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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+.

Amostras de água de chuva foram coletadas no campus da USP Ribeirão Preto (RP) de agosto de 2002 a dezembro de 2005. Cerca de 84% (n=127) das amostras apresentaram excesso de acidez, com pH médio de 5,12. Não se observou sazonalidade no pH de acordo com o período de safra da cana. As concentrações médias ponderadas pelo volume (MPV, em mol L-1): K+ 3,9 (n=175), Na+ 2,1 (n=172), Ca2+ 5,0 (n=175) e Mg2+ 1,8 (n=168), observadas em RP, bem como seus fluxos de deposição por via úmida, foram ligeiramente mais elevadas que aquelas encontradas em chuvas de regiões com características semelhantes. As concentrações destes cátions foram sazonais, com um aumento no período de safra, sendo que a maior diferença foi observada para o íon K+, indicando a sua importante fonte na queima de biomassa. A sazonalidade do íon Ca2+ aponta para a importância das atividades agrícolas, intensificadas no período de safra, na emissão deste cátion para a atmosfera. Observaram-se boas correlações lineares entre as concentrações de Na+ e K+ (0,67626) e de Na+ e Ca2+ (0,77822), indicando a possibilidade de emissões pirogênicas e a ressuspensão do solo serem fontes de emissão de Na+. A MPV de carbono orgânico dissolvido (COD) encontrada em RP foi mais elevada que na Amazônia, onde também há intensa queima de biomassa, porém seus fluxos por via úmida em ambas as regiões foram similares (0,42 molCm-2ano-1). As concentrações de COD em RP apresentaram correlações lineares significativas com K+ (0,70341) e com Ca2+ (0,61638), apontando para a queima de biomassa e ressuspensão do solo como fontes importantes de emissão de carbono orgânico para a atmosfera. As concentrações de COD nas chuvas de Araraquara foram ainda maiores que em RP, indicando pronunciadas fontes locais naquela cidade. As MPV (nmol L-1) de Cd 0,54 (n=56), Pb 3,02 (n=94) e Cu, 19,9 (n=98), encontradas nas chuvas de RP foram semelhantes a regiões urbanas e industriais do hemisfério norte, enquanto a concentração de Al (448 nmol L-1, n=126) foi menor, e a de Zn (405 nmol L-1, n=120) apresentou-se dentro das faixas de concentrações relatadas nestes locais. Com exceção de Cd, os demais metais analisados (Pb, Cu, Zn e Al) também apresentaram concentrações significativamente maiores (P=0,05) nas chuvas durante o período de safra, indicando que a queima de biomassa e as atividades agrícolas podem aumentar a emissão destes metais para a atmosfera de RP. A correlação linear significativa entre Pb e Ca2+ (0,53845), indica a participação da ressuspensão do solo no aporte atmosférico de Pb em RP, enquanto a ausência de correlação linear entre Zn e K+ (0,20182) parece indicar a presença de outras fontes significativas de Zn para a atmosfera de RP, além da queima de biomassa. O cálculo do fator de enriquecimento demonstra que Cd, Zn, Pb e Cu estão enriquecidos com relação ao solo na chuva de RP, sugerindo que estes podem ter fontes antrópicas locais e / ou distantes. A análise preliminar de componentes principais não esclareceu o peso das diferentes fontes de emissão atribuídas neste trabalho. / Rain water samples were collected based on events at the University of São Paulo - campus Ribeirão Preto - from August 2002 to December 2005. About 84% (n=127) of the samples had excess of acidity, with an average pH of 5.12. There was no correlation between the pH values and the sugar cane harvest period. The Volume Weighed Means (VWM, in mol L-1) for K+ 3.9 (n=175), Na+ 2.1 (n=172), Ca2+ 5.0 (n=175) and Mg2+ 1.8 (n=168), and their wet fluxes in RP were slightly higher than those reported to regions with similar characteristics. The concentrations for these cations were seasonal, with higher values during the harvest period. The largest difference was observed for K+, indicating its important source in the biomass burning activity. The seasonality showed for Ca2+ is probably related to the higher soil resuspension during the more intense agricultural activities. A good linear correlation observed between Na+ and K+ (0.67626) and between Na+ and Ca2+ (0.77822), suggest that Na+ may have important pirogenic as well as soil dust sources. The VWM for Dissolved Organic Carbon (DOC) in RP was higher than that reported for rainwater in the Amazon region (where the biomass burning is also intense); however, the wet fluxes from both sites were very similar (0.42 mol C m-2 ano-1). DOC concentrations were well correlated with K+ (0.70341) and Ca2+ (0.61638), suggesting that the biomass burning as well as soil dust can be important sources of organic carbon to the atmosphere. DOC concentrations in rainwater from Araraquara were even higher than those for RP, showing a high local source of organic carbon. The