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Soils are the largest pool of carbon (C) in terrestrial ecosystems and store 1500 Gt of C in their soil organic matter (SOM). SOM is a dynamic, complex and heterogeneous mixture, which influences soil quality through a wide range of soil properties. Labile SOM comprises a small fraction of total SOM (approximately 5%), but due to its rapid turnover has been suggested to be most vulnerable to loss following soil disturbance. This research was undertaken to examine the consequences of soil disturbance on labile SOM, its availability and protection in soils using the isotopic analysis of soil-respired CO₂ (δ¹³CO₂). A range of soils were incubated in both the short- (minutes) and long-term (months) to assess changes in labile SOM. Shifts in soil-respired δ¹³CO₂ over the course of soil incubations were found to reflect changes in labile substrate utilisation. There was a rapid depletion of δ¹³CO₂ (from a starting range between -22.5 and -23.9‰, to between -25.8 and -27.5‰) immediately after soil sampling. These initial changes in δ¹³CO₂ indicated an increased availability of labile SOM following the disturbance of coring the soil and starting the incubations. Subsequently δ¹³CO₂ reverted back to the initial, relatively enriched starting values, but this took several months and was due to labile SOM pools becoming exhausted. A subsequent study was undertaken to test if soil-respired δ¹³CO₂ values are a direct function of the amount of labile SOM and soil physical conditions. A range of pasture soils were incubated in the short-term (300 minutes), and changes in soil-respired δ¹³CO₂ were measured along with physical and chemical soil properties. Equilibrium soil-respired δ¹³CO₂, observed after the initial rapid depletion and stabilisation, was a function of the amount of labile SOM (measured as hot water extractable C, HWEC), total soil C and soil protection capacity (measured as specific soil surface area, SSA). An independent experimental approach to assess the effect of SSA, where labile SOM was immobilised onto allophane – a clay mineral with large, active surface area – indicated limited availability of labile SOM through more enriched δ¹³CO₂ (in a range between -20.5 and -20.6 ‰) and a significant (up to three times) reduction in HWEC. In the third study, isotopic measurements were coupled with CO₂ evolution rates to directly test whether equilibrium soil-respired δ¹³CO₂ can reflect labile SOM vulnerability to loss. Soils were sampled from an experimental tillage trial with different management treatments (chemical fallow, arable cropping and permanent pasture) with a range of C inputs and soil disturbance regimes. Soils were incubated in the short- (300 minutes) and long-term (600 days) and changes in δ¹³CO₂ and respiration rates measured. Physical and chemical fractionation methods were used to quantify the amount of labile SOM. Pasture soils were characterised by higher labile SOM estimates (HWEC; sand-sized C; labile C respired during long-term incubations) than the other soils. Long-term absence of plant inputs in fallow soils resulted in a significant depletion of labile SOM (close to 50% based on sand-sized C and HWEC estimates) compared with pasture soils. The values of δ¹³CO₂ became more depleted in 13C from fallow to pasture soils (from -26.3 ‰ to -28.1 ‰) and, when standardised (against the isotopic composition of the solid soil material), Δ¹³CO₂ values also showed a decrease from fallow to pasture soils (from -0.3 ‰ to -1.1 ‰). Moreover, these patterns in isotopic measures were in strong agreement with the amount of labile SOM and its availability across the soils, and were best explained by the isotopic values of the labile HWEC fraction. Collectively, these results confirm that labile SOM availability and utilisation change immediately after soil disturbance. Moreover, isotopic analysis of soil-respired CO₂ is a powerful technique, which enables us to probe mechanisms and examine the consequences of soil disturbance on labile SOM by reflecting its availability and the degree of SOM protection.

