No description available.

No description available.

The working hypothesis for this study was that small elevation differences in field depressions affect the availability of redox active nutrients because the bottom of the depression remains waterlogged and in reducing conditions longer than the edge of the depression. Mn, Fe, S and P availabilities were investigated in a field depression with a 20 meter radius and 0.5 meter depth on a flood-prone, organic vegetable farm. One depression (Depression 1) was sampled seven times during three field seasons (May 2012-June 2014). The last two dates included sampling in an additional three depressions to allow a comparison among depressions on the same date. Sampling dates were categorized by the severity of flooding into the three following kinds of events: Post-Irene, Peak, and Non-Peak. The Post-Irene category includes sampling dates in the agricultural season following prolonged snow melt and flooding from Tropical Storm Irene in 2011. Sampling dates in the Peak category occurred within 30 days after one of the the top 12 greatest rainfalls, snowfalls, or heights of Winooski River Gage in the 30 month sampling period. Sampling on Non-Peak events occurred at least one month after a preceding Peak event. Repeated waterlogging events can increase redox cycling directly affecting the interchange of Mn, Fe, and S oxides and the soil solution. Indirectly, waterlogging can increase phosphorus release into the soil solution by reduction of iron. The results of this experiment indicate that some redox-sensitive soil nutrients correlated with elevation on some dates regardless of event type. Mn was more consistently affected by waterlogging events than Fe and S. Any relationship between sulfur and elevation may have been obscured by the strong relationship of sulfur with organic matter. This data suggests that phosphorus availability depended to some extent on available iron concentration.

D. Phil. / The Kalahari Manganese Deposit (KMD) is the largest of five erosional relics of the Hotazel Formation that are located near Kuruman in the Northern Cape Province of South Africa. Manganese ores are exploited from the lowermost of three manganiferous beds that are interbedded with banded iron-formation (BIF) and hematite lutite, that together constitute the Hotazel Formation. Two major ore types have been delineated previously, viz. low grade braunite lutite of the Mamatwan-type, and high grade oxidic ores of the Wessels-type, with the latter spatially restricted to the northern KMD. Genesis of the ores was temporally distinct, with the Mamatwan-type ore considered as a sedimentary-diagenetic precursor to the hydrothermally altered Wessels-type ore. Drill core samples from the Nchwaning-Gloria area of the northern KMD were analysed, with the aim to better characterise ore genesis, with emphasis on ore alteration. A second part of the study aimed at the application of mineralogical and geochemical information to aspects of ore smelting for the production of Mn alloy for use in the steel industry. Methods employed were drill core logging, X-ray diffraction (XRD), petrography, electron probe microanalysis (EPMA), major and trace element (including REE) analysis (employing artificial neural networks for evaluation of elemental trends), and stable isotope (C and O) analysis. Significant effort was invested in method development for quantitative mineralogical modal analysis using Rietveld refinement of XRD data. The study shows that a number of ore types can be differentiated in the northern KMD on the basis of mineral assemblage, grade, texture and geochemical characteristics. The ores are broadly classified into least altered (LA), partially altered (PA) and advanced altered (AA) types. The LA ores are low grade (<40 wt%Mn) Mn lutites, with dolomite-group carbonate a significant component in addition to braunite. Serpentine is a ubiquitous trace mineral, and boron is a characteristic trace element hosted predominantly by braunite in these ores. Ores of the PA type comprise either braunite-hausmannite-calcite or hausmannite-calcite assemblages, are fine to coarse grained, and display intermediate Mn grades (40-45 wt%Mn). They exhibit a transitional trace element signature. Advanced altered ores may be classified into five different types, based on mineral assemblages that contain hausmannite and/or braunite as significant minerals. Carbonates occur predominantly in the form of calcite, present in minor to trace proportions. Textures vary from fine to very coarse grained, and high Mn grades (typically >45 wt%Mn), are recorded. Trace elements of significance include Zn, associated with hausmannite, B, associated with massive braunite and a number of trace minerals, and P, typically present in trace quantities of apatite. In terms of ore genesis, mineralogical, geochemical and geological considerations suggest that Mn (and Fe) originated from submarine hydrothermal vents, from which it travelled in hydrothermal plumes, prior to rapid deposition ~2.2 Ga ago. Diagenesis followed soon after deposition, through redox reactions involving organic matter and higher oxides of Mn to produce the braunite-carbonate assemblage primarily observed in LA ores. The carbonate:oxide ratio and nature of the carbonates varied slightly depending on fluctuations in organic matter flux to the sediment, as well as marine bicarbonate concentrations. Metamorphism, in relation to diagenesis and metasomatism, is poorly understood, but is perceived to have resulted in serpentine formation, as observed in LA and PA ores.

