Thesis (Ph.D.)--Mississippi State University. Dave C. Swalm School of Chemical Engineering. / Title from title screen. Includes bibliographical references.

Thesis (M.S.) -- University of Tennessee, Knoxville, 2006. / Title from title page screen (viewed on Sept. 19, 2006). Thesis advisor: Joanne Logan. Vita. Includes bibliographical references.

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Orientador: Wanilson Luiz Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-10T23:28:06Z (GMT). No. of bitstreams: 1 Campaner_VeridianaPolvani1981-_M.pdf: 789477 bytes, checksum: 2fc8ab44d662b02cf37a6481c9ac9f7d (MD5) Previous issue date: 2008 / Resumo: Este estudo foi desenvolvido em área de mineração de carvão, na região de Figueira (PR). A primeira parte deste trabalho investigou processos físico-químicos da drenagem ácida antes e após o tratamento com CaO e sua evolução em drenagem natural em área com presença de rochas calcárias. Os resultados mostraram um incremento no pH da drenagem ácida após o tratamento (de 3,2 para 4,6) e redução nas concentrações dos constituintes analisados. A evolução deste efluente ácido na rede de drenagem local resultou em um novo sistema físico-químico, inicialmente com pH 6,4 e menores níveis de Eh e dos constituintes químicos, em especial para SO4 2¯ (1578 mg L¯1), Al (0,07 mg L¯1), Fe (17,8 mg L¯1) e Mn (2,48 mg L¯1). Entretanto, as concentrações destes constituintes foram ainda menores nesta drenagem com incremento do pH para 10,8, exceto para Al. O incremento na concentração de Al (de 0,07 mg L¯1 para 0,63 mg L¯1) é atribuído à lixiviação de minerais silicáticos sob condições alcalinas, as quais favoreceram a solubilização do metal. Este aumento do pH pode ser conseqüência de rochas calcárias da região que se encontram a partir de 10,5 m de profundidade. Águas subterrâneas que alimentam a drenagem local devem contribuir com o incremento das concentrações de HCO3¯ até que as condições de equilíbrio do sistema carbonático sejam rompidas com o excesso de CO3 2¯, aumentando o pH para 10,8. Neste ponto ocorreram condições físico-químicas favoráveis para a remoção de Mn, um dos problemas encontrados em processos de neutralização de drenagem ácida. A segunda parte deste trabalho avaliou as características geoquímicas de drenagens ácidas desta região e seus impactos em águas e em sedimentos de corrente. Os resultados mostraram que as drenagens ácidas são geradas tanto em galerias de extração do minério como em depósitos de rejeito, com pH entre 3,2 e 4,1. Estas últimas drenagens apresentaram as maiores concentrações dos elementos investigados, com destaque para o As (0,25 mg L¯1 a 0,68 mg L¯1). O impacto destas soluções ácidas nos rios da área foi pouco significativo. As concentrações de SO4 2¯, Al, Cd, Co, Fe, Mn, Ni e Zn (nas proximidades de minas ativas) e SO4 2¯, Al, Cd, Fe, Mn e Zn (nas proximidades de depósitos de rejeito e minas desativadas) excederam levemente os padrões brasileiros de qualidade para águas superficiais. As águas subterrâneas de poços de monitoramento das atividades mineiras apresentaram o mesmo intervalo de pH e concentrações químicas semelhantes aqueles das drenagens ácidas, revelando o seu comprometimento. Entretanto, as amostras de águas subterrânea e fluvial de abastecimento público municipal revelaram pH entre 7,2 e 7,5 e baixas concentrações dos componentes analisados. A geoquímica de sedimentos de corrente mostrou maiores fatores de enriquecimento para As, Cd, Mn, Ni e Zn, e foram restritos aos locais mais róximos das fontes geradoras de drenagens ácidas. Neste caso, os processos de sedimentação ocorreram em zonas de mistura das soluções ácidas com águas fluviais, as quais contribuíram para a neutralização da acidez e a conseqüente precipitação das espécies químicas / Abstract: This study was developed in coal mining area, region of Figueira (PR). The first part of this study searched physico-chemical processes of the acid mine drainage before and after the neutralization with CaO and the evolution of these acid waters in natural stream in area with presence of carbonatic rocks. The results showed an increasing in pH of acid mine drainage after the treatment (from 3.2 to 4.6) and a reduction in concentrations of analyzed constituents. The evolution of these acid waters within the tributary stream resulted in new physicochemical system, initially with pH 6.4 and lower levels of Eh