VWM (nmol L-1) for Cd 0.54 (n=56), Pb 3.02 (n=94) and Cu 19.9 (n=98) found in the rainwater from RP were similar to urban and industrialized regions of the Northern Hemisphere, while for Al (448 nmol L-1, n=126) it was lower, and for Zn (405 nmol L-1, n=120) the VWM was within the range reported for such areas. Except for Cd, all the other metals measured (Pb, Cu, Zn and Al) also showed higher concentrations (P=0.05) in rainwater samples during the harvest period, suggesting that biomass burning and intensive agricultural activities can increase these species concentrations in the atmosphere. The significant linear correlation between Pb and Ca2+ (0.53845) indicates that soil inputs can be of relevance for Pb atmospheric inputs in RP. On the other hand, the absence of linear correlation between Zn and K+ (0.20182) seems to indicate the presence of other important sources for Zn to the atmosphere besides biomass burning. The calculated Enrichment Factor showed that Cd, Zn, Pb and Cu are anomalously enriched in RP rainwater in relation to soil, suggesting these metals may have antroprogenic local sources as well as distant ones. The preliminary statistical analysis of principal components did not clarify the weight of the different sources of emission attributed in this work.

The aim of this study was to investigate the factors that affect the dissolution of a suite of trace metals from aerosols into seawater from wet and dry deposition, with a focus on important trace metals: manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and lead (Pb). To this end, aerosol and rainwater samples were collected from Tudor Hill (Bermuda) and Penlee Point (Cornwall) atmospheric observatories and surface seawater samples were collected from the Sargasso Sea and the Celtic Sea. These representative aerosol, rainwater and seawater samples were used in aerosol leaching and rainwater mixing experiments, which simulated the processes of mixing and trace metal dissolution following wet and dry deposition as closely as possible within the laboratory. Key variables were changed to investigate the effect of aerosol source/composition, seawater temperature, pH, dissolved oxygen concentration and organic ligand amendments on aerosol and rainwater trace metal dissolution. Results for aerosol leaching experiments revealed that changes to key physico-chemical conditions had little effect on the amount of Mn, Fe, Co, Ni and Pb leached from aerosols and therefore plausible future changes in ocean surface temperature, pH and oxygenation are unlikely to affect the flux of these important trace metals to surface waters. Conversely, aerosol source and composition had a significant effect on the dissolution of aerosol Fe, Co and Pb, with the most anthropogenically influenced aerosol samples displaying the highest solubilities. Therefore, future changes in land use and fossil fuel combustion are likely to affect the flux of these metals to the surface ocean. Fractional solubilities were in the range of 50 – 104% for Mn, 0.3 – 3.2% for Fe, 29 – 58% for Co, 40 – 85% for Ni and 67 – 112% for Pb. In addition, novel empirical relationships were found between the fractional solubilities of Fe, Co and Pb and enrichment factors for antimony, vanadium, Ni and Cu. This suggests that these fractional solubilities in seawater could be predicted using only total aerosol trace metal concentrations. The use of ultrafiltration provided unique insight into the size fractionation (colloidal 0.02 – 0.4 μm; soluble < 0.02 μm) of dissolved aerosol trace metals and showed Fe and Pb were mostly colloidal (77 – 98% colloidal), Mn and Co were mostly soluble (0 – 48% colloidal) and Ni showed a mixed profile (6 – 58% colloidal) when released from aerosols into ambient seawater. However, in the presence of a sufficient concentration of strong organic ligands the majority colloidal Fe was converted to soluble Fe (up to 100% soluble). Some of these organic ligands were also able to increase the soluble fraction of dissolved aerosol Mn. Similarly, the presence of organic ligands in rainwater maintained Mn, Fe, Co, Cu and Pb in the dissolved phase following delivery by rain into seawater. Rainwater ligands had no effect on the typically varied size fractionation profile of Mn, Fe, Co and Cu in rainwater mixed with seawater, UV-irradiation of rainwater, however, shifted the size fractionation of Pb in rainwater/seawater mixtures from 80 – 100% colloidal to 13 – 63% soluble, indicating that Pb-binding rainwater ligands are either colloidal or attached to colloidal matter. These findings highlight the importance of organic ligands in rainwater and seawater for retaining trace metal micronutrients and toxicants in the surface ocean, with implications for primary production.

