The Tahorakuri Formation was introduced as a stratigraphic term to simplify the sometimes complex and inconsistent naming conventions in subsurface deposits within the geothermal fields of the central Taupo Volcanic Zone (TVZ). It consists of all volcaniclastic and sedimentary deposits between the ~350 ka Whakamaru-group ignimbrites and the greywacke basement that cannot be correlated with known ignimbrites. As such, it represents a long period in which relatively little is known about the volcano-tectonic history of the TVZ. The thesis focuses on the Tahorakuri Formation at Ngatamariki and Rotokawa geothermal fields and the implications for the volcano-tectonic evolution of the TVZ. Drill cuttings from wells NM5 and NM6 are re-examined, and new U-Pb zircon dates from the Tahorakuri Formation are presented and implications discussed. Potassium feldspars identified in the drill cuttings from NM5 were examined by Raman spectroscopy and electron microprobe (EMP) analysis. Although petrographically many of the feldspars appear similar to sanidine, a primary volcanic mineral phase, this showed them to be adularia which formed during hydrothermal alteration. Raman spectroscopy was found to be ideal for analysing a large number of grains quickly, with the spectral peak at ~140 cm⁻¹ being particularly useful for identifying adularia as it is absent in sanidine. EMP analysis was found to be somewhat slower, but definitively identified the feldspars as adularia, with typical potassium-rich compositions of Or₉₄-Or₉₉. U-Pb dating shows that the Tahorakuri Formation formed over a very long time, with pyroclastic deposits ranging from 1.89 - 0.70 Ma. This was followed by a period with little or no explosive volcanism until ~0.35 Ma during which sediments were deposited at Ngatamariki. The periods at ~1.9 Ma and ~0.9 Ma were particularly active phases of pyroclastic deposition, with the second phase likely correlating with the Akatarewa ignimbrite. The oldest deposits overlie a large andesitic composite cone volcano. Significant subsidence of the andesite must have preceded emplacement of the silicic deposits, indicating that rifting within the central TVZ may have started earlier than previously thought. While the origin of the deposits is uncertain, the distribution of the oldest deposits outcropping at the surface, as well as the likely early initiation of rifting, would suggest a source within the TVZ is likely.

Identifying the crustal affinity of Grenville basement rocks in the Dellwood quadrangle, western NC, provides insight into the tectonic evolution of eastern Laurentia during Grenville orogenesis. U-Pb zircon geochronology of orthogneiss, augen gneiss, and mafic xenoliths in orthogneiss reveal magmatic pulses at 1130, 1180, and 1330 Ma and metamorphic episodes at 450 and 1040 Ma. Xenoliths in 1330 Ma orthogneiss are as old as 1382 Ma and represent the oldest component of Blue Ridge basement identified to-date. Feldspar Pb isotope values span a range between juvenile-Laurentian and southern-central Appalachian basement/Amazonia. Most Pb isotope data define an array consistent with crustal mixing between Laurentia and Amazonia, however, one xenolith has a unique Pb isotopic composition interpreted as Laurentian crust. Sm-Nd isotope data yield depleted mantle model ages ranging from 1.52 to 1.79 Ga (200 to 650 Ma older than their crystallization ages) indicating a broadly non-juvenile heritage for Dellwood basement. Three biotite gneiss samples contain detrital zircon grains derived from 1060, 1160, 1330, and 1750 Ma sources. Multiple magmatic zircon age populations, variable depleted mantle modelages, and regionally unique isotopic Pb signatures are evidence of protracted Grenville magmatism in the southern Appalachians involving both Laurentian and Amazonian crustal components.