and of chemical constituents, particularly SO4 2¯ (1578 mg L¯1), Al (0.07 mg L¯1), Fe (17.8 mg L¯1) and Mn (2.48 mg L¯1). However, the concentrations of these constituents were lower in natural stream with increment of pH to 10.8, except Al. Aluminum increasing concentration (from 0.07 mg L¯1 to 0.63 mg L¯1) during this evolution seems to be related to an input of Al-enriched waters due the leaching of silicate minerals in alkaline conditions. This increasing in pH can be resulted from local bedrock that contains limestone from 10.5 meters depth. Groundwater input to the natural stream contributes to the increase in HCO3¯ concentrations until the conditions of carbonate system equilibrium are broken with the excess CO3 2¯, increasing the water pH to 10.8. In this point, favorable conditions happened to the removal of Mn, a problem found in neutralization process of acid drainage. The second part of this work evaluated the geochemistry characteristics of acid drainage in this region, and the impacts in waters and surface sediments. The results showed that the acid drainage is generate as much in coal extraction gallerias as in tailing deposits, with pH from 3.2 to 4.1. These last drainages showed the higher concentrations of analyzed elements, especially As (from 0.25 mg L¯1 to 0.68 mg L¯1). The impact of these acid solutions to the rivers in the area had little meaning. The concentrations of SO4 2¯, Al, Cd, Co, Fe, Mn, Ni and Zn (near to the active mines) and SO4 2¯, Al, Cd, Fe, Mn and Zn (near the tailing deposits and abandoned mines) exceeded the Brazilian quality standards to stream waters. Groundwater monitoring wells from the active mines showed the same interval of pH and chemical concentrations were similar to those of acid drainages, which represented significant impacts. However, the stream water and groundwater samples of municipal public provision revealed pH from 7.2 to 7.5 and low concentrations of analyzed components. The geochemistry of stream sediments showed higher enrichment factors to As, Cd, Mn, Ni e Zn, and were restrict to the nearest places of acid drainages generation source. In this case, the sedimentation processes happened in the mixing zone of the acid solutions with stream waters, which caused the neutralization of acidity and the precipitation of the chemical species / Mestrado / Geologia e Recursos Naturais / Mestre em Geociências

Orientadores: Regina Maura Bueno Franco, Romeu Cantusio Neto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-20T10:40:41Z (GMT). No. of bitstreams: 1 BarrosJunior_AntoniodeLima_M.pdf: 1672242 bytes, checksum: 0bd26a05a56bc387ae7abcdcf5d0c478 (MD5) Previous issue date: 2011 / Resumo: Os protozoários patogênicos gastrointestinais, Cryptosporidium spp. e Giardia spp. estão amplamente presentes em ambientes aquáticos e suas formas infectantes (oocistos e cistos), são resistentes às condições ambientais (temperatura e radiação solar) e ao processo de desinfecção da água (principalmente à cloração). Inúmeros surtos de gastroenterite foram causados por estes organismos devido à veiculação hídrica, sendo que estes protozoários patogênicos tornaram-se uma preocupação constante para os sistemas produtores de água. Os objetivos desta pesquisa foram: verificar a ocorrência de cistos de Giardia spp. e oocistos de Cryptosporidium spp. em amostras de água do rio Capivari em dois pontos, identificados como CAP1 (localizado na estação de tratamento de água ETA Capivari) e CAP2 (à montante da mesma estação), avaliar a interface sedimento-água no ponto CAP1, com periodicidade mensal de agosto 2009 à Janeiro 2011, avaliar a qualidade da água mediante análise microbiológica e físico-química deste manancial. Para os ensaios parasitológicos, foi empregada a técnica de filtração em membrana de acordo com Franco et al., (2001) e visualização mediante reação de imunofluorescência direta (RID) com anticorpos monoclonais comerciais para visualização de cistos e oocistos; para ensaios microbiológicos visando a detecção de coliformes termotolerantes, utilizou-se a técnica de tubos múltiplos de acordo com os procedimentos descritos no STANDARD METHODS 21a edição (APHA, AWWA, WEF, 2005). As análises das amostras da Interface sedimento-água foram processadas pela técnica de centrífugo-concentração através da metodologia que emprega desagregação química acrescida de desagregação físico-química por ultrassom. Ao