Devido aos crescentes problemas relacionados com a poluição atmosférica na região metropolitana de São Paulo que atingem o ambiente e a saúde das populações, toma-se de grande interesse o estabelecimento de metodologias tal como a de monitoramento da qualidade do ar usando organismos cosmopolitas. O biomonitoramento é um método experimental que permite avaliar a resposta de organismos vivos à poluição, oferecendo vantagens como custos reduzidos, eficiência no monitoramento de amplas áreas geográficas e de elementos químicos poluentes presentes em baixas concentrações no ambiente e acumulados no biomonitor ao longo de um período. No presente trabalho, o método de análise por ativação neutrônica foi aplicado à determinação de elementos acumulados em amostras do fungo liquenizado Canoparmelia texana coletadas em duas áreas distintas: (1) Parques Estaduais Carlos Botelho (PECB) e Intervales (PEI), área considerada não-poluída pertencente ao ecossistema de Mata Atlântica - SP e (2) área metropolitana de São Paulo em pontos localizados nas proximidades das estações automáticas de monitoramento da Companhia de Tecnologia de Saneamento Ambiental (CETESB). Os liquens coletados dos troncos de árvores foram previamente limpos, moídos e posteriormente irradiados com nêutrons do reator IEA- R1 juntamente com os padrões sintéticos dos elementos. A precisão e exatidão dos resultados analíticos foram avaliadas por meio das análises dos materiais certificados de referência IAEA-336 LICHEN e Mixed Polish Herbs (INCT-MPH-2). Os resultados obtidos nestes materiais de referência foram concordantes com os valores certificados e apresentaram, em geral, uma boa precisão com coeficientes de variação variando de 0,9 a 14,6%. Os resultados das análises de liquens indicaram que os elementos As, Co, Cr, Cs, La, Mo, Sb, Sc, Se e U estão presentes aos níveis de ng g-1, Ba, Br, Cl, Fe, K, Mn, Na, Rb e Zn aos niveis de mg g-1 e Ca aos níveis de μg g-1. Por meio da aplicação das análises de cluster e de discriminate, aos resultados obtidos nas amostras coletadas em áreas com diferentes níveis de poluição, os pontos de amostragens foram agrupados segundo similaridades químicas no que diz respeito às suas composições elementares. Também foi observado que as amostras do PECB e do PEI separaram-se dos grupos e subgrupos formados pelas amostras da região metropolitana e este resultado indica a preservação das áreas consideradas não-poluídas. Os liquens coletados no PEI apresentaram, em geral, concentrações inferiores àquelas obtidas para a região metropolitana de São Paulo principalmente para os elementos relacionados com ações antrópicas. Os mapas de distribuição das concentrações de elementos permitiram a visualização e identificação de pontos que apresentam concentrações de elementos mais altas na região metropolitana. Estes mapas de distribuição também mostraram que a poluição na região metropolitana de São Paulo apresenta perfis diferentes devido às inúmeras fontes de emissão de poluentes. Os elementos determinados nos liquens da área metropolitana indicaram ser de origens industrial, veicular e do solo. Os resultados obtidos neste trabalho mostraram a viabilidade do uso da C. texana na avaliação da poluição no biomonitoramento passivo de diversos elementos contaminantes presentes na atmosfera da região metropolitana de São Paulo. / Due to the increasing problems of atmospheric pollution in the Sao Paulo metropolitan region that affect the environment and human health the application of biomonitoring methodologies using cosmopolite organisms has now become relevant. Biomonitoring is a method to evaluate the response of live organisms to pollution. This method offers advantages such as reduced costs, efficient monitoring of large geographic areas and accumulated pollutants over a large period in which low concentrations of chemicals elements in the environment can be evaluated. In the present study, neutron activation analysis method was applied to determine elements accumulated in Canoparmelia texana lichenized fungi. Samples were collected in two distinct areas: Carlos Botelho (PECB) and Intervales (PEI) State Parks that are considered as non-polluted areas and that belong to the Atlantic Forest - SP ecosystem; and Sao Paulo city metropolitan region in sites near automatic monitoring stations of the Environmental Protection Agency of the State of Sao Paulo (CETESB). The lichens collected from the bark of the trees were properly treated, and irradiated with neutrons from IEA-R1 nuclear reactor along with synthetic standards of elements. The precision and the accuracy of the results were evaluated by the analyses of IAEA-336 LICHEN and Mixed Polish Herbs (INCT -MPH-2) certified reference materials. The results obtained for these materials were in accordance with the certified values and presented good precision with variation coefficients ranging from 0.9 to 14.6%. Results obtained for lichens showed that elements As, Co, Cr, Cs, La, Mo, Sb, Sc, Se and U are present at ng g-1 levels, Ba, Br, Cl, Fe, K, Mn, Na, Rb and Zn at μg g-1 and Ca at mg g-1. By applying cluster and discriminant analyses to the results for the lichen samples from areas with different levels of pollution, the sampling sites were grouped according to their chemical similarities and their elemental composition. It was also observed that samples from PECB and PEI were separated from groups and subgroups formed by the samples from the metropolitan region. This result indicates the preservation of PECB and PEI areas considered non-polluted. The lichens collected in the PEI presented, in general, lower concentrations of the elements than those from the metropolitan region of São Paulo in regards to those elements related to anthropogenic actions. The distribution maps of element concentrations allowed identification of sites in the metropolitan region that present higher elemental concentrations. Furthermore the distribution maps also showed that the pollution in the metropolitan region presents different profiles due to many sources and different pollutant emissions. The probable sources of elements determined in lichens from the metropolitan region are industrial, vehicular and soil. Results obtained indicate that the C. texana species can be used as a passive biomonitor of element pollution in the Sao Paulo metropolitan area. This species is abundant in both polluted and non-polluted areas and thus allows to distinguish regions with distinct levels of pollution.