An acid rock drainage (ARD) stream emanating from the Zn-Pb XY-deposit in the Yukon Territory was examined in order to evaluate the physico-chemical and geochemical processes governing the distribution of dissolved elements from the creek. The creek showed very high concentrations of metals (300 mg/L Fe, 500 mg/L Zn, 15 000 µg/L Ni, 1300 µg/L Cu and 4500 µg/L Cd), low water temperatures (1 – 12°C) and was acidic to moderately acidic (pH 3.1 – 5.0). It was found that this stream experienced a strong seasonal evolution, with increased sulphate and metal concentrations and decreased pH over the course of the summer. The mineral precipitates that formed under low pH conditions were a mixture of schwertmannite, goethite, jarosite and barite, while those that formed under moderately acidic conditions were a mixture of jurbanite, hydrobasaluminite, gibbsite and an X-ray amorphous Al-sulphate phase. Most of the mineral precipitates were of inorganic origin, although microbes may have played a role in mineral formation and trace metal sequestration in some of the precipitates. All of the mineral precipitates contained anomalous concentrations of trace elements (up to 1.5 % wt Zn) and showed a seasonal evolution in their mineralogy, both of which were determined to be a function of the pH and prevailing geochemical conditions. The geochemistry of the ARD creek draining the XY-deposit was compared to another ARD creek in the area that was likely draining shales. The two creeks were compared in order to determine if ARD geochemical characteristics can be used as a tool for the mineral exploration industry.

Racemic metyhl 3-cyclohexene-1-carboxylate was resolved via enzymatic hydrolysis to afford the enantiomerically enriched 3-cyclohexene-1-carboxylic acid with PLE (S-configuration), HLE (S-configuration), CCL (S-configuration) and PPL (R-configuration) . The nucleoside&amp / #65533 / s precursor, 5-(hydroxymethyl)-2-cyclohexen-1-ol (19), was synthesized by iodolactonization, followed by iodine elimination and the reduction of the lactone. In connection with this work, alpha,beta-unsaturated and saturated cyclic ketones were selectively oxidized on alpha&#039 / - and alpha-positions using Mn(OAc)3 and Pb(OAc)4, respectively. The resultant racemic alpha&#039 / - and alpha-acetoxylated substrates were resolved into corresponding enantiomerically enriched alpha&#039 / - and alpha-hydroxylated and acetoxylated compounds via PLE hydrolysis.

Biosorption is a phenomenon involving the mechanisms that basically mediate heavy metal tolerance of microorganisms as well as sequestration of heavy metals from environment. Different classes of microorganisms have different biosorption capacities, as a result of the differences in composition and types of functional groups found on cell surfaces. The present study was undertaken to identify the molecular mechanisms for lead [Pb(II)] biosorption in the white-rot fungus, Phanerochaete chrysosporium. The methodology involved selective blocking of the functional groups known to participate in heavy metal biosorption and allowed us to determine their relative roles in Pb (II) biosorption in this organism. The relative concentrations of the Pb (II) sorbed from the aqueous environment and Mg2+ and Ca2+ ions released to the aqueous environment were measured and compared with both native and chemically-modified biomasses by using atomic absorption spectroscopy. Fourier-Transform Infrared (FTIR) spectroscopy technique was used to monitor and analyze the molecular-level changes in both native and chemically modified cell surfaces upon Pb (II) exposure. Interactions of Pb (II) with the biomass surface was determined by observing the changes in wavenumber and absorbance of NH stretching and Amide I bands arising from the amine groups and C=O stretching band arising from the carboxyl groups. The roles of phosphate groups and lipids were also investigated. Carboxyl groups seemed to be the most important functional groups for Pb (II) biosorption in P. chrysosporium, since the biosorption capacity dramatically decreased (by 92.8 %) in carboxyl groups-blocked biomass. Amine groups were found to play a secondary and minor role in Pb (II) biosorption, only a slight decrease (6 %) in Pb (II) biosorption was detected with amine groups-blocked biomass. Blocking of phosphate groups provided a small increase in biosorptive capacity and did not appear to have much significant role in biosorption. Upon chemical treatment with acetone to extract lipids of the cell surfaces, an increase of 20.3 % in the Pb (II) biosorptive capacity was determined. It was concluded that carbonyl and carboxyl groups of chitin and glucan are the major sites and ion exchange via these groups is the main mechanism for Pb (II) biosorption in P. chrysosporium.

