The presence of trace transition metal species in the atmosphere can be attributed to the emission of particulate matter into the atmosphere by anthropogenic activities, as well as from natural sources. Trace metals emitted into the atmosphere can cause adverse health–related and environmental problems. At present, limited data exists for trace metal concentrations in South Africa. In this investigation, the general aim was to determine the concentrations of trace metals in atmospheric aerosols in the industrialised western Bushveld Igneous Complex, as well as to link the presence of these species in the atmosphere to possible sources in the region. The measurement site was placed in Marikana, a small rural town situated 35 km east from Rustenburg in the North West Province of South Africa. It is surrounded by numerous industrial and metallurgical operations. MiniVolumeTM samplers and Teflon® filters (2 ;m pores) were utilised to collect PM2.5 and PM10 particulate samples. The MiniVolumeTM samplers were programmed to filter 5 litres of air per minute for 12 hours per day, over a six–day period. The starting time for sampling was altered every six days, in order to obtain both day and night samples. Sampling was performed for a period of one year. The collected samples were chemically analysed with inductively coupled plasma mass spectroscopy (ICP–MS). Surface analysis of the sampled filters was performed with a scanning electron microscope (SEM) in conjunction with energy–dispersive spectroscopy (EDS). The dataset was also subjected to factor analysis in an attempt to identify possible sources of trace metal species in the atmosphere. The concentrations of 27 trace metals (Be, B, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Pd, Cd, Ba, Pt, Au, Hg, Tl, Pb, U) were determined. Pd, Hg, Tl, U, Ca, Co, As, Cd, Ba and Au were above the detection limit 25% or less of the time during the sampling period. With the exception of Ni, none of the trace metals measured at Marikana during the sampling period exceeded local and international standards. Higher Ni levels were possibly due to base metal refining in the region. Pb, which is the only metal species that has a standard prescribed by the South African Department of Environmental Affairs (DEA), did not exceed any of the standards. It is also significant to refer to Hg that was below the detection limit of the analytical instrument for the entire sampling period. The impact of meteorological conditions revealed that wet removal of atmospheric PM10 trace metals was more significant than the wind generation thereof. During the dry months, the total trace metal concentrations in the PM10 fraction peaked, while PM10 particles were mostly washed out during the wet season. Wind speed showed an unexpected inverse pattern compared to wet deposition. A less significant seasonal trend was observed for the trace metal concentrations in the PM2.5 fraction, which was attributed to a faster replenishment of smaller particles into the atmosphere after rain events. Separation of trace metal concentrations into PM10–2.5 and PM2.5 fractions indicated that 79% of the total trace metal levels that were measured were in the PM2.5 fraction, which indicated a strong influence of industrial and/or combustion sources. Fractionalisation of each of the trace metal species detected showed that for each metal species, 40% and more of a specific metal was in the PM2.5 fraction, with Cr, V, Ni, Zn and Mn occurring almost completely in the PM2.5 fraction. Surface analysis with SEM supported results from the chemical analysis, which indicated that a large fraction of the particles was likely to originate from anthropogenic activities and from wind–blown dust. SEM–EDS also detected nonmetallic S that is usually associated with the Pt pyrometallurgical industry that is present in the western Bushveld Igneous Complex. Correlations between Cr, V, Ni, Zn and Mn revealed that the main sources of these species were pyrometallurgical industries. Explorative factor analysis of the unprocessed and Box–Cox transformed data for all 27 metals detected, resolved four meaningful emission sources, i.e. crustal, vanadium related, base metal related and chromium related. Comparison of trace metal species to other parameters measured (e.g. CO, BC) also indicated pyrometallurgical activities and wind–blown dust to be the main sources of trace metals in this region. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2011.

In this work, dry deposition of metals is investigated in an urban area / city of Ankara using snow as a surrogate surface. Two sampling campaigns were conducted to determine dry deposited amount of 13 species namely / H+, Na, K, Al, Mg, Fe, V, Cd, Cr, Cu, Pb, Zn, Ni. First sampling was performed after a major snow fall in Ankara in January 2001, from 4 points according to a predetermined sampling procedure in order to assess background composition of snow. After 12 days, snow samples were collected from 54 points. All samples are filtered, digested and divided into two aliquots in order to investigate soluble and insoluble fractions separately. Temporal changes of snow showed that snow is a good surrogate surface for dry deposition of metals and provide multifunctional informative data. Pollution maps of the city are drawn using Mapinfo software to investigate spatial pollution distributions. Factor analysis are applied and five main factors for these elements are found, indicating three main sources as traffic, soil and combustion. Enrichment factor calculations showed that Ni, Ca, Pb, Zn, Ni, Cu and Cd are highly enriched pointing out the anthropogenic sources affecting the city atmosphere drastically.