Devido aos crescentes problemas relacionados com a poluição atmosférica na região metropolitana de São Paulo que atingem o ambiente e a saúde das populações, toma-se de grande interesse o estabelecimento de metodologias tal como a de monitoramento da qualidade do ar usando organismos cosmopolitas. O biomonitoramento é um método experimental que permite avaliar a resposta de organismos vivos à poluição, oferecendo vantagens como custos reduzidos, eficiência no monitoramento de amplas áreas geográficas e de elementos químicos poluentes presentes em baixas concentrações no ambiente e acumulados no biomonitor ao longo de um período. No presente trabalho, o método de análise por ativação neutrônica foi aplicado à determinação de elementos acumulados em amostras do fungo liquenizado Canoparmelia texana coletadas em duas áreas distintas: (1) Parques Estaduais Carlos Botelho (PECB) e Intervales (PEI), área considerada não-poluída pertencente ao ecossistema de Mata Atlântica - SP e (2) área metropolitana de São Paulo em pontos localizados nas proximidades das estações automáticas de monitoramento da Companhia de Tecnologia de Saneamento Ambiental (CETESB). Os liquens coletados dos troncos de árvores foram previamente limpos, moídos e posteriormente irradiados com nêutrons do reator IEA- R1 juntamente com os padrões sintéticos dos elementos. A precisão e exatidão dos resultados analíticos foram avaliadas por meio das análises dos materiais certificados de referência IAEA-336 LICHEN e Mixed Polish Herbs (INCT-MPH-2). Os resultados obtidos nestes materiais de referência foram concordantes com os valores certificados e apresentaram, em geral, uma boa precisão com coeficientes de variação variando de 0,9 a 14,6%. Os resultados das análises de liquens indicaram que os elementos As, Co, Cr, Cs, La, Mo, Sb, Sc, Se e U estão presentes aos níveis de ng g-1, Ba, Br, Cl, Fe, K, Mn, Na, Rb e Zn aos niveis de mg g-1 e Ca aos níveis de μg g-1. Por meio da aplicação das análises de cluster e de discriminate, aos resultados obtidos nas amostras coletadas em áreas com diferentes níveis de poluição, os pontos de amostragens foram agrupados segundo similaridades químicas no que diz respeito às suas composições elementares. Também foi observado que as amostras do PECB e do PEI separaram-se dos grupos e subgrupos formados pelas amostras da região metropolitana e este resultado indica a preservação das áreas consideradas não-poluídas. Os liquens coletados no PEI apresentaram, em geral, concentrações inferiores àquelas obtidas para a região metropolitana de São Paulo principalmente para os elementos relacionados com ações antrópicas. Os mapas de distribuição das concentrações de elementos permitiram a visualização e identificação de pontos que apresentam concentrações de elementos mais altas na região metropolitana. Estes mapas de distribuição também mostraram que a poluição na região metropolitana de São Paulo apresenta perfis diferentes devido às inúmeras fontes de emissão de poluentes. Os elementos determinados nos liquens da área metropolitana indicaram ser de origens industrial, veicular e do solo. Os resultados obtidos neste trabalho mostraram a viabilidade do uso da C. texana na avaliação da poluição no biomonitoramento passivo de diversos elementos contaminantes presentes na atmosfera da região metropolitana de São Paulo. / Due to the increasing problems of atmospheric pollution in the Sao Paulo metropolitan region that affect the environment and human health the application of biomonitoring methodologies using cosmopolite organisms has now become relevant. Biomonitoring is a method to evaluate the response of live organisms to pollution. This method offers advantages such as reduced costs, efficient monitoring of large geographic areas and accumulated pollutants over a large period in which low concentrations of chemicals elements in the environment can be evaluated. In the present study, neutron activation analysis method was applied to determine elements accumulated in Canoparmelia texana lichenized fungi. Samples were collected in two distinct areas: Carlos Botelho (PECB) and Intervales (PEI) State Parks that are considered as non-polluted areas and that belong to the Atlantic Forest - SP ecosystem; and Sao Paulo city metropolitan region in sites near automatic monitoring stations of the Environmental Protection Agency of the State of Sao Paulo (CETESB). The lichens collected from the bark of the trees were properly treated, and irradiated with neutrons from IEA-R1 nuclear reactor along with synthetic standards of elements. The precision and the accuracy of the results were evaluated by the analyses of IAEA-336 