ABSTRACT SYNTHESIS AND ENZYMATIC RESOLUTION OF VARIOUS CYCLOPENTENOID AND CYCLOHEXENOID TYPE COMPOUNDS iyig&uuml / n, &Ccedil / igdem Ph. D., Department of Chemistry Supervisor: Prof. Dr. Cihangir Tanyeli June 2005, 174 pages The aim of this thesis is to synthesize enantiomerically enriched cyclopentenoid and cyclohexenoid type of compounds with quaternary carbon stereocenters that are the simplest precursors of the complex natural products. The first part of the study involves the preparation of &amp / #945 / &#039 / -acetoxy &amp / #945 / &#039 / -substituted &amp / #945 / ,&amp / #946 / -unsaturated cyclic ketones. Methylation, ethylation, benzylation and allylation of cyclohexenone and cyclopentenone derivatives are performed. Then, these compounds are regioselectively oxidized at the &amp / #945 / &#039 / -position by Mn(OAc)3. This is the first successful example in the literature that &amp / #945 / &#039 / -tert-position is oxidized by Mn(OAc)3. The oxidations were also performed by Pb(OAc)4 and both methods were compared. Related to this study, in the second part, the enantiomeric resolution of the acetoxy derivatives were performed by various hydrolases. This study is the first example where the hydrolases are used to resolve tertiary positions. Among the enzymes used, Candida cylindracea lipase (CCL) showed the best enantioselectivity.

Two ombrotrophic peat bogs (NC2 and BL2) from North Stradbroke Island, Australia, were precisely dated using 210Pb and analyzed by scanning electron microscopy. Sub-samples were total digested and sequentially leached for trace and major elements concentrations using ICP-MS and ICP-OES. Total Pb concentrations in both profiles increased with the time. PAAS normalized REE patterns were characterized by relatively flat patterns, with slight enrichment in LREE, and a significant negative Eu anomaly. The temporal changes in metal concentrations, 206Pb/207Pb ratios, REEs, and ash content observed in the two profiles suggest three different periods with distinct conditions in terms of dust provenance and atmospheric pollution: (1) Pre-anthropogenic (pre-1842); (2) Early industrial (from 1840s to 1920s); (3) Industrial (post-1930s). Ombrotrophic peat bogs may be reliable archives of environmental pollution, but also shows that adjacent sites may provide contrasting evidence. Despite their close proximity, the two sites show different trends in metal deposition. Metals in NC appear to be largely bound to minerals and inorganic materials, while in BL they are mainly organic-related. Indeed the peculiar behaviour of Pb in the BL profile suggests that biological process may cause Pb isotopic fractionation. Ash contents, texture, Pb isotopic compositions, Sb/Pb values, patterns of selected trace elements (Pb, Cu, Zn, Cd, Cr, Co, Sb, Ni, Se, As, Be and Mo), and their leaching behaviours suggests that NC and BL are chemically different types of peat bogs. NC peat bog is an open sink for elements, and can be used to define regional anthropogenic impacts. In contrast, the BL site appears to be influenced by local natural and anthropogenic processes and activities, such as changes in land use. Furthermore, it demonstrated that only some of the environmental-related trace elements preserve their original depositional record. Arsenic, Be, Co, and Zn are highly mobile under weak acid conditions, and are therefore not suitable for assessing temporal trends of pollution. Cadmium, Ni, and V may also be highly mobile under certain conditions. In contrast, Pb, Cu, Cr, Mo, and Sb are not subject to vertical migration, and are useful for establishing the pollution record of ombrotrophic peat bogs.

Two ombrotrophic peat bogs (NC2 and BL2) from North Stradbroke Island, Australia, were precisely dated using 210Pb and analyzed by scanning electron microscopy. Sub-samples were total digested and sequentially leached for trace and major elements concentrations using ICP-MS and ICP-OES. Total Pb concentrations in both profiles increased with the time. PAAS normalized REE patterns were characterized by relatively flat patterns, with slight enrichment in LREE, and a significant negative Eu anomaly. The temporal changes in metal concentrations, 206Pb/207Pb ratios, REEs, and ash content observed in the two profiles suggest three different periods with distinct conditions in terms of dust provenance and atmospheric pollution: (1) Pre-anthropogenic (pre-1842); (2) Early industrial (from 1840s to 1920s); (3) Industrial (post-1930s). Ombrotrophic peat bogs may be reliable archives of environmental pollution, but also shows that adjacent sites may provide contrasting evidence. Despite their close proximity, the two sites show different trends in metal deposition. Metals in NC appear to be largely bound to minerals and inorganic materials, while in BL they are mainly organic-related. Indeed the peculiar behaviour of Pb in the BL profile suggests that biological process may cause Pb isotopic fractionation. Ash contents, texture, Pb isotopic compositions, Sb/Pb values, patterns of selected trace elements (Pb, Cu, Zn, Cd, Cr, Co, Sb, Ni, Se, As, Be and Mo), and their leaching behaviours suggests that NC and BL are chemically different types of peat bogs. NC peat bog is an open sink for elements, and can be used to define regional anthropogenic impacts. In contrast, the BL site appears to be influenced by local natural and anthropogenic processes and activities, such as changes in land use. Furthermore, it demonstrated that only some of the environmental-related trace elements preserve their original depositional record. Arsenic, Be, Co, and Zn are highly mobile under weak acid conditions, and are therefore not suitable for assessing temporal trends of pollution. Cadmium, Ni, and V may also be highly mobile under certain conditions. In contrast, Pb, Cu, Cr, Mo, and Sb are not subject to vertical migration, and are useful for establishing the pollution record of ombrotrophic peat bogs.