The Bells Creek catchment covers an area of 100 km2 in the northern part of the Pumicestone Passage region of southeast Queensland. This catchment is an example of a low-lying sub-tropical coastal plain including both freshwater and estuarine settings. The main creeks drain into Pumicestone Passage, a large shallow estuary, which is a declared marine habitat and a Ramsar listed wading bird location. The Bells Creek catchment has undergone land-use change from bushland to grazing to pine plantations and is now coming under pressure for urban development. Quaternary age unconsolidated sediments are the dominant surface material in this area and formed during the last marine transgression. Of significance for such a setting is that estuarine sediments can retain metals mobilised as a result of natural processes (e.g. weathering) and anthropogenic activities (e.g. land-use disturbance). As trace metals can also occur naturally in rocks and their weathered products, it is of value to clearly distinguish natural and anthropogenic controls over metal source, distribution and mobility. To achieve this aim two approaches were taken: 1) to determine the factors controlling the geochemistry of weathered profiles, unconsolidated sediments, soils and natural waters, and 2) to identify the most effective analytical and numerical methods for evaluating metal concentration in different solid materials. This investigation is structured around four linked papers. The influence of mineralogy, geological setting, location of water table and depth of burial on the geochemistry of weathered profile are assessed in Paper 1. The second paper is an investigation of different analytical approaches for studying weathered sedimentary rocks, as well as the testing of several numerical methods for evaluating geochemical data from weathered profiles. In paper 3, a large heterogeneous geochemical data set including trace metals, total organic carbon and sulfur content, in addition to mineralogy and land use practices are integrated to enable evaluation of geochemical and anthropogenic processes controlling metal distribution. The fourth paper considers the distribution of iron and its transport as well as variations in size and morphology of different forms of framboidal pyrite within a smaller sub-catchment in the southern part of the study area. The labile and heterogeneous nature of the bedrock of the region, the Landsborough Sandstone, along with the sub-tropical climate of the area have resulted in weathering profiles up to 26 m deep. Due to the absence of industrial activity in the Bells Creek catchment, such weathering of the bedrock constitutes the major process governing metal distribution throughout the area. Analysis by X-ray diffraction (XRD) shows that the primary minerals occurring in the weathered profiles are quartz, plagioclase and K-feldspars while kaolinite is the most dominant secondary mineral present. Overall, parent rock silicates have been extensively replaced by clay minerals and Fe oxides. The relative influence of mineralogy, geological setting and groundwater over chemical weathering and geochemical cycling of metals can be summarised as follows: Mineralogy>geological setting>watertable position>depth of profile burial As the relationship between the total metal composition and the extractable and mobile component has environmental significance, a comparison was made between these forms of metals in weathered material. This comparison shows that metals such as V, Cr and Fe are part of the aluminosilicate matrix and remain largely in primary mineral structures. The retention of these metals may lead to their future release to the environment during on-going weathering. Other elements such as Cu, Zn, Pb, however, are found to be primarily adsorbed to sediment particles and therefore, easily releasable to the environment. As limited information on weathering of sedimentary rocks is reported in the literature, a variety of chemical analysis and numerical assessment methods were used to understand the geochemical processes involved in trace metal mobility in the weathered profiles. Two analytical methods of digestion, hydrofluoric acid and x-ray fluorescence were tested and found to be highly comparable except for refractory elements such as V and Cr. Among the numerical methods applied to the dataset were "chemical and mineralogical indices", "weight loss factor" and "immobile element approach". The "immobile element approach" was found to be the most appropriate method to characterise the weathering profiles typical of the catchment. This method considers a weathering system to be open and transforms the absolute values of trace metals enabling a quantitative evaluation of metal mobility. The following sequence of mobility was determined after applying this method to the data generated in this study: Zn>Pb>Cu>Cr>V The above sequence of mobility is supported by the comparison between extractable and total metal concentrations where Cr and V were identified as being part of aluminosilicate matrix and less mobile. On the other hand, Zn, Pb and Cu were found to exist in adsorbed form and to be readily released to the environment. Trace elements released through weathering and erosion of the bedrock can accumulate in estuarine and coastal sediments. Therefore, both the lateral and vertical distribution