LICHEN and Mixed Polish Herbs (INCT -MPH-2) certified reference materials. The results obtained for these materials were in accordance with the certified values and presented good precision with variation coefficients ranging from 0.9 to 14.6%. Results obtained for lichens showed that elements As, Co, Cr, Cs, La, Mo, Sb, Sc, Se and U are present at ng g-1 levels, Ba, Br, Cl, Fe, K, Mn, Na, Rb and Zn at μg g-1 and Ca at mg g-1. By applying cluster and discriminant analyses to the results for the lichen samples from areas with different levels of pollution, the sampling sites were grouped according to their chemical similarities and their elemental composition. It was also observed that samples from PECB and PEI were separated from groups and subgroups formed by the samples from the metropolitan region. This result indicates the preservation of PECB and PEI areas considered non-polluted. The lichens collected in the PEI presented, in general, lower concentrations of the elements than those from the metropolitan region of São Paulo in regards to those elements related to anthropogenic actions. The distribution maps of element concentrations allowed identification of sites in the metropolitan region that present higher elemental concentrations. Furthermore the distribution maps also showed that the pollution in the metropolitan region presents different profiles due to many sources and different pollutant emissions. The probable sources of elements determined in lichens from the metropolitan region are industrial, vehicular and soil. Results obtained indicate that the C. texana species can be used as a passive biomonitor of element pollution in the Sao Paulo metropolitan area. This species is abundant in both polluted and non-polluted areas and thus allows to distinguish regions with distinct levels of pollution.

ABSTRACT Foraminiferal Assemblages on Sediments and Reef Rubble at Conch Reef, Florida USA Christy Stephenson Benthic foraminiferal assemblages are widely used to interpret responses of the benthic communities to environmental stresses. This study compares epibiotic foraminiferal assemblages, collected from reef rubble, with those from reef sediments. The study site, Conch Reef, is the site of the Aquarius Underwater Habitat research facility and includes protected areas used only for scientific studies. Although a number of studies have enumerated foraminiferal taxa from the Florida reef tract, no projects have focused on the assemblages that occur at Conch Reef. Sediment and reef rubbles samples were collected via SCUBA from a depth range of 13 to 26 m during October 2008. Foraminiferal assemblages were assessed and compared between the two sample types. A total of 117 foraminiferal species, representing 72 genera, 37 families, and 8 orders were identified in 13 sediment samples and 21 rubble samples. In the rubble samples, 70 genera were identified, including 12 symbiont-bearing genera representing 20% of the total assemblage, 12 stress-tolerant genera representing 6%, planktic foraminifers representing 1%, and 46 other smaller foraminiferal genera representing 73% of the total foraminiferal assemblage. The rubble samples were quite homogenous. The mean (+SD) Fisher alpha α diversity of genera in these samples was 12.9 + 1.4. Sediment samples included 60 of the same genera. The 12 symbiont-bearing genera represented 41% of the total assemblage, 10 stress-tolerant genera represented 3%, planktic taxa represented 2%, and 40 other smaller foraminiferal genera represented 54% of the total assemblage. Overall, the taxonomic assemblages were very similar between the sample types, with sediment assemblages clearly representing the local and regional reef foraminiferal assemblage. The mean (+SD) Fisher alpha α for sediment samples was 11.4 + 2.3, which is not significantly different from that found for the rubble samples. A concentration ratio comparing relative abundances in sediment vs. rubble samples revealed that shells of larger, symbiont-bearing taxa were about 2.5-5.5 times more concentrated in the sediment, indicating winnowing of smaller taxa. Shells of Siphonatera, an agglutinated miliolid, and Textularia, an agglutinated textularid, were more abundant in sediments than in rubble, indicating high preservation potential. The concentration ratio provides a new taphonomic index that reflects the size and durability of foraminiferal taxa. The mean FORAM Index (FI) for the sediment samples (5.57 + 0.83) indicates that water quality at Conch Reef is suitable for calcifying symbioses. The most abundant symbiont-bearing genera were Amphistegina, Laevipeneroplis, Asterigerina, and Archaias.