D.Sc. / Please refer to full text to view abstract

Information from soil geochemical mapping programmes is useful within a number of different fields including for example mineral exploration and environmental research. The purpose of this thesis was to investigate the relationship between soil metal concentrations and geological factors such as bedrock lithology, structural geology, mineralizations etc. The study used data acquired in association with a nationwide soil geochemical mapping programme conducted by the Geological Survey of Sweden, SGU. These data contained both total element concentrations measured via X-ray fluorescence spectroscopy and acid leached concentrations measured with plasma technique. Basic statistical compilations were made, including classification of element concentrations into percentiles according to SGU standards, calculation of leachability and correlation analyses. Spatial analyses were also done, using GIS-software. The results showed that all investigated elements except zinc had elevated median values for total concentrations in the project area compared to the natural median values. The strongest correlation for total element concentrations was that between iron and cobalt with Spearman ρ=0.88. Furthermore, the results of this study indicated that sampling sites superimposing volcanic rocks contained the highest total concentrations of manganese. The results also suggested that manganese content increased with increasing age of the underlying bedrock. The highest median concentration of 0.80 g/kg was found in Archean rocks. Known mineralizations were often reflected in the form of positive element anomalies in the till geochemistry. The obtained results were also consistent with the average composition of the bedrock. No clear connections with any of the other investigated geological factors could be made.

No description available.

Orientador: José Anchieta Gomes Neto / Coorientador: Adriana Paiva de Oliveira / Banca: Márcia Andreia Mesquita Silva da Veiga / Banca: Gian Paulo Giovanni Freschi / Resumo: Este trabalho descreve estratégias instrumentais para a determinação de Mn em amplo intervalo de concentração por espectrometria absorção atômica em chama com fonte contínua e de alta resolução (HR-CS FAAS), por meio do uso de diferentes linhas atômicas (principal, secundária, alternativa ou o ajuste do arranjo instrumental) desde que seus intervalos de concentração se completem, sem a necessidade de amplas diluições da amostra. O método proposto foi aplicado as amostras de água de abastecimento, fertilizante foliar, poli vitamínico e material certificado de ligas metálicas. A exaltidão e precisão foram avaliadas por testes de significância (t de student e t - pareado), adição e recuperação, e materiais de referência do Instituto de Pesquisa Tecnológica do Estado de São Paulo, e os resultados foram concordantes ao nível de 95% de confiança em sua grande maioria. Obteve-se curvas analíticas nos intervalos 0,1-2 mg L-1 (279,482 nm), 2-25 mg L-1 (403,075 nm), 25-500 mg L-1 (209,250 nm ou 403,075 nm com queimador a 90 graus), com coeficiente de correlação linear melhor do que 0,9936 em ambas as técnicas (utilizou a espectrometria de absorção atômica em chama com fonte de linhas - LS FAAS - como técnica comparativa). Os limites de detecção para a HR-CS FAAS foram 1,1x10-3 mg L-1 (279,482 nm), 9,8 x 10-3 mg L-1 (403,075 nm), 1,7 mg L-1 (209,250 nm), 7,3x10-2 mg L-1 (403,075 nm com queimador a 90 graus), e para a LS FAAS foram 1,0x10-2 mg L-1, 0,10 mg L-1, 24,8 mg L-1, 7,0 mg L-1, respectivamente. Em HR-CS FAAS, o RSD% variou 0,9 a 1,3, enquanto para a LS FAAS variou 1,1 a 11,8%. As concentrações encontradas pela HR-CS FAAS foram: < 1,1x10-3 mg L-1 (água de abastecimento)... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This paper describes instrumental strategies for the determination of Mn in a wide range concentration by high-resolution continuum source flame atomic absorption spectrometry technique (HR-CS FAAS) by means of different atomic lines (primary, secondary, alternative or adjusting the instrumental arrangement) provided that their concentration intervals complete one another, without need for large sample dilutions. The proposed method was applied to water, foliar fertilizer, poly vitamin and metal alloys certified materials. Accuracy and precision were evaluated by tests of significance (Student's t test and paired - t test), addition and recovery, and reference materials from the Institute of Technological Research of São Paulo. Analytical curves in the intervals 0.1-2 mg L-1 (279.482 nm), 2-25 mg L-1 (403.075 nm), 25-500 mg L-1 (209.250 nm or 403.075 nm burner 90 degrees) were obtained with linear correlation coefficient better than 0.9936. Line source flame atomic absorption spectrometry (LS FAAS) were used as a comparative technique. The detection limits HR-CS FAAS were 1.1x10-3 mg L-1 (279.482 nm), 9.8 x 10-3 mg L-1 (403.075 nm), 1.7 mg L-1 (209.250 nm), 7.3x10-2 mg L-1 (403.075 nm burner 90 degrees). And by LS FAAS were 1.0x10-2 mg L-1, 0.10 mg L-1, 24.8 mg L-1, 7.0 mg L-1 respectively. In HR-CS FAAS, the RSD ranged from 0.9 to 1.3%, while for LS FAAS from 1.1 to 11.8%. The Mn concentrations found by HR-CS FAAS were < 1.1x10-3 mg L-1 (water supply), 4728 ± 62 mg L-1 (foliar fertilizer), 3.65 ± 2 mg g-1 (poly vitamin), 0.709 ± 0.116 mg L-1 (Alloy 14A), 0.998 ± 0.042 mg L-1 (alloy 25). For LS FAAS, the concentrations wer... (Complete abstract click electronic access below) / Mestre