todo, 36 amostras de água bruta superficial e 18 amostras da interface sedimento-água foram coletadas. Nos pontos CAP1 e CAP2, cistos de Giardia spp. foram detectados em 94,1 % e 100,0 % das amostras, respectivamente; na interface sedimento-água 94,5 % das amostras foram positivas para cistos de Giardia spp. Oocistos de Cryptosporidium foram detectados no ponto CAP1 em 6,6 % das amostras, em 13,3 % das amostras no ponto Cap2 e em 16,6 % das amostras da interface sedimento-água durante toda a pesquisa. Ambos os protozoários foram detectados nas diferentes amostras do rio Capivari / Abstract: The gastrointestinal pathogenic protozoa Cryptosporidium spp. and Giardia spp. are ubiquitous in aquatic environment and their infectious forms (cysts and oocysts) are resistant to environmental conditions (temperature and solar radiation) and the water disinfection process (mainly chlorination). Numerous outbreaks of gastroenteritis were caused by these organisms due to waterborne transmission and these parasitic protozoa have become a constant concern for systems producing water. The aims of this research were: to investigate the occurrence of Giardia cysts and Cryptosporidium oocysts in water samples of Capivari River in two sites identified as CAP1 ( in the plant of water treatment named ETA Capivari) and CAP2 (upstream from the same plant); to evaluate the sediment-water interface in site CAP1, from august 2009 to january 2011, to assess water quality of this source by microbiological and physical-chemical analysis. For parasitological assays, the membrane filter technique according to Franco et al. (2001) was employed followed by visualization by direct immunofluorescence assay (IFA) with commercial monoclonal antibody kit for enumerating cysts and oocysts. For microbiological tests aiming the detection of thermo tolerant coliforms, multiple tubes technique was used according to the procedures described in STANDARD METHODS 21a edition (APHA, AWWA, WEF, 2005). The analysis of the sediment-water interface samples were made by centrifugation and concentration technique through the methodology that uses chemical disaggregation followed by physical-chemical disaggregation using ultrasonic equipment. 36 fresh water samples and 18 sediment-water interface samples were collected. In CAP1 and CAP2 sites, cysts of Giardia were detected in 94,1 % and 100% of the samples, respectively; in sediment-water interface, 94,5 % of the samples presented Giardia cysts. Cryptosporidium oocysts were detected in 6,6 % of the samples from CAP1 site, in 13,3 % samples from CAP2 site and in 16,6 % of the samples from sediment-water interface during all the research. Both protozoa were detected in different samples of the Capivari river / Mestrado / Parasitologia / Mestre em Parasitologia

M.Sc. / Please refer to full text to view abstract

M.Sc. / The study looks into the sediment-bound metals (Fe, Mn, Cu, Cr, Cd, Co, Pb, Ni, Zn and Hg) of the Leeu/Taaibospruit catchment, which is impacted by agricultural, industrial and urban development. A number of chemical procedures, including total metal determination, the Tessier-sequential extraction scheme, the BCR Protocol, evaluation of the % TOC and determination of AVS to SEM ratios were applied to sediment samples collected from eight sites along the two rivers in the study area. Samples were collected during both high flow (summer) and low flow (winter) conditions. Following the chemical characterisation, bioaccumulation testing was conducted by exposing chironomid larvae to the sediment samples collected in from the study sites and determining their metal uptake relative to control specimens in uncontaminated sediments. These bioaccumulation results were then considered in conjunction with the chemical parameters in an attempt to identify any trends and correlations. Significant spatial and temporal differences were found in the metal concentrations from the study area. The total extraction results indicated that abundant amounts of Cr and Fe are present throughout the system. This was expected based on the make-up of the underlying geology. In addition, one of the sites, which is in close proximity to the town of Sasolburg, was identified as a potentially contaminated site. This site had significantly higher concentrations of Zn, Cu, Pb and, most notably, Hg when compared to the other sites. The elevated metal concentrations are