Luminescence measurements have been applied to three different structures namely, sulphate, fluorides and YAG. In all cases the RE doping suppresses the intrinsic emission and results in intense luminescence characteristic of the RE dopant. Additionally, in double doped samples, or contaminated ones, the TL data show that each dopant defines a glow peak, which is displaced in temperature relative to the others. Examples of this were discussed for CaS04:Ce,Mn; YAG:Nd,Tb,Cr,Mn; BaF2:Ho,Ce and BaF2:Tm,Ce. The data are discussed in terms of an energy transfer model between different parts of extended defect complexes which encompass the RE ion and the lattice defects. Calcium sulphate doped with Dy define a TL peak near 200°C suitable for radiation measurements, but when co-doped with Ag the TL peak move to higher temperatures with minor effects on the peak sensitivity. In Ce,Mn double doped samples, the peak temperatures differ by -7°C between the Ce and Mn sites. The TL glow curves from alkaline earth fluorides are complex and contain several overlapping peaks. Curve fitting show that the peak maxima below room temperature are insensitive to the RE dopant. Additionally the host material has a modest effect on the peak positions. Above room temperature each dopant provides a TL curve specific to the added RE ion and do not show common peaks. Concentration has many effects on the resultant glow curve, and even at the lowest concentration used here (0.01%) there is evidence of cluster formation. Samples with high RE content show low values of the frequency factor consistent with the energy transfer model in that the emission from RE-RE cluster dominates over the emission from direct charge recombination within the defect complex. The effect of concentration and the TL mechanism operating below room temperature are also discussed. Luminescence signals from the near surface of YAG:Nd (via CL) were contrasted with those from the bulk material via RL. Results indicate that the outer few micron layers differ significantly in luminescence response from the bulk crystal. The differences were ascribed to result from solvents that enter the YAG lattice during the growth stage or subsequently from cleaning treatments via the dislocations caused by cutting and polishing. Additionally, the growth stage may include gases from the residual air in the growth furnace trapped into the YAG lattice. In each case there is a discontinuity in luminescence intensity and/or emission wavelengths at temperatures which mach the phase transitions of the contaminants. At the transition temperature there will be a sudden pressure change and this will induce surface expansion or bulk compression. The differences between the two cases were detected by the alternatives of CL and RL excitation, where the Nd or Er lines have moved in opposite directions. The detection of such low concentrations of solvents/trapped gases by luminescence is extremely difficult due to experimental limitations. Hence their role in luminescence generation is normally ignored.

No description available.

Hydrocarbon chains are a basic component in a number of systems as diverse as biological membranes, phospholipids and polymers. A better understanding of the physical properties of n-alkane chains should provide a better understanding of these more complex systems. With this aim, vibrational spectroscopy has been extensively used. This technique, sensitive to molecular details, is the only one able to both identify and quantify conformational disorder present in paraffinic systems. To achieve this, methyl deformations have been widely used as "internal standards" for the normalisation of peak areas. However, in the case of n-alkanes with short chain length, such as n-C[44]H[90] for example, the infrared spectra recorded at liquid nitrogen temperature and reported here show the sensitivity of these latter peaks to the various crystal structures formed. Indeed, the main frequencies of the symmetric methyl bending mode were found between 1384 cm[-1] and 1368 cm[-1] as a function of the crystal form. Changes in the frequency of the first order of the L.A.M. present in the Raman spectra were also observed. At higher temperatures, non all-trans conformers, inferred from different infrared bands present in the wagging mode region, were found to be essentially placed at the end of the n-alkane chains. At the monoclinic phase transition, the concentration of end-gauche conformers, proportional to the area of the infrared band at 1342 cm[-1], increases abruptly. On the contrary, in the spectra recorded at liquid nitrogen temperature no such band is observed. We also studied the degree of disorder in two purely monodisperse long chain n-alkanes, namely n-C[198]H[398] and n-C[246]H[494]. The chain conformation as well as the tilt angle of the chains from the crystal surfaces were determined by means of low frequency Raman spectroscopy and S.A.X.S. measurements on solution-crystallised samples. The increase in the number of end-gauche conformers which was expected to occur with the increase of the tilt angle as a function of the temperature was not detected due to a perfecting of the crystals. Indeed, due to successive heating and cooling to -173°C, the concentration of non all-trans conformers was found to decrease within the crystals. Their numbers were found to be up to six times higher in n-C[198]H[398] crystallised in once folded form than when crystallised in extended form. The C-C stretching mode region of the spectra was used to identify the chain conformation and to estimate the length of the all-trans stem passing through the crystal layers at -173°C. The transition between once folded and extended form crystals was indicated by the presence of additional bands in this region at 1089 cm[-1], 1078 cm[-1] and 1064 cm[-1]. Some of those bands may be related to the fold itself. At the same time, a strong decrease of the intensity of the infrared bands present in the wagging mode region was observed. Finally, the triple layered structure proposed on the basis of X-ray measurements obtained from the crystals of a binary mixture of long chain n-alkanes, namely n-C[162]H[326] and n-C[246]H[494], was confirmed from the study of the C-C stretching mode region of the infrared spectra.