Les métaux traces comme le plomb, le zinc sont essentiellement émis par les activités anthropiques et se retrouvent de ce fait à des concentrations beaucoup plus élevées en milieux urbains qu’en milieux ruraux. Durant ma thèse, j’ai tout d’abord testé les effets écotoxicologiques d’une exposition chronique au plomb et/ou au zinc, deux métaux particulièrement abondants en milieu urbain, chez le pigeon biset (Columba livia). J’ai ainsi pu montrer des effets nocifs du plomb, et bénéfiques du zinc sur l’immunité, le maintien de la corpulence et plusieurs paramètres de la reproduction. Du fait de la variabilité des réponses écophysiologiques des individus, les métaux traces sont susceptibles d’exercer de nouvelles pressions de sélection sur les populations urbaines et favoriser les individus capables de se détoxifier ou de tolérer de fortes concentrations en métaux. Au cours de ma thèse, j’ai mis en évidence le rôle de la mélanine dans la fixation du zinc et du plomb au niveau des plumes. Par ailleurs la coloration mélanique du plumage semblent moduler les effets du plomb et du zinc sur certains paramètres physiologiques, et les juvéniles au plumage davantage mélanique survivent mieux dans un environnement pollué en plomb. Quels que soient les mécanismes sous-jacents (i.e. rôle détoxifiant de la mélanine ou effets pléiotropes associés à sa synthèse), mes résultats soulignent l’avantage sélectif potentiel de la mélanisation du plumage dans un environnement pollué en métaux traces, dont notamment le milieu urbain. Cette étude apporte des réponses essentielles sur l’impact écologique de l’urbanisation et les mécanismes permettant le maintien du polymorphisme de coloration mélanique du plumage, et plus largement des phanères. / Trace metals, such as lead and zinc are mainly emitted by human activities, explaining their high concentrations in urban areas in comparison with rural environments. During my PhD, I first investigated the ecotoxicological effects of a chronic exposure to lead and/or zinc, two abundant metals in urban areas, in feral pigeons (Columba livia). I stressed deleterious effects of lead, while beneficial effects of zinc on immunity, body mass index maintenance and several parameters of reproduction. Because sensitivity to trace metals differs between individuals, trace metals may exert new selective pressures on urban populations and favour individuals with higher detoxification capacities and that are more tolerant to elevated environmental trace metals concentrations. My work puts ahead the role of melanin in the storage of zinc and lead in the feathers. Moreover, melanin-based plumage colouration seems to modulate the effects of lead and zinc on some of the physiological parameters measured and darker juveniles were more prone to survive than paler ones when exposed to lead. Whatever the underlying mechanism (i.e. the detoxification role of melanin or the pleiotropic effects associated with its synthesis), my results suggest a selective advantage of plumage melanism in environments polluted with trace metals, such as urban areas. This study brings key answers on the ecological impact of urbanization and on the mechanisms explaining melanin-based plumage colouration polymorphism maintenance.