most evident in samples collected under low flow conditions, but are also seen in the high flow Hg concentrations. Sequential extractions showed that Fe and Cr are concentrated in the residual phases of the sediment. Copper is largely present in the oxidisable fraction under low flow conditions, but also has considerable residual and reducible chemical forms. Manganese and Zn are distributed among all the different chemical phases and are therefore likely to be readily available for uptake by benthic organisms. The TOC was found to be highest during low flow conditions and at those sites with observable amounts of organic debris from the surrounding reeds and other vegetation. The AVS/SEM ratios were used to predict that due to the formation of insoluble metal sulphides, Cd, Cu, Hg, Ni, Pb and Zn are unlikely to be bioavailable at certain sites, i.e. the contaminated site 1 and at site 5, which only has agricultural impacts. In general, the bioaccumulation of Fe, Co, Ni, Cr and Mn was higher in the test larvae than the control larvae. Bioaccumulation of Cu, Pb, Zn and Hg levels were only higher than the control worms at sites where contamination was suspected to have taken place. Average bioaccumulation factors indicated that Hg is the metal that is most readily available for bioaccumulation, followed by Cu, Zn and Mn. All of these metals were bioconcentrated in the tissues of the test chironomids, while levels of Fe, Ni, Cr and Pb were found to be lower in the organisms than in the sediments. Although many of the chemical fractions were found to correlate significantly with the uptake of the different metals, the best overall correlation existed between the bioaccumulated metal and the total non-residual fraction. In fact, the sum of the first four steps of the Tessier-scheme correlated significantly with the bioaccumulated metal for all elements considered in the calculation, except for Pb. Additionally, the predictions made by the AVS model were found to be useful in justifying the behaviour and accumulation patterns of Hg, Zn and Cu at certain sites. The correlations and bioavailability clearly differed spatially, temporally and among the different elements. It is therefore suggested that prediction of the bioavailability and subsequent uptake of sediment-bound metals will require as many chemical and environmental factors as possible, and should include bioaccumulation and toxicity testing in order to examine the validity and completeness of these predictions.

The Triassic Molteno Formation is a clastic sedimentary sequence consisting of a series of cycles, dominated lithologically by coarse grained sandstones. Aspects of the petrography have been examined using the conventional petrographic microscope as well as the scanning electron microscope. Both solution and overgrowth features are present not only on the quartz grains but also on certain of the heavy mineral species present. Intrastratal solution of garnet would appear to be a significant feature in the Molteno Formation. Mineralogical examination of the laterally persistent Indwe Sandstone Member indicates no significant variation in heavy mineral content. Evidence from a study of zircon elongation ratios shows the presence of two distinct zircon populations indicating two provenance areas. X-ray diffraction and electron microprobe analysis has identified mineral species characteristic of granites, pegmatitic granite and metamorphic rocks, especially amphibolites. Palaeocurrent data indicates that this source area lay to the south-east; to the south the source area consisted mainly of the Cape Supergroup sediments. Analysis for Nb, Zr, Y, Sr, Rb, Zn, Mn, Ba, Cu, Ni, Co, Cr, V and Ti for 22 samples from the Molteno Formation, indicates, as expected for a highly arenaceous sequence, a substantial depletion in these trace elements. No consistent variation of trace element concentration occurs with height in the sequence so trace element content may not be used for purposes of stratigraphic correlation. There are indications of trace element variation with geographical position, no doubt a reflection of the contribution of 2 source areas of different compositions. Factor analysis of the interelement correlations has identified 3 factors which influence the trace element content of the Molteno Formation these are a "heavy mineral" factor, a "pH-Eh" factor and a "clay mineral" factor. These trace factors are ultimately an expression of the source rock composition, the prevailing climate and a combination of the two. Comparison with the more argillaceous overlying Elliot Formation, indicates that factors influencing geochemical variation in this sequence were far more complex than for the Molteno Formation

