932 resultados para Replica method in organic matrix
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In this thesis, I explore the meaning behind sustainable living among organic farmers and their families in two countries. It is based on original, ethnographic research that I conducted in New Zealand in fall 2012 and Peru in summer 2012 with support from the Department of Sociology and Anthropology Meerwarth Undergraduate Research Fund. In carrying out my research I relied on participant-observation, semi-structured interviews, focus groups, and writing ethnographic fieldnotes. Drawing on contemporary scholarship in the anthropology of food and the environment, my thesis contributes to cross-culturally understandings of sustainability and local and global foodways. Specifically, I will interpret the meaning and significance of my informants’ decision to live sustainably through their participation in wwoofing. The global network of wwoofing aims to connect volunteers interested in learning about organic farming techniques with farmers looking for labor assistance. Volunteers exchange work for food, accommodation, knowledge, and experience. As a method of farming and a subjective ideological orientation, this global movement allows travelers from all over the world to experience organic lifestyles worldwide. In my thesis, I connect my experiences of organic living in Peru and New Zealand. In comparing wwoofing practices in these two field sites, I argue that despite observable differences in organic practices, a global organic culture is emerging. Here I highlight some shared features of this global organic culture, such as food authenticity, sustainability of the earth, and a personal connection of individuals to the land. The global organic culture emphasizes a conscious awareness of what is going into one’s body and why. Using food as an expression of values and beliefs, organic farmers reconnect to the land and their food in attempts to construct an alternative identity. By focusing on food authenticity, my informants develop vast relationships with the land, which shapes their identity and creates new forms of self-enhancement.
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Two-thirds of the organic matrix in urinary stones consists of proteins. Their relationship to calculogenesis remains controversial with regard to their effect as inhibitors or promoters during stone formation. The purpose of the present study was to determine the differences in peptide and protein pattern between the urine of stone formers (n = 23) and control dogs (n = 12), as well as between organic matrix of different urinary stones (struvite n = 11, calcium oxalate n = 8, uric acid n = 4) using surface-enhanced laser desorption/ionization time-of-flight mass spectrometry. Specific differences in protein and peptide profiles were found in the organic matrix of different mineral compositions. Characteristic differences were also found in urinary peptide and protein pattern especially in molecular masses below 20 kDa between affected and healthy dogs. Based on the obtained molecular masses they were in some cases tentatively identified as proteins that are known to be involved in stone formation in humans. The study shows that in dogs, specific-urinary peptides and proteins might be associated with urolithiasis. It indicates the importance to further characterize those proteins for possible diagnostic purposes in prognosis and therapy
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Petrographical and geochemical studies of Neogene marine sediments from the Oman Sea (Leg 117, Sites 720, 724, 726 and 730), show a close relationship between the nature and amount of the organic matter, and the degree of degradation of organic matter by sulfate reduction, i.e. pyritization. Petrographically, three major pyritization types were observed: (1) Finely dispersed pyrite framboids in sediments from Oman Margin and Indus Fan, enriched in autochthonous marine organic matter. (2) Infilling of pores by massive pyrite crystals in Oman Margin sediments with a low TOC and a high microfossil content. (3) Pyrite mineralization of lignaceous fragments in organic-depleted sediments from the Indus Fan leading to more massive pyrite. Geochemically, we can define a sulfate reduction index (SRI) as the percentage of initial organic carbon versus that of residual organic carbon. Finely laminated Pliocene-Pleistocene sediments from the Oman Margin exclusively contain organic matter deriving from organic phytoplankton, for which the quantity (TOC) positively correlates with the geochemical quality (Hydrogen Index). We think that the occurrence of this residual organic matter is linked mainly to a high primary paleo-productivity. The intensity of sulfate reduction is constant for sediments with TOC up to 2% and becomes more important when organic input decreases. This degradation process can destroy up to 50% of the initial organic matter, but is not sufficient to explain some of the encountered very low TOC values. It can be seen that sharp increases of certain plankton species (with mineral skeletons) are responsible for a pronounced degradation of organic matter, due to increased sulfate reduction. In that case, the organic matter may be strongly degraded (high SRI), although deposited in an oxygen-depleted environment. Conversely, Miocene-Pliocene sediments contain an autochthonous organic matter that is typical of both low productivity and oxic processes; their very low sulfate reduction index indicates that very little metabolizable organic matter was initially present.