of trace metals within sediments and soils of Bells Creek catchment were investigated. Natural and anthropogenic factors controlling metal distribution were compared and it was concluded that the natural sediment character such as its mineral content is more significant than anthropogenic influences in controlling lateral and vertical metal distribution. Further, due to varying degrees of weathering and the heterogeneous nature of soils and sediments, the data were normalised. After testing several methods, it was concluded that calculation of an enrichment factor was the most appropriate. The enrichment factor revealed that elevated trace metal concentrations at some sites are due to bedrock weathering. Due to the environmental persistence of iron, excess of this common metal has always been of environmental concern in many coastal settings. In the small Halls Creek sub-catchment, for example, iron anomalies were detected in bottom sediments (Fe up to 14%). This finding has significance in the area, as iron has been identified as one of the major contributors in the growth of the toxic cyanobacteria "Lyngbya majuscula" which can negatively impact on aquatic fauna. Iron concentrations were also shown to be high in natural stream waters of this coastal zone (up to 16 mg/L); in the bottom sediments of the creek, iron occurs as hematite (freshwater section) or pyrite (estuarine section). A variety of pyrite morphologies were identified in both bottom sediments and particulate matter samples including spherical closely packed framboids, and the rare form of euhedra which indicates slow crystallisation. The different components of this investigation have: 1) established the order and extent to which natural factors control weathering, 2) tested a number of analytical and numerical methods in evaluating weathering profiles, 3) assessed natural and anthropogenic factors and established the mobility sequence for trace metals in weathered profiles and, 4) determined the iron mineral speciation and established morphological variations of pyrite. As the area of Bells Creek catchment will be under development pressure in the future, findings of this study represent a baseline of comparison for environmental assessment and are of importance for environmental management.

Thesis (Ph.D.) - Carleton University, 2002. / Includes bibliographical references (p. 188-198). Also available in electronic format on the Internet.

abstract: Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients, such as iron, copper, and molybdenum. This work investigated the effects of BSC activity on soil solution concentrations of bioessential elements and examined the microbial production of organic chelators, called siderophores. I found that aluminum, vanadium, copper, zinc, and molybdenum were solubilized in the action of crusts, while nickel, zinc, arsenic, and zirconium were immobilized by crust activity. Potassium and manganese displayed behavior consistent with biological removal and mobilization, whereas phosphorus and iron solubility were dominated by abiotic processes. The addition of bioavailable nitrogen altered the effects of BSCs on soil element mobilization. In addition, I found that the biogeochemical activites of BSCs were limited by molybdenum, a fact that likely contributes to co-limitation by nitrogen. I confirmed the presence of siderophore producing microbes in BSCs. Siderophores are low-molecular weight organic compounds that are released by bacteria to increase element solubility and facilitate element uptake; siderophore production is likely the mechanism by which BSCs affect the patterns I observed in soil solution element concentrations. Siderophore producers were distributed across a range of bacterial groups and ecological niches within crusts, suggesting that siderophore production influences the availability of a variety of elements for use in many physiological processes. Four putative siderophore compounds were identified using electrospray ionization mass spectrometry; further attempts to characterize the compounds confirmed two true siderophores. Taken together, the results of my work provide information about micronutrient cycling within crusts that can be applied to BSC conservation and management. Fertilization with certain elements, particularly molybdenum, may prove to be a useful technique to promote BSC growth and development which would help prevent arid land degradation. Furthermore, understanding the effects of BSCs on soil element mobility could be used to develop useful biomarkers for the study of the existence and distribution of crust-like communities on ancient Earth, and perhaps other places, like Mars. / Dissertation/Thesis / Ph.D. Geological Sciences 2012

