourenço river, located in the main agriculture region of the State of Rio de Janeiro, Brazil, represents an important water supply for the Municipality of Nova Friburgo. This region is very fertile concentrating most of the vegetables production of Rio de Janeiro. The area presents an expressive rate of pesticides consumption per worker, estimated in about 56 kg/worker/year. The São Lourenço river receives all residues from the area and, with no water treatment, provides the water supply for the population living in its margins. After conventional treatment its water also supplies the metropolitan area of the City of Nova Friburgo. This study focuses its levels of contamination by pesticides. Water samples were collected, monthly, from april/07 february/08 at six points of the São Lourenço river using sterile 1 L plastic bottles previously washed with methanol and rinsed several times with distilled water. Evaluation of the pesticides levels were carried out a through an enzymatic method described by Cunha Bastos et al (1991), with presents the advantages of low cost and rapid assessment, for initial screening. Water collected at the source of the São Lourenço was used as a negative control. This spring is located at the same region but in the middle of forest with no cultivated lands around it. Concentrations of acetylcolinesterase inhibitors was found in 33 analisys, but only one apresented concentraition of inhibitors some than the method limity (5 ppb), detected in point number 3, in may/07, located in the main agriculture in the region of São Lourenço. These results, suggests that besides recent use of anticholinesterasic compounds, others factors are to be considered: climatologic factors and the regimen of use of such compounds. They are considered altogether interfering in a significant way in the detection of the residues in subject. Although the remaining water samples of the study presented values lower than possible for the enzymatic method detect, its use is highly recommended for agricultural areas, due to the need of simples and low cost routine screening methods to alert on risks for human population an environmental

Submitted by Bruno Galvão de Campos null (bruno12323@hotmail.com) on 2017-02-02T21:45:41Z No. of bitstreams: 1 Dissertacao Bruno Campos-revisada-pos-defesa.pdf: 1612994 bytes, checksum: 8486d4d50565a54b53b33f19060e0263 (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-02-06T17:38:53Z (GMT) No. of bitstreams: 1 campos_bg_me_svic.pdf: 1612994 bytes, checksum: 8486d4d50565a54b53b33f19060e0263 (MD5) / Made available in DSpace on 2017-02-06T17:38:53Z (GMT). No. of bitstreams: 1 campos_bg_me_svic.pdf: 1612994 bytes, checksum: 8486d4d50565a54b53b33f19060e0263 (MD5) Previous issue date: 2017-01-06 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A Baía de Guanabara concentra aproximadamente 70% das indústrias do Estado do Rio de Janeiro. Os resíduos produzidos por essas fontes, somados à carga de esgoto doméstico, transformaram a região em umas das áreas mais poluídas da costa Brasileira. O presente estudo realizou a avaliação do risco ecológico dos metais em sedimentos da Baía de Guanabara, por meio de um método escalonado utilizando múltiplas linhas de evidência: caracterização do sedimento quanto à sedimentologia e concentração de metais, comparação das concentrações ambientais com guias de qualidade de sedimento, ensaios de toxicidade crônica utilizando os organismos Anomalocardia brasiliana e Nitocra sp., ensaios de toxicidade aguda utilizando os organismos Tiburonella viscana, Kalliapseudes schubartii, e Anomalocardia brasiliana. Para comprovar existência de relação causa e efeito entre os metais e a toxicidade, foram empregadas a técnica do TIE, análises multivariadas (PCA) e matrizes qualitativas. Os sedimentos mostraram níveis altos a moderados de metais (Zn, Pb, Cu, Cr) associados com a toxicidade. O TIE revelou que, além dos metais, amônia e compostos orgânicos são contaminantes presentes na região que tem a capacidade de causar toxicidade. Desse modo constatou-se que os metais constituem uma importante classe de contaminantes para a Baía de Guanabara, os quais, além de estarem presentes em altas concentrações, interagem com outros contaminantes e são também (co)responsáveis por efeitos biológicos negativos. / The Guanabara Bay (GB) comprises approximately 70% of the industries of Rio de Janeiro State. The wastes produced by these sources, combined with the domestic sewage loads, have transformed the region into one of the most polluted areas of the Brazilian coast. The present study evaluated the ecological risk of metals in sediments from the GB by the use of a tiered approach. The chosen method combines the following lines of evidence: geochemistry, comparison of environmental concentrations of metals with sediment quality guidelines, chronic sediment toxicity tests with Anomalocardia brasiliana and Nitocra sp.; and acute sediment toxicity tests with Tiburonella viscana, Kalliapseudes schubartii, and Anomalocardia brasiliana. To verify the existence of cause and effect relationships between metals and toxicity, the Toxicity Identification Evaluation (TIE) technique, multivariate analysis (PCA) and qualitative matrices were used. Sediments showed high to moderate levels of metals (Zn, Pb, Cu, Cr) associated with toxicity. In addition, the TIE has revealed that metals, ammonia and organic compounds contribute to cause sediment toxicity. We concluded that metals are an important class of contaminants for the GB, together with other chemicals, as they are present in high concentrations, interact with other substances and are (co)responsible for the negative biological effects. / FAPESP: 2015/13143-0