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.

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)

Trace element bioaccumulation in benthic organisms is important part of aquatic environment pollution research, since water and sediment analysis itselfs do not provide significant information about bioavailability of contaminants and the results mostly shows just current pollution at the time of sampling. This study focuses on urban streams contamination which are currently significant source of trace elements. Botic stream was chosen as exemplary, because it is affected by many combined sewer system overflows which are sources of contamination in times of heavy rain and flood. Load several sampling took place on 10 stream sites during the year of 2012. This thesis deals with 11 trace elements concretelly Cd, Co, Cr, Cu, Hg, Ni, Zn, As, Fe, Pb and Al. Trace elements were assessed in both benthic organisms and sediment. As well taxons were selected from benthic organisms, which are widely found at any time of the reference year: caddisflies of family Hydropsychidae, leeches Erpobdella sp. and mayflies of Baetidae family. Sediment analysis included sequential extraction which divided trace elements into 4 fractions according to mobility. Based on the results, bioavailability was assessed on observed elements and correlation between concentration in bethos and sediment was tested. Finally, impact of...

O processamento anaeróbio da vinhaça se apresenta como uma alternativa para a recuperação de energia (biogás), e reaproveitamento das suas características nutricionais através da disposição no solo. Com o intuito de elevar a eficiência energética, o presente trabalho teve como objetivo estimular a produção de metano em reatores anaeróbios em batelada de lodo granular adaptado, alimentados com vinhaça de usina sucroalcooleira, por meio da adição de metais traço. Foram avaliadas as suplementações da vinhaça com Co, Zn, Mo, Ni, Mn e W. Na Fase 1 foram realizados 4 ensaios, os reatores foram analisados individualmente nas concentrações 200 &#956;g.L-1, 350 &#956;g.L-1, 500 &#956;g.L-1 e 800 &#956;g.L-1. Na Fase 2 verificou-se o comportamento dos metais em conjunto, à concentração de 350 &#956;g.L-1 de cada micronutriente (Co, Ni, Zn, Mo, Cu e Mn). Os dados de produção acumulada de CH4 foram ajustados pelo modelo modificado de Gompertz, e foram obtidas as constantes cinéticas. Na Fase 1, verificou-se que a concentração de 200 &#956;g.L-1 de Co foi a mais adequada aos experimentos e apresentou a maior velocidade máxima de produção de CH4, 121,30 mL.d-1 (aumento de 17% na taxa de produção de metano). Nesta mesma Fase, o W apresentou indícios de inibição à concentração de 800 &#956;g.L-1, e os demais metais exibiram os melhores resultados nesta mesma concentração, a velocidade de produção (Rm) aumentou para o Mn (26%), Ni (25%), Cu (21%) e Mo (19%), e os rendimentos mais expressivos foram para Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) e Ni (0,232 mL CH4.mg-1 DQOrem). A Fase 2 não apresentou resultados satisfatórios, as verificações não indicaram variação relevante entre os reatores do ensaio e controle. / Anaerobic processing of vinasse is presented as an alternative to energy recovery (biogas), and reuse of its nutritional characteristics through the provision on the ground. In order to increase energy efficiency, this study aimed to stimulate methane production in adapted anaerobic batch reactors with granular sludge fed with vinasse from sugarcane biorefineries, through the addition of trace metals. The supplementation vinasse were evaluated with Co, Zn, Mo, Ni, Mn and W. In phase 1 four essays were realized, and micronutrient were analyzed individually in concentrations of 200 &#956;g.L-1, 350 &#956;g.L-1, 500 &#956;g.L-1 and 800 &#956;.L-1. In phase 2 it was observed the behavior of metal together, with micronutrients concentration of 350 &#956;g.L-1 (Co, Ni, Zn, Mo, Cu e Mn). The data of methanes production were adjusted by Gompertz modified model and kinetics constants were obtained. In phase 1 it was verified that the concentration of 200 &#956;g.L-1 of Co was optimal for the experiments and showed the highest maximum production velocity of CH4, 121,30 mL.d-1 (increase of 17%). In this phase W showed evidence of inhibition at a concentration of 800 &#956;g.L-1, and other metals showed the best results in the same concentration. The velocity of production (Rm) increased to Mn (26%), Ni (25%), Cu (21%) e Mo (19%), and the most significant yields were to Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) and Ni (0,232 mL CH4.mg-1 DQOrem). Phase 2 did not show satisfactory results.