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Made available in DSpace on 2014-10-09T12:52:23Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:36Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Devido aos crescentes problemas relacionados com a poluição atmosférica na região metropolitana de São Paulo que atingem o ambiente e a saúde das populações, toma-se de grande interesse o estabelecimento de metodologias tal como a de monitoramento da qualidade do ar usando organismos cosmopolitas. O biomonitoramento é um método experimental que permite avaliar a resposta de organismos vivos à poluição, oferecendo vantagens como custos reduzidos, eficiência no monitoramento de amplas áreas geográficas e de elementos químicos poluentes presentes em baixas concentrações no ambiente e acumulados no biomonitor ao longo de um período. No presente trabalho, o método de análise por ativação neutrônica foi aplicado à determinação de elementos acumulados em amostras do fungo liquenizado Canoparmelia texana coletadas em duas áreas distintas: (1) Parques Estaduais Carlos Botelho (PECB) e Intervales (PEI), área considerada não-poluída pertencente ao ecossistema de Mata Atlântica - SP e (2) área metropolitana de São Paulo em pontos localizados nas proximidades das estações automáticas de monitoramento da Companhia de Tecnologia de Saneamento Ambiental (CETESB). Os liquens coletados dos troncos de árvores foram previamente limpos, moídos e posteriormente irradiados com nêutrons do reator IEA- R1 juntamente com os padrões sintéticos dos elementos. A precisão e exatidão dos resultados analíticos foram avaliadas por meio das análises dos materiais certificados de referência IAEA-336 LICHEN e Mixed Polish Herbs (INCT-MPH-2). Os resultados obtidos nestes materiais de referência foram concordantes com os valores certificados e apresentaram, em geral, uma boa precisão com coeficientes de variação variando de 0,9 a 14,6%. Os resultados das análises de liquens indicaram que os elementos As, Co, Cr, Cs, La, Mo, Sb, Sc, Se e U estão presentes aos níveis de ng g-1, Ba, Br, Cl, Fe, K, Mn, Na, Rb e Zn aos niveis de mg g-1 e Ca aos níveis de μg g-1. Por meio da aplicação das análises de cluster e de discriminate, aos resultados obtidos nas amostras coletadas em áreas com diferentes níveis de poluição, os pontos de amostragens foram agrupados segundo similaridades químicas no que diz respeito às suas composições elementares. Também foi observado que as amostras do PECB e do PEI separaram-se dos grupos e subgrupos formados pelas amostras da região metropolitana e este resultado indica a preservação das áreas consideradas não-poluídas. Os liquens coletados no PEI apresentaram, em geral, concentrações inferiores àquelas obtidas para a região metropolitana de São Paulo principalmente para os elementos relacionados com ações antrópicas. Os mapas de distribuição das concentrações de elementos permitiram a visualização e identificação de pontos que apresentam concentrações de elementos mais altas na região metropolitana. Estes mapas de distribuição também mostraram que a poluição na região metropolitana de São Paulo apresenta perfis diferentes devido às inúmeras fontes de emissão de poluentes. Os elementos determinados nos liquens da área metropolitana indicaram ser de origens industrial, veicular e do solo. Os resultados obtidos neste trabalho mostraram a viabilidade do uso da C. texana na avaliação da poluição no biomonitoramento passivo de diversos elementos contaminantes presentes na atmosfera da região metropolitana de São Paulo. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:03/03387-1