Made available in DSpace on 2014-06-11T19:32:55Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-12-07Bitstream added on 2014-06-13T20:44:20Z : No. of bitstreams: 1 schoenlein_nc_dr_rcla.pdf: 708327 bytes, checksum: 8cde8b071e32b6d7c6b3ae6e75ecacae (MD5) / O solo do pólo cerâmico de Santa Gertrudes tem sido poluído há décadas por diversos elementos, como Pb, Zn e outros. Foram realizadas quatro coletas de solo (duas durante a época chuvosa e duas na seca), em cinco locais, entre novembro de 2002 a junho de 2003; mediram-se temperaturas, pH, teores de Pb, Zn e umidade. Os fungos foram isolados através do método de Warcup, modificado, com a utilização de meios de extrato de malte agar (MEA) a 2%, adicionados com doses crescentes de nitrato de Zn e de Pb, sendo as colônias purificadas e identificadas. Foram obtidos 70 táxons de fungos anamorfos com 70% de similaridade entre as micotas obtidas com os dois metais. Foram isolados 43 taxons dos meios de cultura com Pb, havendo predominância de isolamentos nos teores mais elevados (500 a 1000 mg Pb/dm3). Foram obtidos 63 táxons nos meios com Zn, com teores de 200 a 500 mg /dm3. Predominaram espécies de Trichoderma, Penicillium e outras usualmente associadas a substratos em decomposição. Estabelecida a diversidade dos fungos, estudou-se a tolerância do Aspergillus terreus e do Paecilomyces lilacinus a nitratos de Pb e Zn. Foi usado o meio Czapek, com a adição de 250; 500; 750 e 1000 mg de Pb por dm3 e 1.000; 2.000; 3.000; 4.000; 6.000; 8.000 e 10.000 mg de Zn por dm3 .Com os dados obtidos, foi possível cálcular o teor do metal que inibe 50% e 100% do crescimento da biomassa EC 50 e/ou EC100 .Para o A. terreus foram encontrados: EC 50 Pb= 489,05 mg/dm3 ; EC 100 Pb = 1.049,08 mg/dm3 ; EC50 Zn = 81,26 mg/dm3 ; EC100 Zn= 6.360,98 mg/dm3 . Para o P. lilacinus foram encontrados: EC 50 Pb = 1.147,89 mg/dm3; EC 100 Pb = 2.389,45 mg/dm3 ; EC 50 Zn= 8.323,75 mg/dm3; EC 100 Zn= 15.995,36 mg/dm3 . Em relação à sensibilidade a Pb e a Zn, o A. terreus apresentou sensibilidades maiores do que o P. lilacinus. Constatou-se também, que a sensibilidade do A . terreus a Zn foi maior do que ao Pb. / The soil of the ceramic pole, has been polluted since decades by several elements, mainly lead and zinc. Four soil sample collections were conducted (2 during the rainy and 2 in the dry season) at 5 sites, between november 2002 and june 2003, measuring the temperature, pH and the content of Pb, Zn and moisture in the soil. The fungi were obtained by the modified Warcup's soil plate method, using malt extract agar (2%), added of increasing dosis of Zn and Pb salts.The colonies were purified and identified .Seventy anamorphs were obtained, with 70% of similarity between the mycotas isolated from the culture media added with the metals. Fourty three taxa were isolated from the culture media with Pb, with predominance of isolations in higher Pb concentrations (500 to 1000 mg Pb per dm3). 63 taxa were obtained in the media with Zn, mainly in the concentrations between 200 and 500 mg Zn per dm3. Species of Trichoderma, Penicillium and several fungi usually found in decomposing plant debris prevailed. After determining the diversity of fungi in the ceramic pole, Aspergillus terreus and Paecilomyces lilacinus were submitted to tests of tolerance to Pb and Zn. A modified medium Czapek was used amended with 250; 500; 750 and 1000 mg of Pb per dm3 and 1000; 2000; 3000; 4000; 6000; 8000 and 10000 for Paecilomyces lilacinus mg of Zn per dm3 . Afterwards it was possible to calculate the effective concentrations inhibiting growth by 50% and 100% values ( EC50 and EC100 ). Values obtained for A terreus: EC 50 Pb = 489,05 mg/dm3 ; EC 100 Pb= 1.049,08 mg/dm3 ; EC 50 Zn= 81,26 mg/dm3; EC 100 Zn= 6.360,98 mg/dm3 .Values obtained for P. lilacinus; EC 50 Pb = 1.147,89 mg/dm3 ; EC 100 Pb = 2.389,45 mg/dm3 ; EC 50 Zn = 8.323,79 mg/dm3 ; EC 100 Zn = 15.995,36 mg/dm3 . With regards to the sensitivity to lead and zinc, A. terreus showed greater sensitivity than P. lilacinus. A greater sensitivity of A. terreus for zinc than lead was recorded.