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A comparison was made of capability of two methods: photochemical oxidation and high-temperature catalytic combustion - to oxidize organic carbon in organic substances different in their element composition and in their degree of complexity. Results of measurements of dissolved organic carbon obtained by both of these methods in waters of the Black, Bering and Okhotsk Seas are presented. Varying oxidation degree of organic matter was shown to be dependent on the region and depth. A conclusion was made that the high-temperature catalytic combustion method was to be preferred for dissolved organic carbon determination due to its easier standardization, while values obtained by the wet-oxidation method may be influenced by a great number of factors that are difficult to be controlled.
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C—H stretching bands, νCH, in the infrared spectrum of single crystals of nominally high purity, of laboratory-grown MgO, and of natural upper mantle olivine, provide an “organic” signature that closely resembles the symmetrical and asymmetrical C—H stretching modes of aliphatic —CH2 units. The νCH bands indicate that H2O and CO2, dissolved in the matrix of these minerals, converted to form H2 and chemically reduced C, which in turn formed C—H entities, probably through segregation into defects such as dislocations. Heating causes the C—H bonds to pyrolyze and the νCH bands to disappear, but annealing at 70°C causes them to reappear within a few days or weeks. Modeling dislocations in MgO suggests that the segregation of C can lead to Cx chains, x = 4, with the terminal C atoms anchored to the MgO matrix by bonding to two O−. Allowing H2 to react with such Cx chains leads to [O2C(CH2)2CO2] or similar precipitates. It is suggested that such Cx—Hy—Oz entities represent protomolecules from which derive the short-chain carboxylic and dicarboxylic and the medium-chain fatty acids that have been solvent-extracted from crushed MgO and olivine single crystals, respectively. Thus, it appears that the hard, dense matrix of igneous minerals represents a medium in which protomolecular units can be assembled. During weathering of rocks, the protomolecular units turn into complex organic molecules. These processes may have provided stereochemically constrained organics to the early Earth that were crucial to the emergence of life.
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We identify geochemical features of sedimentary organic matter in various morphostructural zones of the Antarctic sector of the Atlantic. We present background geochemical organic parameters for shelf and deep-sea sediments from the Weddell and Scotia Seas and the Bransfield Strait. Geochemical organic parameters are good indicators of environmental and facial variations in sediments and could be used for environmental monitoring of the World Ocean.
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Matrix application continues to be a critical step in sample preparation for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI). Imaging of small molecules such as drugs and metabolites is particularly problematic because the commonly used washing steps to remove salts are usually omitted as they may also remove the analyte, and analyte spreading is more likely with conventional wet matrix application methods. We have developed a method which uses the application of matrix as a dry, finely divided powder, here referred to as dry matrix application, for the imaging of drug compounds. This appears to offer a complementary method to wet matrix application for the MALDI-MSI of small molecules, with the alternative matrix application techniques producing different ion profiles, and allows the visualization of compounds not observed using wet matrix application methods. We demonstrate its value in imaging clozapine from rat kidney and 4-bromophenyl-1,4-diazabicyclo(3.2.2)nonane-4-carboxylic acid from rat brain. In addition, exposure of the dry matrix coated sample to a saturated moist atmosphere appears to enhance the visualization of a different set of molecules.