abstract: Particulate trace metals can enter the atmosphere as mineral dust, sea spray, anthropogenic emissions, biomass burning, etc. Once in the atmosphere they can undergo a variety of transformations including aqueous phase (cloud) processing, photochemical reactions, interact with gases, and ultimately deposit. Metals in aerosols are of particular interest because of their natural and anthropogenic sources as well as their effects on local (human health) and global (climate change) scales. This work investigates the metal component of atmospheric particles and how it changes during physical and chemical processes at local, regional and global scales, through laboratory and field studies. In the first part of this work, the impact of local dust storms (haboobs) on ambient metal concentrations and speciation is investigated in Tempe, AZ. It was found that metal concentrations substantially increase (> 10 times) during these events before returning to pre-storm levels. In a second part of this work, the impact of fog processing on metal concentrations, solubility and speciation is examined through field observations in California’s Central Valley. The observations show that fog processing has a profound effect on local metal concentrations but the trends are not consistent between sites or even between events, indicating complex processes that need further investigation. For example, fogs have an effect on scavenging and solubility of iron in Davis, while in Fresno soluble iron content is indicative of the source of the aerosol. The last part of the thesis investigates the role of particle size on the solubilization of iron from mineral dust aerosols during global atmospheric transport through laboratory experiments. The experiments showed that mineralogy and pH have the greatest effect on iron solubility in atmospheric aerosols in general while particle size and photochemistry impact mainly the solubility of iron oxides. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2015

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Sediments have been used as environmental indicator because of its ability to incorporate and accumulate contaminants, with the surface layers it is possible to analyze the increase or decrease of concentrations of trace metals in the environment, since both metals incorporated from natural sources as the of anthropogenic origin. However the bioindicators more accurately reflect the condition of the metal pollutants in the environment that only the measurements of the concentrations of the metals present in the sediment and water. The present study evaluated geochemistry of sediments and of the rocky substrate, together with the chemistry of three species of macroalgae rhodophytas; Gracilaria sp., Hypnea musciformis and Cryptonemia crenulata. We defined two stretches of beaches located in the state of Ceara, which are important environments for macroalgal banks exploited economically in this state. The excerpts represent two different situations investigated the Coqueiros beach in the municipality of Caucaia near sources of pollution, urban and industrial, and beach Flecheiras located in the municipality of Trairi far from urban centers and industries. The sampling occurred in March 2011 and the materials were analyzed by optical emission spectrometry with inductively coupled plasma (ICP-OES) for sediment and via mass spectrometry with inductively coupled plasma source (ICP-MS) for macroalgae. The results obtained in this study showed high levels of barium and zirconium compared to the crustal average latter with values similar in both study sites (837  499 mg kg-1). Ba levels were higher especially in the beach sediments of Coqueiros (1799-38680 mg kg-1) and lower in the beach sediments Flecheiras (1034 to 2148 mg kg-1). The levels of Ba in the rocky substrate were lower but varied between 387 and 1048 mg kg-1 at the beach of Coqueiros beach against 214-524 mg kg-1 at the Flecheiras beach. Although proximity to anthropogenic sources such as industrial and urban centers could put pressure on the found levels especially barium, natural origins of barium and zirconium anomalies cannot be discarded. Chemical analysis revealed Gracilaria sp. species in which the elements Al, Ba, Be, Ca, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Ge, Hf, Ho, Li, Lu, Mn, Mo , Pb, Rb, Sc, Sn, Sr, Tb, Ti, Tl, Tm, U, V, Y, Yb and Zn observed in individuals from Coqueiros was greater than that observed in specimens Flecheiras. However the concentration of the elements As, Cd and B was significantly higher in Flecheiras Beach. In species Hypnea musciformes the concentration of the elements Mo and especially to Ba, the Coqueiros beach was higher than that observed in specimens beach Flecheiras. The elements As, B, Cd, and Sr, the relative concentration of the samples was higher than Flecheiras referring to individuals of Coqueiros, this difference was very significant for the elements As and Cd in relation to the concentration of trace elements in the species Cryptonemia crenulata were observed only for B and Co. The concentration of B in individuals of Coqueiros was greater than that observed in specimens Flecheiras. And the element Co was higher in samples Flecheiras than that observed in specimens of Coqueiros. Referring to verify bioaccumulation factor for macroalgae Gracilaria sp Beach Coqueiros was significantly higher than that observed in specimens Flecheiras for trace elements Sc (P = 0.038), Sr (P = 0.018) and especially Zn (P = 0.005) and Zr (P = 0.007). The difference was significant for trace element Y (P = 0.057). In samples of macroalgae Cryptonemia crenulata bioaccumulation factor, found in individuals originating from Flecheiras was significantly higher than that observed in specimens Coqueiros only for trace element Co (P = 0.037). The bioindicators more efficient in determining the metals in these sectors is the species Gracilaria sp. bioindicator ideal and one being the