The Sustut Group within the study area is a nonmarine succession of fine to coarse grained elastics, deposited in an alluvial fan environment. Regionally, the Sustut Group is divisible into the Tango Creek and Brothers Peak Formations. In the study area, the two formations are entirely Late Cretaceous (Campanian to Maastrichtian) in age, based on palynological evidence. In the southern Sustut Basin, only the uppermost 400 m of the Tatlatui Member of the Tango Creek Formation is exposed. Sediments of the Tatlatui Member are divided into fine and coarse grained lithofacies. The fine grained lithofacies is composed of interbedded mudstone, siltstone and fine grained sandstone, which is interpreted as an alluvial plain deposit. Pebble conglomerate interbedded with coarse to medium grained sandstone comprise the coarse grained lithofacies which is considered to be a braided river deposit. The Brothers Peak Formation comprises 1 000 m of diverse elastics and tuffs, which are divisible into the lower and upper Laslui Member, and the overlying Spatsizi Member. The lower Laslui Member conformably overlies the Tatlatui Member of the Tango Creek Formation, and is characterized by several fining upwards sequences of cobble conglomerate to medium grained sandstone, attributed to deposition by high energy braided streams in the mid-fan region of an alluvial fan complex. Sediments of the upper Laslui Member are divided into a fine grained lithofacies consisting of mudstone, interbedded with lesser amounts of siltstone, fine grained sandstone and tuff beds, and a coarse grained lithofacies composed of orthoconglomerate, paracong1omerate and coarse grained sandstone. The fine grained lithofacies comprises the majority of the sequence and is interpreted as an alluvial plain deposit. Coarse grained sediments of the upper Laslui Member were likely deposited during stages of high water discharge, by major distributaries, sheetfloods and debris flows. The Spatsizi Member is gradational from the upper Laslui Member and is composed of sandstone/mudstone sequences interpreted as sandy braided stream deposits of an alluvial plain. Detrital components of the Tango Creek and Brothers Peak sandstones are mainly chert, quartz, plagioclase and volcanic rock fragments. Paleocurrent measurements and provenance considerations suggest source terranes were located to the east during Tango Creek deposition, and to the west during Brothers Peak deposition. In the southern Sustut Basin, the Tango Creek Formation documents uplift and erosion in the Omineca Belt and Paleozoic rock units, following accretion of the first composite terrane (terrane I) to the North American Margin. The Brothers Peak Formation is considered a result of local uplift and volcanic activity, accompanying the accretion of a second composite terrane (terrane II). / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

As atividades antrópicas impactam de forma significativa os recursos hídricos, especialmente devido ao lançamento de efluentes domésticos e industriais. Os sedimentos constituem o principal compartimento de acumulação de poluentes, particularmente os metais como o chumbo (Pb), o cádmio (Cd), o cromo (Cr), o zinco (Zn) e o cobre (Cu). A persistência ambiental, a toxicidade e a capacidade de bioacumulação e biomagnificação em cadeias alimentares destes poluentes despertam especial interesse no que tange aos diagnósticos ambientais e aos sistemas de gestão de recursos hídricos. O presente estudo objetivou avaliar de forma integrada o comportamento de um corpo hídrico por meio da análise de metais biodisponíveis em sedimentos e na coluna d’água de amostras oriundas de 5 pontos de amostragem da bacia hidrográfica do Rio Tega (RS) visando contribuir para o desenvolvimento de estudos de diagnóstico ambiental e o avanço do conhecimento acadêmico no Brasil acerca do tema. Foram realizadas 5 campanhas de amostragem envolvendo análises “in loco” e laboratoriais da qualidade da água utilizando-se métodos padronizados pelo Standard Methods. Os compostos metálicos em sedimentos foram