The West Pacific Warm Pool (WPWP) plays an important role in the global heat budget and global hydrologic cycle, so knowledge about its past variability would improve our understanding of global climate. Variations in WPWP precipitation are most notable during El Niño-Southern Oscillation events, when climate changes in the tropical Pacific impact rainfall not only in the WPWP, but around the globe. The stalagmite records presented in this dissertation provide centennial-to-millennial-scale constraints of WPWP precipitation during three distinct climatic periods: the Last Glacial Maximum (LGM), the last deglaciation, and the Holocene. In Chapter 2, the methodologies associated with the generation of U/Th-based absolute ages for the stalagmites are presented. In the final age models for the stalagmites, dates younger than 11,000 years have absolute errors of ±400 years or less, and dates older than 11,000 years have a relative error of ±2%. Stalagmite-specific 230Th/232Th ratios, calculated using isochrons, are used to correct for the presence of unsupported 230Th in a stalagmite at the time of formation. Hiatuses in the record are identified using a combination of optical properties, high 232Th concentrations, and extrapolation from adjacent U/Th dates. In Chapter 3, stalagmite oxygen isotopic composition (d18O) records from N. Borneo are presented which reveal millennial-scale rainfall changes that occurred in response to changes in global climate boundary conditions, radiative forcing, and abrupt climate changes. The stalagmite d18O records detect little change in inferred precipitation between the LGM and the present, although significant uncertainties are associated with the impact of the Sunda Shelf on rainfall d18O during the LGM. A millennial-scale drying in N. Borneo, inferred from an increase in stalagmite d18O, peaks at ~16.5ka coeval with timing of Heinrich event 1, possibly related to a southward movement of the Intertropical Convergence Zone (ITCZ). An inferred precipitation maximum (stalagmite d18O minimum) during the mid-Holocene in N. Borneo supports La Niña-like conditions and/or a southward migration of the ITCZ over the course of the Holocene as likely mechanisms for the observed millennial-scale trends. In Chapter 4, stalagmite Mg/Ca, Sr/Ca, and d13C records reflect hydrologic changes in the overlying karst system that are linked to a combination of rainfall variability and cave micro-environmental effects. Dripwater and stalagmite geochemistry suggest that prior calcite precipitation is a mechanism which alters dripwater geochemistry in slow, stalagmite-forming drips in N. Borneo. Stalagmite Mg/Ca ratios and d13C records suggest that the LGM climate in N. Borneo was drier and that ecosystem carbon cycling may have responded to the drier conditions. Large amplitude decadal- to centennial-scale variability in stalagmite Mg/Ca, Sr/Ca and d13C during the deglaciation may be linked to deglacial abrupt climate change events.

La mangrove est un écosystème complexe qui se développe sur les zones intertidales, le long des littoraux (sub)tropicaux. Dû à sa production primaire élevée, couplée à une grande capacité de séquestration du carbone organique, la mangrove a été nommée écosystème à « Carbone Bleu ». Toutefois, le changement climatique à venir, et particulièrement les augmentations en CO2 atmosphérique et en température ainsi que la hausse du niveau marin, pourraient modifier son fonctionnement. Dans de ce contexte, les objectifs étaient de (i) comprendre comment les variations eustatiques passées ont pu impacter les stocks de carbone enfouis dans les sols de mangrove, afin de mieux prévoir l’effet de la future hausse du niveau marin, (ii) caractériser les émissions de CO2 et de CH4 depuis les sols et la colonne d’eau dans la mangrove, et (iii) évaluer l’impact de la hausse des concentrations en CO2 atmosphérique et de la