bioindicators essential tools in the control and monitoring of trace metals in coastal environments both beaches proved to be contaminated with various toxic elements among much more toxic. / Sedimentos tÃm sido utilizados como indicador ambiental devido sua capacidade de incorporar e acumular elementos contaminantes, com as camadas superficiais à possÃvel analisar o aumento ou o decrÃscimo das concentraÃÃes de metais traÃo no ambiente, uma vez que incorporam simultaneamente os metais oriundos de fontes naturais quanto os de origem antrÃpicas. Entretanto os bioindicadores refletem de maneira mais precisa a condiÃÃo dos metais poluentes no ambiente do que somente as medidas das concentraÃÃes dos metais presentes no sedimento e na Ãgua. O presente estudo avaliou a geoquÃmica de sedimentos e do substrato rochoso, juntamente com a quÃmica de trÃs espÃcies de macroalgas rhodophytas; Gracilaria sp., Hypnea musciformis e Cryptonemia crenulata. Delimitamos dois trechos de praias localizadas no estado do CearÃ, os quais sÃo importantes ambientes para bancos de macroalgas explorados economicamente neste estado. Os trechos investigados representam duas situaÃÃes distintas a praia dos Coqueiros situada no municÃpio de Caucaia prÃxima de fontes poluentes, urbana e industrial, e praia Flecheiras situada no municÃpio de Trairi longe de centros urbanos e indÃstrias. A amostragem ocorreu em marÃo de 2011 e os materiais foram analisados via espectrometria de emissÃo Ãptica com plasma indutivamente acoplado (ICP-OES) para os sedimentos e via espectrometria de massas com fonte de plasma indutivamente acoplado (ICP-MS) para as macroalgas. Os resultados obtidos nessa pesquisa mostraram valores altos de bÃrio e zircÃnio em relaÃÃo à mÃdia crustal, este Ãltimo com valores mÃdios semelhantes em ambos os locais de estudo (837  499 mg kg-1). Os nÃveis de Ba foram maiores especialmente nos sedimentos da praia dos coqueiros (1799 a 38680 mg kg-1) e em menor nÃvel nos sedimentos da praia de Flecheiras ( 1034 a 2148 mg kg-1). Os nÃveis de Ba no substrato rochoso foi menor mas variou entre 387 e 1048 mg kg-1 na praia dos Coqueiros contra 214 a 524 mg kg-1 na praia de Flecheiras. Embora a proximidade de fontes antrÃpicas como indÃstrias e centros urbanos possa exercer pressÃo sobre os nÃveis especialmente de bÃrio encontrados, origens naturais das anomalias de bÃrio e zircÃnio nÃo podem ser descartadas. As anÃlises quÃmicas na espÃcie Gracilaria sp. revelaram que os elementos Al, Ba, Be, Ca, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Ge, Hf, Ho, Li, Lu, Mn, Mo, Pb, Rb, Sc, Sn, Sr, Tb, Ti, Tl, Tm, U, V, Y, Yb e Zn, verificada nos indivÃduos oriundos de Coqueiros foi maior que a observada nos espÃcimes de Flecheiras. Entretanto a concentraÃÃo dos elementos As, B e Cd foi significantemente maior na Praia de Flecheiras. Na espÃcie Hypnea musciformis a concentraÃÃo dos elementos Mo e, sobretudo, para Ba, na praia dos Coqueiros foi maior que a observada nos espÃcimes da praia de Flecheiras. Os elementos As, B, Cd, e Sr, a concentraÃÃo relativa Ãs amostras de Flecheiras foi maior que a referente aos indivÃduos de Coqueiros, tal diferenÃa foi muito significante para os elementos As e Cd. Em relaÃÃo à concentraÃÃo de elementos-traÃo na espÃcie Cryptonemia crenulata foram constatadas apenas para B e Co. A concentraÃÃo de B nos indivÃduos de Coqueiros foi maior que a verificada nos espÃcimes de Flecheiras. E o elemento Co foi maior nas amostras de Flecheiras do que a observada nos espÃcimes de Coqueiros. Referente ao fator de bioacumulaÃÃo verificamos para a macroalga Gracilaria sp da praia dos Coqueiros foi significantemente maior que o observado nos espÃcimes de Flecheiras para os elementos-traÃo Sc (P = 0,038), Sr (P = 0,018) e, sobretudo, Zn (P = 0,005) e Zr (P = 0,007). A diferenÃa foi significante para o elemento-traÃo Y (P = 0,057). Nas amostras da macroalga Cryptonemia crenulata o fator de bioacumulaÃÃo, verificado nos indivÃduos originÃrios de Flecheiras foi significantemente maior que o observado nos espÃcimes de Coqueiros apenas para o elemento-traÃo Co (P = 0,037). Os bioindicadores mais eficientes na determinaÃÃo dos metais nesses setores à a espÃcie Gracilaria sp. uma bioindicadora ideal e sendo os bioindicadores ferramentas essenciais no controle e monitoramento de metais traÃo em ambientes costeiros ambas as praias revelaram-se contaminadas por diferentes elementos entre muito tÃxicos a mais tÃxicos.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2018-02-27T16:54:04Z No. of bitstreams: 1 Dissertação Rodrigo Wanick final .pdf: 4229460 bytes, checksum: 57308d047672489aade74b41da93624d (MD5) / Made available in DSpace on 2018-02-27T16:54:04Z (GMT). No. of bitstreams: 1 Dissertação Rodrigo Wanick final .pdf: 4229460 bytes, checksum: 57308d047672489aade74b41da93624d (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Neste trabalho foi realizado a identificação das metalotioneínas na ostra Crassostrea rhizhophore para sua aplicação em estudos de caratér ambiental. Para realizar a identificação, forma necessárias adaptações no metódo de extração protéica descrito por Viarengo et. al (1997). / In this work metallothioneins were identified in the mangrove oyster Crassostrea rhizophorae to be used in environmental studies, employing modifications in the protein extraction method descrived by Viarengo et. al (1997).