Su Pak Lee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 79-84). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgement --- p.iii / Abstract --- p.iv / Abbreviation --- p.vi / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- Stoichiometric Oxidant --- p.4 / Chapter 1.2.1 --- Chromium Trioxide-pyridine --- p.5 / Chapter 1.2.2 --- "Chromium Trioxide-3,5-dimethylpyrazole" --- p.6 / Chapter 1.3 --- Catalytic Allylic Oxidation --- p.8 / Chapter 1.3.1 --- Homogeneous Catalysts --- p.8 / Chapter 1.3.1.1 --- Chromium Catalysts --- p.8 / Chapter 1.3.1.2 --- Iron Catalysts --- p.11 / Chapter 1.3.1.3 --- Copper Catalysts --- p.13 / Chapter 1.3.1.4 --- Palladium Catalysts --- p.14 / Chapter 1.3.1.5 --- Rhodium Catalysts --- p.19 / Chapter 1.3.2 --- Heterogeneous Catalysts --- p.22 / Chapter 1.4 --- Manganese(III) Acetate --- p.24 / Chapter 1.5 --- General Application of Manganese(III) Acetate --- p.25 / Chapter 1.5.1 --- Oxidative Free Radical Cyclization --- p.25 / Chapter 1.5.2 --- α-Acetoxylation --- p.27 / Chapter 1.6 --- Manganese(III) Catalyzed Reactions --- p.28 / Chapter 1.6.1 --- Epoxidation --- p.28 / Chapter 1.6.2 --- Sulfur oxidation --- p.29 / Chapter 2. --- Results and Discussions --- p.31 / Chapter 2.1 --- The Scope --- p.31 / Chapter 2.2 --- Tuning of Reaction Conditions --- p.32 / Chapter 2.2.1 --- Variation of Oxidant --- p.32 / Chapter 2.2.2 --- Variation of the Amount of Oxidant and Catalyst --- p.34 / Chapter 2.2.3 --- Variation of Solvent --- p.36 / Chapter 2.3 --- Results of Allylic Oxidation under Optimized Conditions --- p.39 / Chapter 2.4 --- Modification of Manganese(III) Acetate Catalysed Allylic Oxidation --- p.46 / Chapter 2.4.1 --- By Adding Base --- p.46 / Chapter 2.4.2 --- Assistance by Oxygen --- p.49 / Chapter 2.5 --- Mechanism --- p.53 / Chapter 3. --- Conclusion --- p.60 / Chapter 4. --- Experimental Section --- p.62 / Chapter 5. --- References --- p.79 / Chapter 6. --- Appendix --- p.85