The work has been focused on the preconcentration techniques for determination of 9Be, 51V, 59Co, 60Ni, 89Y, 111Cd, 208Pb, 232Th and 238U on the modified sorbents, all measurements were performed on ICP-MS. The instrument setup was optimized. The solution of internal standard (200 µg•l-1) was used during all measurements. The internal standard were chosen as follows: 6Li for 9Be, 45Sc (51V), 72Ge (59Co, 60Ni, 89Y), 103Rh (111Cd), 209Bi (206Pb, 207Pb, 208Pb, 232Th and 238U). Another parameters such as influence of mineral acids (HCl, HNO3), surfactant (Septonex®, Zephyramin, Ajatin, Brij 35 and Sodium dodecyl sulphate) and organic reagents (Ammonium pyrrolidinedithiocarbamate, 8-Hydroxyquinoline-5-sulphonic acid, 1,2-Dihydroxyanthraquinone-3-sulphonic acid and 4-(2-Pyridylazo)resorcinol) and the effect of some matrix components on intensity of instrument signal determination was investigated. For preconcentration polar Silicagel and modified nonpolar Silicagels (Silicagel-C18, C8 nad Phenyl) were used. Another experimantal part was dedicated to preconcentration on nonpolar Amberlite XAD-16 and Strata SDB-L and intermediately polar sorbent Amberlite XAD-7. Recoveries of sorption process were observed in the presence of all testing types of surfactants in certified concentration 5•10-4 mol•l-1. Surfactants were always applied in the conditioning step. The suitable combinations of surfactant and organic reagent were tested for increasing of recoveries of analytes. Testing organic reagents were added in five times mass excess againts concentration of analytes, the concentration of the organic reagents was 900 µg•l-1. The organic reagent was always added to the solution for preconcentration before this solution was led on the sorbent. The composition and a necessary volume of elution mixture for quantitative elution were tested, too. Only one sorbent was chosen from each group of sorbents with similar properties. The chosen sorbent showed the best recoveries in majority of target analytes. The highest recoveries from silica-group was reached for Silicagel-C18, from nonpolar Amberlite was chosen Strata SDB-L and intermediately polar Amberlite XAD-7. The influence of some matrix components (anionts and cations) on recoveries of analytes was investigated for chosen sorbent. The optimized process was applied on real samples of nature water and industry water. In experimental part all analytes are marked as specific izotopes, which were measured by ICP-MS. Of course, all izotopes of analytes undergo preconcentration techniques.

There is growing interest in the use of geochemical analyses for the evaluation of anthropogenically altered soils and other archaeological deposits. Areas of human habitation and activity tend to accumulate greater levels of soil phosphorus and trace metals. These elevated concentrations leave permanent signatures that can only be removed by erosion of the soil itself, and so phosphorus and trace metal mapping have become popular field procedures to identify areas of habitation and activity. Gridded soil samples were collected and soil phosphate and trace metal ions were extracted to identify these activity areas at the ancient Fremont site Wolf Village located in Goshen, UT. The geochemical analysis of the chemical patterns indicates possible areas of ancient activity such as food preparation, craft production, and waste. These results and techniques will be used to help locate additional activity areas for future excavation of the site as well as settlement and activity areas of ancient sites in the western US.

No description available.

The application of olivine to coastal areas is a proposed method of removing carbon dioxide from the atmosphere for climate change mitigation. Olivine is abundant and dissolves relatively fast, but it contains trace amounts of nickel (Ni), chromium (Cr), and cobalt (Co) which may be toxic to marine biota in cases of widespread coastal olivine spreading. Prior studies have suggested that Ni concentrations in marine sediments and/or the overlying water column due to olivine dissolution could be a limiting factor for its carbon capture potential. Therefore, it is critical to understand and model the processes affecting trace metal bioavailability after olivine application. This research used sand and sediments collected from a natural olivine beach (Papakōlea) and a black sand control beach (Richardson) in Hawaii to measure the adsorption of Ni, Cr, and Co to suspended particulate matter (SPM) in the water column and to beach sediments in equilibrium with pore water. The experimentally derived adsorption isotherms were then used for phase distribution modeling in the water column and sediment pore water at both sites. Cr was observed to readily precipitate in seawater without