Dissertação(mestrado) - Universidade Federal do Rio Grande, Programa de Pós-Graduação em Oceanografia Física, Química e Geológica, Instituto de Oceanografia, 2005. / Submitted by Cristiane Silva (cristiane_gomides@hotmail.com) on 2013-01-28T12:25:06Z No. of bitstreams: 1 2005_Carlos_de_Andrade.pdf: 1453728 bytes, checksum: 61ca4996bcaf13cd39bc0418f7b5608b (MD5) / Approved for entry into archive by Bruna Vieira(bruninha_vieira@ibest.com.br) on 2013-06-13T18:51:07Z (GMT) No. of bitstreams: 1 2005_Carlos_de_Andrade.pdf: 1453728 bytes, checksum: 61ca4996bcaf13cd39bc0418f7b5608b (MD5) / Made available in DSpace on 2013-06-13T18:51:07Z (GMT). No. of bitstreams: 1 2005_Carlos_de_Andrade.pdf: 1453728 bytes, checksum: 61ca4996bcaf13cd39bc0418f7b5608b (MD5) Previous issue date: 2005 / A cidade de Rio Grande, localizada às margens do estuário da Lagoa dos Patos, possui uma intensa atividade portuária e industrial, fatores que promoveram nas últimas décadas, alterações significativas nas paisagens e na degradação dos recursos hídricos, incluindo a contaminação por nutrientes e por metais. Por ser um estuário semi-fechado, possui uma alta taxa hidrodinâmica, condicionada principalmente pela força e direção dos ventos. Os ciclos biogeoquímicos naturais dos metais na coluna dágua, podem ser alterados devido ao lançamento de metais oriundos das atividades humanas. Alterações na fração dos metais podem ocasionar uma maior biodisponibilidade destes elementos para os organismos. A determinação das espécies de metais biodisponíveis (lábil) por técnicas instrumentais ou analíticas, possuem implicações quanto à obtenção da concentração representativa do meio, por estar sujeita a erros de amostragem e preparo das amostras. Com o desenvolvimento da técnica de gradiente difusivo de membranas (DGT), obtem-se a concentração da fração lábil in situ em distintos ambientes sob diversas condições de pH, temperatura e salinidade. O presente trabalho tem como objetivo avaliar e aplicar a técnica DGT, para o monitoramento e detecção da concentração de elementos traço em distintos locais da área estuarina da Lagoa dos Patos. Para avaliar a aplicabilidade da técnica para o estuário, foram considerados dois períodos de exposição do sistema DGT em três locais: um com pouca influência (Ilha dos Marinheiros - IM) e dois com maior influencia dos despejos industriais e urbanos (Capitania dos Portos - CP e Museu Oceanográfico - MO). Para o primeiro período de exposição (2, 6 e 10 dias) das unidades de DGT foram analisados Cd, Co, Cu, Mn, Ni, Pb e Zn em DGT e água nos locais IM e CP. Para o segundo período de exposição (2, 4, 6 e 8 horas) DGT e água foram analisados para Cd, Cu, Pb e Zn no local MO em duas amostragens, uma com salinidade intermediária (MO1) e a outra com salinidade alta (MO2). Para ambos períodos de exposições, amostras de água analisadas para a fração lábil de metais com resina Chelex 100, demonstraram concentrações distintas em comparação ao DGT, evidenciando a diferença entre os dois métodos. Os resultados no DGT para o primeiro período de exposição (IM e CP) mostraram um decréscimo nas concentrações de todos os elementos, com o aumento do tempo de exposição. Isto provavelmente tenha ocorrido devido à baixa concentração de metais lábeis na água e/ou possível presença de biofilm nas unidades de DGT. Não foram reveladas concentrações significativas de Cu, Pb, Ni e Zn nos locais IM e