durée d’immersion sur la physiologie de plantules de palétuviers. L’augmentation des concentrations CO2 atmosphérique modifiera la productivité des palétuviers, notamment en stimulant leur activité photosynthétique, facilitant ainsi leurs capacités à coloniser de nouveaux espaces disponibles du fait de la hausse des océans. Cette hausse aura également un effet conséquent sur les stocks de carbone dans les sols, comme nous l’avons montré pour les variations eustatiques de l’Holocène tardif, impliquant également une migration des strates de mangrove. Finalement, les émissions de CO2 et de CH4 vers l’atmosphère sont non négligeables, tout particulièrement celles émises depuis la colonne d’eau, qui devront être pris en compte dans les futurs bilans carbone de l’écosystème. / Mangroves are complex and unique ecosystems that develop on intertidal areas along (sub)tropical coastlines. Due to their position, they are considered as major ecosystems in the coastal carbon cycle. Thanks to their high primary productivity, coupled with a high carbon sequestrating capacity in both biomass and soils, mangroves have been called “Blue Carbon” ecosystems. However, future climate change, and particularly increases in atmospheric CO2 concentrations, temperatures and sea-level rise, may alter its functioning. Within this context, the objectives were to (i) understand how eustatic variations may have impacted soil carbon stocks by the past, in order to better predict the effects of future sea-level rise, (ii) characterize CO2 and CH4 emissions from the soil and also from the water column within the mangrove forest, and (iii) evaluate the impact of future increase in atmospheric CO2 concentrations and in sea-level may affect the physiology of young mangrove seedlings. Increases in atmospheric CO2 concentrations will modify either the seedlings productivity and photosynthetic activity, therefore facilitating their ability to colonize new accommodation spaces due to the rising sea-level. This increase in sea-level will also have a consequent impact on soil carbon stocks, as we showed for the past eustatic variations of the late Holocene, also implying a migration of mangroves stands. Eventually, CO2 and CH4 emissions to the atmosphere were non-neglectable, particularly the one emitted from the water column.

Trees are long living plants, which use carbon from the air and hydrogen and oxygen predominantly from soil water for their growth. They deposit these elements largely into a wood where they may persist for thousands of years. Tree growth is influenced by environment, especially by air temperature and precipitation. These factors have an effect on stomatal conductance and photosynthesis rate which influence carbon stable isotope ratio (13C/12C) in the tree tissue. This thesis is focus on stable carbon isotopes in tree-rings of Norway spruce attacked by honey mushroom, and Norway spruce which doesn?t show any signs of disease. The hypothesis of the thesis is based on an expected difference in carbon isotope fractionation during photosynthesis between the spruce attacked by honey mushroom and a ?healthy? spruce. The difference in isotope fractionation could be caused by water deficit induced by honey mushroom disease in the tree. We expect that the attacked spruce defends against water loss by closing stomata, and it could lead to lower CO2 concentration in the needles and higher ?13C value in tree-rings biomass The stable carbon isotope analysis (IRMS) was done on tree-rings of four spruce pairs, each one including an attacked spruce and spruce which didn?t show any signs of disease. Carbon isotope ratio of early wood, late wood and in biomass of the whole annual increment was measured. In contrary to our hypothesis we did not fined any systematic difference in isotopic composition between the attacked spruce and the spruce which did not show any signs of disease.