suspended solids, meaning its exposure pathway for marine organisms will likely be via sediment, regardless of interactions with solid phases. Co uptake from solution may have been influenced by biological processes based on its continuous adsorption over 30 days, but more study ofcobalt adsorption to SPM is required because of conflicting results in a repeated experiment. Thus, Ni was the focus of the phase distribution modeling in this work. Ni adsorption from seawater to SPM generated from both Papakōlea and Richardson sediments followed Langmuir adsorption models. Parameters for Ni adsorption to SPM from Papakōlea at pH 7.81 were KL = 2.74 L/kg and qmax = 931 mg/kg and for Richardson SPM at pH 8.00 they were KL = 5.69 L/kg and qmax = 1446 mg/kg. Ni adsorption to SPM was strongly affected by pH with the qmax for Richardson SPM nearly eight times greater at pH 8.00 than at pH 7.77. Ni adsorption to Papakōlea SPM was five times greater than Ni adsorption to Richardson SPM at comparable pH. Ni adsorption to beach sediments from both sites was measured for five pHs between 7.27 and 8.73. Ni adsorption was observed to be strongly affected by pH and sediment type. A significant adsorption edge was observed for the Papakōlea sediment between pH 8.00 and 8.22, while a gradual increase in adsorption was observed between pH 7.27 and pH 8.15 for the Richardson sediment. Ni adsorption to the beach sediments from pore water at the typical seawater pH of 8.05 was calculated by interpolation between adsorption models at surrounding pH values. Calculated Ni adsorption to Papakōlea sediment at pH 8.05 was linear with Kd = 22.4 L/kg while Ni adsorption to Richardson sediment at pH 8.05 followed a Langmuir model with KL = 0.8 L/kg and qmax = 179 mg/kg. Phase distribution models constructed with the experimentally derived adsorption isotherms predicted that over 85% of the Ni in the water column is dissolved. This result was similar for the water columns at both beaches and was based on typical coastal total suspended solids (TSS) concentrations (5-20 mg/L). Therefore, it is predicted that transport of Ni into marine sediments by SPM settling is much smaller than bulk transport of dissolved Ni into the open ocean. In contrast, the pore water models predict that over 95% of total Ni is adsorbed to the solid phase for both sediments. In a scenario where dissolved Ni concentration in the pore water is the maximum safe level of 8.2 ppb (US EPA environmental quality standard; EQS), Ni adsorbed to the sediment at both sites is predicted to be less than 10% of safe levels, the Florida Department of Environmental Protection’s threshold exposure limit (TEL) of 15.9 mg Ni per kg of sediment. These adsorbed Ni concentrations are likely a better indicator of threshold sediment Ni concentrations because presumably Ni adsorbed to sediments is more readily bioavailable than Ni in the structure of the olivine. In this case, dissolved Ni would be of more environmental concern than Ni in seabed sediments at sites of olivine enrichment. However, it will be important to investigate the bioavailability of Ni directly from the olivine structure to confirm this conclusion. If dissolved Ni concentration in the pore water is the limiting factor for safe application of olivine, then olivine loading rates should be based on site-specific conditions (mixing regime and the residence time of seawater in the sediment pores) to maintain a dissolved Ni concentration less than the EQS. For Papakōlea Beach, with 70% olivine in thesediments, the dissolved Ni concentrations in the pore waters were measured to be at background seawater concentrations. This is likely because of the rapid mixing and high- energy wave action at this beach. Under these conditions, very little Ni would be adsorbed to the sediments. Additional site-specific studies of Ni and Co adsorption to beach sediments should be conducted to gain a more complete understanding of the fate and transport of these trace metals and the risks posed to coastal ecosystems by their release. More experiments are needed to characterize Co adsorption in seawater to SPM and beach sediment. Additionally, Ni adsorption experiments should be performed on a wider variety of beach sediments to estimate its fate and transport at specific locations of potential olivine enrichment. Also, Ni adsorption to Papakōlea SPM was measured at pH 7.81, and since adsorption is expected to be much greater at seawater pH, the Ni adsorption experiment should be repeated at a pH greater than that of seawater to allow the construction of adsorption isotherms for Papakōlea SPM at seawater pH by interpolation. Additionally, experiments need to be conducted to determine the bioavailability of trace metals in the olivine itself and adsorbed to the olivine.