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The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.^
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Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62 %), followed by nitrate (15 %), sulphate (9 %) and ammonium (9 %), and chloride (5 %). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18 %, "biomass burning" organic aerosol (BBOA) comprised 23 %, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21 %, and finally a species type characterized by primary m/z peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18 %. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).Ambient wintertime background urban aerosol in Cork city, Ireland, was characterized using aerosol mass spectrometry. During the three-week measurement study in 2009, 93% of the ca. 1 350 000 single particles characterized by an Aerosol Time-of-Flight Mass Spectrometer (TSI ATOFMS) were classified into five organic-rich particle types, internally mixed to different proportions with elemental carbon (EC), sulphate and nitrate, while the remaining 7% was predominantly inorganic in nature. Non-refractory PM1 aerosol was characterized using a High Resolution Time-of-Flight Aerosol Mass Spectrometer (Aerodyne HR-ToF-AMS) and was also found to comprise organic aerosol as the most abundant species (62 %), followed by nitrate (15 %), sulphate (9 %) and ammonium (9 %), and chloride (5 %). Positive matrix factorization (PMF) was applied to the HR-ToF-AMS organic matrix, and a five-factor solution was found to describe the variance in the data well. Specifically, "hydrocarbon-like" organic aerosol (HOA) comprised 20% of the mass, "low-volatility" oxygenated organic aerosol (LV-OOA) comprised 18 %, "biomass burning" organic aerosol (BBOA) comprised 23 %, non-wood solid-fuel combustion "peat and coal" organic aerosol (PCOA) comprised 21 %, and finally a species type characterized by primary m/z peaks at 41 and 55, similar to previously reported "cooking" organic aerosol (COA), but possessing different diurnal variations to what would be expected for cooking activities, contributed 18 %. Correlations between the different particle types obtained by the two aerosol mass spectrometers are also discussed. Despite wood, coal and peat being minor fuel types used for domestic space heating in urban areas, their relatively low combustion efficiencies result in a significant contribution to PM1 aerosol mass (44% and 28% of the total organic aerosol mass and non-refractory total PM1, respectively).
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Ancient starch analysis is a microbotanical method in which starch granules are extracted from archaeological residues and the botanical source is identified. The method is an important addition to established palaeoethnobotanical research, as it can reveal ancient microremains of starchy staples such as cereal grains and seeds. In addition, starch analysis can detect starch originating from underground storage organs, which are rarely discovered using other methods. Because starch is tolerant of acidic soils, unlike most organic matter, starch analysis can be successful in northern boreal regions. Starch analysis has potential in the study of cultivation, plant domestication, wild plant usage and tool function, as well as in locating activity areas at sites and discovering human impact on the environment. The aim of this study was to experiment with the starch analysis method in Finnish and Estonian archaeology by building a starch reference collection from cultivated and native plant species, by developing sampling, measuring and analysis protocols, by extracting starch residues from archaeological artefacts and soils, and by identifying their origin. The purpose of this experiment was to evaluate the suitability of the method for the study of subsistence strategies in prehistoric Finland and Estonia. A total of 64 archaeological samples were analysed from four Late Neolithic sites in Finland and Estonia, with radiocarbon dates ranging between 2904 calBC and 1770 calBC. The samples yielded starch granules, which were compared with the starch reference collection and descriptions in the literature. Cereal-type starch was identified from the Finnish Kiukainen culture site and from the Estonian Corded Ware site. The samples from the Finnish Corded Ware site yielded underground storage organ starch, which may be the first evidence of the use of rhizomes as food in Finland. No cereal-type starch was observed. Although the sample sets were limited, the experiment confirmed that starch granules have been preserved well in the archaeological material of Finland and Estonia, and that differences between subsistence patterns, as well as evidence of cultivation and wild plant gathering, can be discovered using starch analysis. By collecting large sample sets and addressing the three most important issues – preventing contamination, collecting adequate references and understanding taphonomic processes – starch analysis can substantially contribute to research on ancient subsistence in Finland and Estonia.