Orientador: Helena Teixeira Godoy / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T19:42:12Z (GMT). No. of bitstreams: 1 RobertoSobrinho_Merenice_D.pdf: 1477674 bytes, checksum: 5fe6158bfbdcf36f980d7b9780573936 (MD5) Previous issue date: 2013 / Resumo: A legislação brasileira define o vinho como um produto elaborado com uvas frescas, sãs e maduras, produzido por processo fermentativo adequado. Não é permitida a adição de água como constituinte do produto; a adição de sacarose na correção do mosto é restrita a 3ºGL (20ºC) e a presença de contaminantes deve controlada a fim de garantir a saúde pública. A vitivinicultura do estado de São Paulo está passando por um processo de revitalização cujo objetivo é a melhoria da qualidade do produto. As variedades de uvas mais utlizadas, Vitis labrusca e híbridas não são as mais indicadas para a vinificação. O uso de matéria prima inadequada ou a realização do processo fermentativo de forma equivocada pode levar à obtenção de um vinho com parâmetros de identidade e qualidade em desacordo com a legislação brasileira, comprometendo a ascenção de mercado. Dentre a literatura consultada, são escassos os dados quanto a composição dos vinhos produzidos no estado de São Paulo. O objetivo desse trabalho foi realizar a caracterização físico-quimica e investigar os padrões de identidade e qualidade dos vinhos paulistas. Neste estudo, foram realizadas diversas análises a fim de proporcionar dados que possam contribuir para a avaliação da qualidade do vinho paulista e, consequentemente, direcionar as correções necessárias nos processos de vinificação. Para tanto, foram realizadas análises de pH, acidez total, acidez volátil bruta, acidez volátil corrigida, açúcares totais, anidrido sulfuroso total, grau alcoólico, acetaldeído, metanol, razão isotópica de carbono e oxigênio. Foram analisadas 24 amostras de vinhos paulistas, elaborados por 12 produtores, a partir de uvas americanas, híbridas e viníferas na safra de 2011. A partir dos resultados obtidos foi possível observar que 87,5% das amostras estudadas atenderam aos requisitos legais do Padrão de Identidade e Qualidade. Apenas duas amostras, de produtores diferentes, excederam os limites legais para acidez, que pode ser explicado pelo excesso de chuvas verificado durante a safra de 2011 na região. Quanto ao teor de açúcares, apenas uma amostra apresentou divergência entre o valor referenciado na rotulagem e o encontrado nos ensaios. Todos os vinhos avaliados apresentaram graduação alcoólica adequada aos limites legais, porém houve divergência de até 16,4% entre os teores registrados nos rótulos e os verificados nos ensaios. Os níveis de metanol encontrados estiveram abaixo do limite máximo estabelecido. Para o acetaldeído as concentrações variaram entre 4,51± 0,52 mg.L-1 e 87,22 ± 2,21 mg.L-1, sendo que o recomendado na literatura é de até 50 mg.L-1. Os resultados para a razão isotópica de carbono demonstraram que 55% dos vinhos avaliados se apresentaram fora dos limites legais para a correção da graduação alcoólica. Para a razão isotópica de oxigênio todas as amostras analisadas se encontraram acima dos valores de referência para vinhos de São Paulo da safra de 2011, indicando que não há adição de água exógena. No entanto, amostras que se apresentaram em desacordo com a legislação, indicam que há necessidade de intensificar as orientações aos produtores para que possam realizar um controle mais efetivo no processo de produção para a melhoria da qualidade do produto / Abstract: The wine industry in the state of São Paulo is undergoing a revitalization process aimed at improving the quality of the product. Brazilian law defines wine as a product made from fresh, healthy and ripe grapes, produced by appropriate fermentation. It is not permitted to add water as a constituent of the product; adding sucrose to correct the wort is restricted to 3 GL (20 ° C) and the presence of contaminants must be controlled to ensure public health. The most utilized varieties are vitis labrusca and hybrid, but they are not quite suitable for winemaking. The use of inappropriate raw material or inadequate performance of the fermentation process can lead to obtaining a wine with parameters of quality and identity that differ from the Brazilian legislation, undermining the rising market. Among the literature, there are few data regarding the composition of the wines produced in the state of São Paulo. In this study, several analysis were conducted to provide data that can help to evaluate the quality of the Paulista wine and