CP. Para o segundo período de exposição, as concentrações de metais foram mais elevadas para Cd, Cu e Pb em alta salinidade (MO2), além de ter indicado aporte para este elementos no meio, quando comparado com outros estuários. Em conseqüência das variabilidades do estuário, conclui-se que uma resposta mais representativa para o sistema DGT, seria mantê-lo num período fixo de 8 a 48 horas em exposição no ambiente. / Rio Grande is a city located in the margin of the Patos Lagoon estuary and its maritime harbour and industries are very developed. During the last decades, these activities were responsible for many changes of the landscape and degradation of water resources, including contamination by nutrients and metals. This semi-closed estuary has a high hydrodynamic rate, which is determined manly by the wind direction and strength. The natural biochemical cycles of metals can be modified by discharge of metals originated by human activities. Changes in the metal fractions can lead to a higher bioavailability of these elements to the organisms. The determination of bioavailable (labile) metals by instrumental or analytical techniques can have implications on the representative environmental concentration, since errors during sample collection and preparation can occur. The development of the diffusive gradient thin-films (DGT) technique made possible the determination of labile metals in situ in distinct environments with different conditions of pH, temperature and salinity. The main objective of the present study is to apply and to evaluate the DGT technique, for the monitoring and detection of trace elements concentrations in different areas of the Patos Lagoon estuary. To evaluate the applicability of this technique to the estuary, two deployment periods of the DGT units were considered in three areas: one with low antropogenic influence (Ilha dos Marinheiros – IM) and two in high urban and industrial discharge areas (Capitania dos Portos – CP – and Museu Oceanográfico – MO). For the first period of the DGT deployment (2, 6 and 10 days) DGT and water samples were analyzed for Cd, Co, Cu, Mn, Ni, Pb and Zn at the IM and CP sites. For the second deployment period (2, 4, 6 and 8 hours), Cd, Cu, Pb e Zn were analyzed for DGT and water samples were collected at the MO point, during two different conditions of salinity, one with intermediate values (MO1) and the other with high salinity (MO2). For both deployment periods, water samples analyzed for labile fraction with Chelex-100 resin showed distinct concentrations, when compared with the DGT, indicating differences between the two methods. The DGT results showed for the first deployment period (IM and CP) a decrease with time in the concentration for all elements. Probably this had occurred due to variations on the labile form of the metals and/or the presence of biofilm. No significant differences were found in the concentration of Cu, Pb, Ni and Zn between IM and CP sites. For the second deployment period, trace metal concentrations showed higher values for Cd, Cu and Pb during high salinity (MO2) condition, as well as indicating input of these elements in the surroundings when compared with other estuaries. As a consequence of variability’s in the estuary, it can be concluded that for a more representative result of the DGT units, these should be deployed during 8 to 48h on a fixed period in the environment.