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International audience
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The Water Framework Directive (WFD) establishes Environmental Quality Standards (EQS) in marine water for 34 priority substances. Among these substances, 25 are hydrophobic and bioaccumulable (2 metals and 23 organic compounds). For these 25 substances, monitoring in water matrix is not appropriate and an alternative matrix should be developed. Bivalve mollusks, particularly mussels (Mytilus edulis, Mytilus galloprovincialis), are used by Ifremer as a quantitative biological indicator since 1979 in France, to assess the marine water quality. This study has been carried out in order to determine thresholds in mussels at least as protective as EQS in marine water laid down by the WFD. Three steps are defined: - Provide an overview of knowledges about the relations between the concentrations of contaminants in the marine water and mussels through bioaccumulation factor (BAF) and bioconcentration factor (BCF). This allows to examine how a BCF or a BAF can be determined: BCF can be determined experimentally (according to US EPA or ASTM standards), or by Quantitative Activity-Structure Relationship models (QSAR): four equations can be used for mussels. BAF can be determined by field experiment; but none standards exists. It could be determined by using QSAR but this method is considered as invalid for mussels, or by using existing model: Dynamic Budget Model, but this is complex to use. - Collect concentrations data in marine water (Cwater) in bibliography for those 25 substances; and compare them with concentration in mussels (Cmussels) obtained through French monitoring network of chemicals contaminants (ROCCH) and biological integrator network RINBIO. According to available data, this leads to determine the BAF or the BCF (Cmussels /Cwater) with field data. - Compare BAF and BCF values (when available) obtained with various methods for these substances: BCF (stemming from the bibliography, using experimental process), BCF calculated by QSAR and BAF determined using field data. This study points out that experimental BCF data are available for 3 substances (Chlorpyrifos, HCH, Pentachlorobenzene). BCF by QSAR can be calculated for 20 substances. The use of field data allows to evaluate 4 BAF for organic compounds and 2 BAF for metals. Using these BAF or BCF value, thresholds in shellfish can be determined as an alternative to EQS in marine water.
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Tese de dout. em Química, Faculdade de Ciências do Mar e do Ambiente, Univ. do Algarve, 2002
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This work considered the micro-mechanical behavior of a long fiber embedded in an infinite matrix. Using the theory of elasticity, the idea of boundary layer and some simplifying assumptions, an approximate analytical solution was obtained for the normal and shear stresses along the fiber. The analytical solution to the problem was found for the case when the length of the embedded fiber is much greater than its radius, and the Young's modulus of the matrix was much less than that of the fiber. The analytical solution was then compared with a numerical solution based on Finite Element Analysis (FEA) using ANSYS. The numerical results showed the same qualitative behavior of the analytical solution, serving as a validation tool against lack of experimental results. In general this work provides a simple method to determine the thermal stresses along the fiber embedded in a matrix, which is the foundation for a better understanding of the interaction between the fiber and matrix in the case of the classical problem of thermal-stresses.
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The main purpose of this thesis is to go beyond two usual assumptions that accompany theoretical analysis in spin-glasses and inference: the i.i.d. (independently and identically distributed) hypothesis on the noise elements and the finite rank regime. The first one appears since the early birth of spin-glasses. The second one instead concerns the inference viewpoint. Disordered systems and Bayesian inference have a well-established relation, evidenced by their continuous cross-fertilization. The thesis makes use of techniques coming both from the rigorous mathematical machinery of spin-glasses, such as the interpolation scheme, and from Statistical Physics, such as the replica method. The first chapter contains an introduction to the Sherrington-Kirkpatrick and spiked Wigner models. The first is a mean field spin-glass where the couplings are i.i.d. Gaussian random variables. The second instead amounts to establish the information theoretical limits in the reconstruction of a fixed low rank matrix, the “spike”, blurred by additive Gaussian noise. In chapters 2 and 3 the i.i.d. hypothesis on the noise is broken by assuming a noise with inhomogeneous variance profile. In spin-glasses this leads to multi-species models. The inferential counterpart is called spatial coupling. All the previous models are usually studied in the Bayes-optimal setting, where everything is known about the generating process of the data. In chapter 4 instead we study the spiked Wigner model where the prior on the signal to reconstruct is ignored. In chapter 5 we analyze the statistical limits of a spiked Wigner model where the noise is no longer Gaussian, but drawn from a random matrix ensemble, which makes its elements dependent. The thesis ends with chapter 6, where the challenging problem of high-rank probabilistic matrix factorization is tackled. Here we introduce a new procedure called "decimation" and we show that it is theoretically to perform matrix factorization through it.