consequently direct the necessary corrections in the process of winemaking. The aim of this study was to characterize physico-chemically and investigate the patterns of identity and quality of the wines described by Brazilian law. Thus, we performed analyzes of pH, total acidity, volatile acidity crude, volatile acidity adjusted, total sugars, total sulfur dioxide, alcohol content, acetaldehyde, methanol, and carbon isotope ratio of oxygen. We analyzed 24 samples of Paulista wines, processed by 12 producers from American, wine grapes and hybrid grapes from the 2011harvest. From the results, it was observed that 87.5% of the samples met the legal requirements. Only two samples from different producers, exceeded the legal limits for acidity, which can be explained by excessive rainfall occurred during the harvest of 2011. As for the sugar content, only one sample showed divergence between the value found in the assays and the value referenced in labeling. All wines showed high alcohol content appropriate to the legal limits, but there was a difference of up to 15% percent from the levels recorded on labels and checked in for tests. The levels of methanol were found below the limit. For acetaldehyde concentrations ranged between 4.51 ± 0.52 mg.L-1 and 87.22 ± 2.21 mg.L-1, and the recommended is 50 mg.L-1. The results for the carbon isotope ratio demonstrated that 55% of the wines evaluated were out of the legal limits for correction of alcoholic content. For oxygen isotope ratio of all samples were found above the reference values for wines from São Paulo crop of 2011, indicating no addition of exogenous water. However, the samples that are at odds with the legislation indicate that there is a need to strengthen the guidelines for producers and perform a more effective control of the production process / Doutorado / Ciência de Alimentos / Doutora em Ciência de Alimentos

We employ the empirical potential function Airebo to computationally model free-standing Carbon-12 graphene in a classical setting. Our objective is to measure the mean square displacement (MSD) of atoms in the system for different average temperatures and Carbon-13 isotope concentrations. From results of the MSD we aim to develop a technique that employs Transmission Electron Microscopy (TEM), using high-angle annular dark filed (HAADF) detection, to obtain atomic-resolution images. From the thermally diffusive images, produced by the vibrations of atoms, we intent to resolve isotopes types in graphene. For this, we establish a relationship between the full width half maximum (FWHM) of real-space intensity images and MSD for temperature and isotope concentration changes. For the case of changes in the temperature of the system, simulation results show a linear relationship between the MSD as a function of increased temperature in the system, with a slope of 7.858×10-6 Å2/K. We also note a power dependency for the MSD in units of [Å2] with respect to the FWHM in units of [Å] given by FWHM(MSD)=0.20MSD0.53+0.67. For the case of increasing isotope concentration, no statistically significant changes to the MSD of 12C and 13C are noted for graphene systems with 2,000 atoms or more. We note that for the experimental replication of results, noticeable differences in the MSD for systems with approximately 320,000 atoms must be observable. For this, we conclude that isotopes in free-standing graphene cannot be distinguished using TEM.

Perm/Trias-Grenzprofile in den Regionen von Julfa (NW-Iran) und Abadeh (Zentral-Iran) zeigen eine Abfolge von drei charakteristischen Gesteinseinheiten, (1) den Paratirolites Limestone mit dem end-permischen Massensterbehorizont an seiner Oberkante, (2) den Boundary Clay und (3) die untertriassische Elikah-Formation mit der mit Conodonten definierten Perm/Trias-Grenze an seiner Basis. Die Karbonatmikrofazies zeigt eine Veränderung in den Profilen bei Julfa; innerhalb des Paratirolites Limestone ist eine zunehmende Anzahl von Intraklasten, Fe-Mn-Krusten und biogenen Verkrustungen erkennbar. Die Karbonatproduktion des späten Perms wurde mit der Ablagerung von mikrobiellen Karbonaten an der Basis der Elikah-Formation in Julfa erneuert. Die in den Profilen von Baghuk (Abadeh-Region) vorkommenden Mikrobialite sind vielfältig; es gibt groß-und kleinskalige, arboreszierendende Mikrobialit-Ansammlungen mit auffälliger Morphologie und innerer Struktur. In den Regionen von Julfa (NW-Iran) und Abadeh (Zentral-Iran) deutet eine deutliche und weltweit nachvollziehbare negative Kohlenstoffisotopenexkursion hin. Die