Orientador: Luiz Carlos Santana / Banca: Michele Tomoko Sato / Banca: Maria Bernadete Sarti de Carvalho / Resumo: O presente estudo tem por objetivo analisar o caso da implementação do Programa Escolas Sustentáveis (PES) em quatro escolas municipais de João Pessoa/PB. O PES, criado pelo Ministério da Educação em 2009, trata-se de uma proposta de política desenvolvida para o ambiente formal de ensino, voltada a apoiar a transição das escolas rumo à sustentabilidade. Disponibiliza recurso financeiro para as escolas desenvolverem ações que estabeleçam relação entre três eixos inter-relacionados: o currículo, a gestão e o espaço físico. Buscamos nesse estudo identificar as ações desenvolvidas pelas escolas, as compreensões de gestores e professores sobre Educação Ambiental e Sustentabilidade e apresentar as contribuições da implementação desse programa para o espaço escolar, revelando as dificuldades e facilidades encontradas pelos educadores na implementação. Esse estudo é caracterizado por uma pesquisa de natureza qualitativa do tipo estudo de caso. Os instrumentos utilizados para a coleta de dados foram entrevistas semi-estruturadas (22 no total), os projetos político pedagógicos e os planos de ações dessas escolas. O procedimento analítico foi feito a partir da técnica de triangulação de dados. De acordo com os dados as três escolas desenvolveram ações contemplando somente o espaço físico, a saber: horta escolar, "espaço de vivência", coleta de óleo de cozinha e papa-pilhas. Foram realizadas também palestras e oficinas. Tais ações foram orientadas por uma concepção de EA pragmática e com... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study aims to analyze the implementation case of the Sustainable Schools Program (SSP) in four public schools in João Pessoa/PB. The SSP, created by the Ministry of Education in 2009, is a policy proposal developed for the formal teaching background, aiming to support the transition of schools towards sustainability. It provides financial resources for schools to develop actions that establish relationship among three interrelated axes: curriculum, management and physical space. We seek to identify in this study actions developed by the schools, understandings on Environmental Education and Sustainability and to present contributions to the implementation of this program for the school space, revealing the difficulties and facilities faced by educators in the implementation. This study is characterized by a qualitative research of a case study. The instruments used for data collection were semi-structured interviews (22 in total), the pedagogical political projects and action plans of these schools. The analytical procedure was conducted from the data triangulation. According to these data, the three schools carried out actions only collection and papa-cells. Workshops and lectures were also held there. Such actions were guided by a pragmatic and behaviorist EE design, focusing on the theme of garbage. According to the data, one of the contributions achieved by the Program to ement in carrying out the activities; have provided through the activities an exchange of knowledge between schools and communities. One of the challenges mentioned was to involve teachers in working with EE projects. Another difficulty punctuated was in the exchange of teachers at the beginning of the school year and the arrival of new teachers through public tender that took place at the time of implementation. Finally, it was highlighted the specific features involved in the projects and their lack of continuity / Mestre