Master of Science / Geology / Matthew W. Totten / The most common practice of typing crude oils utilizes biomarkers to gain insight on the history of the oil. This practice only considers the organic chemistry of the oil, and does not consider the trace element concentrations within the oil. Rare earth element and other trace element concentrations in crude oil might provide further insight into the oil’s source and origin. This study analyzed REE and other trace metal concentrations of crude oil in the Spivey-Grabs field of south-central Kansas through analysis by ICP-MS and ICP-AES that, coupled with visual physical characteristics of oil and FT-IR analysis, could explain the reported “compartmentalization” of the field and provide insight on the origin of the oils. Analysis of physical characteristics of the crude oils suggested the presence of two types of oil, of differing viscosities, in the field. FT-IR confirmed the presence of these two oil types based on functional groups present in the oils. The existence of a high viscosity oil could potentially explain the compartmentalization behavior in the field. PAAS-normalized REE distribution patterns showed a general LREE enrichment, a positive cerium and negative europium anomaly, and a MREE and HREE depletion, but higher viscosity oils showed additional MREE and HREE enrichment. K/Rb values ranged from 2,864 to 44,118, with oils from mixed-viscosity wells having lower ratios overall. K/Rb values of Spivey-Grabs crude oils more closely resembled those of the Lansing-Kansas City formation than the K/Rb values of the Woodford shale and Mississippian formation of the Anadarko basin. Comparing the rare earth element distribution patterns and K/Rb values from this study to those of the Woodford shale suggests the Spivey-Grabs oil originated from a local source and not from the Woodford shale.

The research work is directed towards the investigation, optimization and application of some plant-based waste materials for the removal of some toxic trace metals (Cd, Pb and Mn) as well as selected oxyhalides (CIO3-,IO3- and BrO3-) in aqueous system. Waste materials from three plants; Athrixia philicoide, an indigenous bush tea; the outer covering peels of butternut Squash (Cucurbita Moschata) and pineapple (Ananas comosus) were evaluated for their sorption efficiency of the selected metals. batch and continuous experimental processes as well as conditions that might influence the sorption of the metals were investigated. These conditions include effects of pH sorption time, amount of adsorbent, volume of the aqueous medium, amount of metals etc. Qualitative and quantitative analysis of metal ions in solution was carried out using the ion chromatograph (IC) while the functional group identification present in waste materials was established using the Fourier Transform infr-red spectroscopy (FTIR), Quantitative biosorption equilibrium of 98.99% was reached within 6h at pH 6 and 100 ppm concentration of Pb metal with Athrixiaphilicoide under 30 min contact time. Applicability of the sorption process was tested on wastewater. Results revealed that > 99.93 %; 84.5 % and 64.3 % sorption efficiency was obtained for Mn, Cd and Pb respectively at pH 7 using Ananas Comosus adsorbent. For Athrixia philicoide, sorption efficiency from spiked wastewater ranged from 99.98 % for Cd; 99.96 % for Mn and 82.5 % adsorption for Pb at pH 7. For Juglans Cinerea, wastewater sorption efficiency varied between 78.76 %, 94.50 % and 96.50 % for Cd, Mn and Pb respectively at pH6. Results from the optimized method revealed the applicability of the method to environmental water samples. Possible large scale and industrial/commercial application of developed materials and methods would be explored. ) in aqueous system. Waste materials from three plants; Athrixia philicoide, an indigenous bush tea; the outer covering peels of butternut Squash (Cucurbita Moschata) and pineapple (Ananas comosus) were evaluated for their sorption efficiency of the selected metals. Batch and continuous experimental processes as well as conditions that might influence the sorption of the metals were investigated. These conditions include effects of pH, sorption time, amount of adsorbent, volume of the aqueous medium, amount of metals etc. Qualitative and quantitative analysis of metal ions in solution was carried out using the ion chromatograph (IC) while the functional group identification present in waste materials was established using the Fourier Transform infra-red spectroscopy (FTIR). Quantitative biosorption equilibrium of 96.99 % was reached within 6h at pH 6 and 100 ppm concentration of Pb metal with Athrixia philicoide under 30 min contact time. Cd and Mn adsorption by the same adsorbent under similar condition were less than 50 % for individual metal evaluation experiment. However, > 99 % adsorption was achieved with Cd in a mixture of the three (3) evaluated metals. Highest adsorption of 93 % of Pb was achieved with the Butternut Squash peel (Cucurbita moschata) at the optimal sorption pH of 6 followed by quantitative sorption of 99.2 % of Mn while Cd recorded a sorption level of 45 % all at 6 pH. The sorption efficiency of Pb, Cd and Mn using pineapple peels (Ananas comosus) also at the optimal sorption conditions of (pH 6, 30 min contact time and 100 ppm metal concentration) ranged from 98.7 %, 100 % and 99.90 % respectively. / Enviromental Science / M.Sc (Enviromental Science)