A imobilização da MeP em suportes inorgânicos permite isolar o sítio de reação prevenindo a dimerização e/ou auto-destruição oxidativa da mesma, constituindo-se num catalisador biomimético. Neste projeto foi objetivo avaliar o comportamento biomimético de manganês porfirinas, comparando sistemas imobilizadas de diferentes maneiras em sílica funcionalizada em processos de oxigenação do cicloocteno ecicloexano, incluindo metabolismo de um fármaco. A primeira etapa do projeto consistiu na obtenção dos sistemas catalíticos contendo metaloporfirinas imobilizadas em sílicas modificadas. Para isso foi sintetizada a M(4-N-Py)TFPPH2 base livre, seguida da inserção de manganês (III) e metilação obtendo-se o catalisador Mn[{M(4-N-MePy)TFPP}]2+. Foi inserido manganês também nas porifinas base livre [T(4-N-MePy)P]Cl4 e [TFPP]H2 obtidas comercialmente obtendo-se os catalisadores Mn[T(4-N-MePy)P]5+ e Mn[TFPP]+. Realizou-se a funcionalização da sílica gel com (i) grupos sulfonatofenil e propilimidazol (SiSO3-IPG); (ii) grupos 3-aminopropil (APTES); (ii) grupos 3-(2-(2-aminoetilamino) etilamino) propil (AP(EA)2TS) e (iv) cloropropil e 1,6-diaminoexano (DA1,6Si). Essas sílicas foram imobilizadas nas manganêsporfirinas através de interações eletrostáticas ou via ligação covalente. Esses catalisadores foram usados na oxigenação de (Z)-cicloocteno e cicloexano e no estudo de metabolismo oxidativo do fármaco praziquantel (agente anti-helmíntico). Os catalisadores [Mn(TFPP)]- APTES, [Mn(TFPP)]- AP(EA)2TS, [Mn{M(4-N-MePy)TFPP}]-SiSO3, [Mn{M(4-N-MePy)TFPP}]- SiSO3(IPG), [Mn{M(4-N-MePy)TFPP}]-APTES, [Mn{M(4-N-MePy)TFPP}]- AP(EA)2TS, [Mn{M(4-N-MePy)TFPP}]- DA1,6Si foram usados em reações de epoxidação do (Z)-cicloocteno pelo PhIO e os resultados obtidos foram baixos. Já com H2O2 como oxidantes os resultados foram muito bons quando foi adicionado imidazol. Nas reações de hidroxilação do cicloexano os rendimentos obtidos foram altos quando a MnP foi imobilizada por interação eletrostática. Neste sistema as oxidações competitivas são minimizadas. Os sistemas com melhores resultados foram selecionados para estudos com o praziquantel (PZQ). Diferentemente dos resultados obtidos previamente com FeP, os sistemas com MnPs se revelaram bons catalisadores biomiméticos, uma vez que apresentaram quantidades expressivas do metabólito trans-4\'-OH, o principal metabólito produzido in vivo. As MnPs, em particular as piridis substituídas apresentaram boa conversão de PZQ sendo [Mn{T(4-N-MePy)P}]-SiSO3 o melhor, além de produzir 38 % do trans-4\'-OH, apresentou 87 % de conversão. Estes resultados preliminares indicam um sistema muito promissor com resultados inéditos. / The immobilization of metalloporphyrins in inorganic supports allows to isolate reaction site preventing dimerization and/or catalyst oxidative selfdestruction constituting in a biomimetic system. In this project the aim was evaluate the biomimetic behaviour of manganese porphyrins, comparing systems immobilized on sílica in different ways in oxygenations processes of (Z)- cyclooctene and cyclohexane, including a study of drug metabolism. Initially the catalytic systems containing metaloporphyrins immobilized on modified silica were obtained. The free base M(4-N-Py)TFPPH2 was firstly synthesized, then the MnIII was inserted, methylated obtaining the catalyst Mn[{M(4-N-MePy)TFPP}]2+. The MnIII also was inserted in the commercials free base [T(4-N-MePy)P]Cl4 e [TFPP]H2 obtaining the catalysts Mn[T(4-N-MePy)P]5+ e Mn[TFPP]+. The sílica gel were functionalizated with (i) sulfonatephenyl and propylimidazole groups (SiSO3-IPG); (ii) 3-aminopropil groups (APTES); (ii) 3-(2- (2-aminoethyilamine) ethilamine) propyl groups (AP(EA)2TS) and (iv) chloropropyl e 1,6-diaminehexane (DA1,6Si). Manganese porphyrins were immobilized on these sílica supports through electrostatic interactions or covalent bond. These catalysts were used in the (Z)-ciclooctene and cyclohexane oxigenationand in the oxidative metabolism of praziquantel (antihelmintic agent). 13 The catalysts [Mn(TFPP)]- APTES, [Mn(TFPP)]- AP(EA)2TS, [Mn{M(4-NMePy) TFPP}]-SiSO3, [Mn{M(4-N-MePy)TFPP}]- SiSO3(IPG), [Mn{M(4-NMePy) TFPP}]-APTES, [Mn{M(4-N-MePy)TFPP}]- AP(EA)2TS, [Mn{M(4-NMePy) TFPP}]- DA1,6Si were used in (Z)-ciclooctene epoxidation rendering low yields using PhIO as oxidant, contrasting the good yields when imidazole and H2O2 as oxidant were used. In the hydroxylation of cyclohexane the yields were high when the MnP were immobilized through electrostatic interaction. In this system the competitive oxidations are minimized. The best systems were selected for to study the praziquantel oxidation. Differently from FeP results previously obtained, the MnP systems revealed good biomimetic catalysts for PZQ, since high amount of trans-4\'-OH metabolite was obtained, the principal in vivo metabolites. The pyridil substituted MnP, particularly [Mn{T(4-N-MePy)P}]-SiSO3 showed the best results, besides the high yield of trans-4\'-OH (38%), the convertion attained 87%. These results are inedited and very promising biomimetic catalytic systems.