rasche Exkursion der Kohlenstoffisotopenexkursion unterhalb des Aussterbehorizonts im obersten Bereich des Paratirolites Limestone wird durch eine stratigraphische Kondensation, die ein Defizit der Karbonatproduktion/Akkumulation und/oder eine schnelle geochemische Veränderung in Richtung Karbonatuntersättigung spiegelt, verstärkt. Dies deutet darauf hin, dass ein länger andauernder Mechanismus, wie die thermische Metamorphose von an organischem Material reicher Sedimente, und/oder verstärkte Verwitterung auf den Kontinenten, die negative Perm/Trias- Kohlenstoffisotopenexkursion verursacht haben könnte. Die Stickstoffisotopenwerte zeigen keinen Trend unterhalb des Aussterbehorizonts, was auf eine Kombination verschiedener Prozesse (Stickstofffixierung und ein Gleichgewichtszustand zwischen Nitratassimilation, Stickstoff-Fixierung und Denitrifikation) hinweist. / Permian-Triassic boundary sections in the Julfa (NW Iran) and Abadeh (Central Iran) regions display a succession of three characteristic rock units, (1) the Paratirolites Limestone with the end-Permian mass extinction horizon at its top, (2) the Boundary Clay, and (3) the Early Triassic Elikah Formation with the conodont Permian-Triassic boundary at its base. The carbonate microfacies reveals a change, in the sections near Julfa, within the Paratirolites Limestone with an increasing number of intraclasts, Fe-Mn crusts, and biogenic encrustation. A decline in carbonate accumulation occurs towards the top of this unit, finally resulting in a complete demise of the carbonate factory. The skeletal carbonate factory was restored with the deposition of microbial carbonates at the base of the Elikah Formation at Julfa. At Baghuk Mountain (Abadeh region) large- and small-scale, arborescent microbialite buildups with conspicuous morphology and internal structure occur. In the Julfa and Abadeh regions, a prominent and globally traceable negative carbon isotope excursion indicates major perturbations of the carbon cycle around the P-Tr boundary. The sudden carbonate carbon isotope decrease below the extinction horizon is triggered by stratigraphic condensation that mirrors a deficit of the carbonate production/accumulation and/or a rapid geochemical change towards carbonate undersaturation. The negative carbon isotope trend before extinction horizon is gradual, suggesting that a longer lasting mechanism, such as thermal metamorphism of organic-rich sediments, and/or enhanced weathering on the continents may have caused the negative Permian-Triassic stable carbon isotope excursion. The bulk nitrogen isotope values in the sections of the Julfa region do not show any trend below the extinction horizon, pointing to rather mixing of different processes (nitrogen fixation and an equilibrium state between nitrate assimilation, nitrogen fixation, and denitrification).

No description available.

Yes / Distinguishing animal fats from plant oils in archaeological residues is not straightforward. Characteristic plant sterols, such as ¿-sitosterol, are often missing in archaeological samples and specific biomarkers do not exist for most plant fats. Identification is usually based on a range of characteristics such as fatty acid ratios, all of which indicate that a plant oil may be present, none of which uniquely distinguish plant oils from other fats. Degradation and dissolution during burial alter fatty acid ratios and remove short chain fatty acids, resulting in degraded plant oils with similar fatty acid profiles to other degraded fats. Compound specific stable isotope analysis of ¿13C18:0 and ¿13C16:0, carried out by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), has provided a means of distinguishing fish oils, dairy fats, ruminant and non-ruminant adipose fats but plant oils are rarely included in these analyses. For modern plant oils where C18:1 is abundant, ¿13C18:1 and ¿13C16:0 are usually measured. These results cannot be compared with archaeological data or other modern reference fats where ¿13C18:0 and ¿13C16:0 are measured, as C18:0 and C18:1 are formed by different processes resulting in different isotopic values. Eight samples of six modern plant oils were saponified releasing sufficient C18:0 to measure the isotopic values, which were plotted against ¿13C16:0. The isotopic values for these oils, with one exception, formed a tight cluster between ruminant and non-ruminant animal fats. This result complicates the interpretation of mixed fatty residues in geographical areas where both animal fats and plant oils were in use. / AHRC