analisados por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP-OES) e nas amostras de água por absorção atômica. Os resultados obtidos evidenciam, para os metais estudados, concentrações maiores para as amostras de sedimentos em comparação às amostras de água superficial, especialmente para Cu, Ni, Zn e Cr, que apresentaram também concentrações superiores aos níveis de efeito provável (Probable Effects Level) – PEL, preconizado nos Valores Guia de Qualidade dos Sedimentos (VGQS). As maiores concentrações de metais em sedimento foram observadas nos pontos de amostragem 1 e 2, localizados diretamente na área urbana, os quais também apresentaram os piores índices de qualidade da água. No ponto de amostragem 3, as concentrações médias de metais em sedimento foram as menores, embora esse ponto drene as águas do distrito industrial do município, que não apresentam qualidade. No ponto de amostragem 4, localizado em uma barragem, evidencia-se igualmente o acúmulo de espécies metálicas. O ponto de amostragem 5, localizado no exutório da bacia hidrográfica indica a contribuição desta para o Rio das Antas, da qual é tributária. Sendo o município de Caxias do Sul o segundo polo metal-mecânico do Brasil e tendo este como uma de suas atividades a galvanotécnica, fica evidente a contribuição deste ramo industrial para o aporte de íons metálicos ao corpo hídrico estudado, apontando para a necessidade de medidas de controle e fiscalização mais efetivas no sentido de minimizar os impactos ao ecossistema aquático, considerando-se os efeitos cumulativos destes sobre a cadeia trófica e por consequência sobre a saúde ambiental. Os resultados do estudo ressaltam a importância de monitorar a qualidade dos sedimentos e de promover um controle eficiente das fontes locais de poluição. No entanto, ainda é necessário avançar no desenvolvimento de novas estratégias e introduzir novas ferramentas para gestão ambiental para os recursos hídricos / Human activities may cause significant impacts on water resources, especially due to the release of domestic and industrial effluents. Sediments are the main compartment for accumulating pollutants, particularly metals such as lead (Pb), cadmium (Cd), chromium (Cr), zinc (Zn) and copper (Cu). Environmental persistence, toxicity and the ability to bioaccumulate and biomagnify at food chains of these pollutants play an important role in environmental diagnostics and water resource management systems. This study aimed to evaluate the behavior of a water body through the analysis of bioavailable metals in sediments and in the water column of 5 sampling points of the Rio Tega watershed (RS), in order to contribute to the development of environmental diagnosis studies and the consolidation of academic knowledge in Brazil. Five sampling campaigns involving in situ and laboratorial analyzes of water quality were carried out using Standard Methods. The metal compounds in sediments were analyzed by inductively coupled plasma-optical emission spectrometry (ICP-OES) and in water samples by atomic absorption. The results showed higher concentrations for the sediment samples compared to the surface water samples, especially for Cu, Ni, Zn and Cr, which also showed concentrations above the Probable Effects Level – PEL, recommended in the Sediment Quality Guidelines. The highest concentrations of metals in sediment were observed at sampling points 1 and 2, located in the urban area, which also presented the worst index for water quality. At the sampling point 3, the mean concentrations of metals in sediment were the lowest, although this point drains the industrial zone of the city, which do not present good quality. At sampling point 4, located in a dam, it is also evident the accumulation of metallic species. The sampling point 5, located in the place where the watershed drains out, indicates its contribution to the Rio das Antas, from which it is tributary. Since Caxias do Sul city is the second metal mechanic pole in Brazil, with the development of galvanic activities, it is evident the contribution of this kind of industries to the increase of metal concentration in the water body. The results indicate the importance for monitoring sediment quality and promote efficient control of local sources of pollution. However, further development of new strategies and tools for environmental management related to water resources is still necessary.