Submitted by Alisson Mota (alisson.davidbeckam@gmail.com) on 2015-07-20T19:22:15Z No. of bitstreams: 1 Dissertação - Francisco Alexandre Fernandes Mariano.pdf: 2085876 bytes, checksum: be811ea97cd738da2088f0b8473be519 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-23T13:30:53Z (GMT) No. of bitstreams: 1 Dissertação - Francisco Alexandre Fernandes Mariano.pdf: 2085876 bytes, checksum: be811ea97cd738da2088f0b8473be519 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-23T13:36:28Z (GMT) No. of bitstreams: 1 Dissertação - Francisco Alexandre Fernandes Mariano.pdf: 2085876 bytes, checksum: be811ea97cd738da2088f0b8473be519 (MD5) / Made available in DSpace on 2015-07-23T13:36:28Z (GMT). No. of bitstreams: 1 Dissertação - Francisco Alexandre Fernandes Mariano.pdf: 2085876 bytes, checksum: be811ea97cd738da2088f0b8473be519 (MD5) Previous issue date: 2014-05-06 / FAPEAM - Fundação de Amparo à Pesquisa do Estado do Amazonas / Composites were prepared with activated carbon (AC) of oily sludge impregnated with synthetic iron oxide in proportions 1:1 and 4:1, and temperatures of 400, 600 and 800 °C. Composites and CA were investigated and compared their capability to removal of organic (methylene blue, MB) and inorganic compounds (Cd2+ and Pb2+) in the aqueous system. These materials were characterized by analytical techniques of infrared spectroscopy, thermogravimetry, scanning electron microscopy, X-ray diffraction and Mössbauer spectroscopy (only iron oxide). Except CA, other materials showed varying degrees of magnetization in the presence of magnet hand. This characteristic was due to the presence of magnetite and/or maghemite and/or metallic iron confirmed by infrared spectroscopy and X-ray diffraction. Iron oxide it a stoichiometric and crystalline hematite confirmed mainly by Mössbauer spectroscopy. Composites and CA showed upper thermal stability to 300 °C. Tests removal capability of the MB, Cd2+, and Pb2+ were carried out at room temperature and pH~4.5. Adsorption capacity for MB for the CA was 141.6 mg g-1, this value was higher to that observed for the composites ranged between 128.8 (CP611) and 99.4 mg g-1 (CP811). The adsorption process for the MB showed better correlation values for the Langmuir isotherm, typical monolayer adsorption. The surface area was estimated indirectly by the maximum values of MB adsorption capacity of the studied materials, where AC of 273 m2 g-1 and the composites between 247 m2 g-1 (CP611) and 191 m2 g-1 (CP811). Composites showed excellent results for removal to Cd2+ ranged from 223 mg g-1 (CP411) to 503 mg g-1 (CP611), while Pb2+ ranged from 218 (CP841) to 486 mg g-1 (CP611) compared values found in the literature. Composites are also better represented by Langmuir. The CP611 composite showed higher adsorption affinity Cd2+ the higher presence magnetic phase while the CP811 had higher affinity for Pb2+ to having higher contribution of activated carbon in its composition. These materials are great for remediation of MB, Cd2+ and Pb2+. / Os compósitos foram preparados a partir de carvão ativado (CA) de borra oleosa impregnado com óxido de ferro sintético, nas proporções de 1:1 e 4:1, e temperaturas de 400, 600 e 800 °C. Os compósitos e CA foram investigados e comparados suas capacidades de remoções de compostos orgânico (azul de metileno, MB) e inorgânicos (Cd2+ e Pb2+) em sistema aquoso. Esses materiais foram caracterizados pelas técnicas analíticas de espectroscopia no infravermelho, termogravimetria, microscopia eletrônica de varredura, difração de raios X e espectroscopia Mössbauer (somente óxido de ferro). Exceto o CA, os demais materiais apresentaram variados graus de magnetização frente a imã de mão. Essa característica foi devida a presença de magnetita e/ou maghemita e/ou ferro metálico confirmada pela espectroscopia de infravermelho e difração de raios X. O óxido de ferro trata-se de uma hematita estequiométrica e cristalina confirmada, principalmente pela espectroscopia Mössbauer. Os compósitos e CA apresentaram estabilidade térmica superior a 300 °C. Os testes de capacidade de remoção do MB, Cd2+e Pb2+ foram realizados a temperatura ambiente e em pH ~4,5. A capacidade de adsorção do CA para o MB foi de 141,6 mg g-1, esse valor foi superior ao observado para os compósitos em que variou entre 128,8 (CP611) e 99,4 mg g-1 (CP811). O processo de adsorção para o MB apresentou melhores valores de correlações para isoterma de Langmuir, típico de adsorção em monocamada. A área superficial foi estimada indiretamente pelos valores máximos de capacidade de adsorção do MB pelos materiais estudados, para o CA com 273 m2 g-1 e para os compósitos entre 247 m2 g-1 (CP611) e 191 m2 g-1 (CP811). Os compósitos apresentaram excelentes resultados para remoção para o Cd2+ que variou de 223 (CP411) a 503 mg g-1 (CP611), enquanto que o Pb2+ variou de 218 (CP841) a 486 mg g-1 (CP611), em comparação valores encontrados na literatura. Os compósitos também são melhores representados por Langmuir. O compósito CP611 apresentou maior afinidade de adsorção pelo Cd2+ a maior presença de fase magnética enquanto que o CP811 teve maior afinidade pelo Pb2+ por ter maior contribuição de carvão ativado na sua composição. Esses materiais são ótimos para remediação de MB, Cd2+ e Pb2+.