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I investigated how land use and human activities affect the sources and cycling of carbon (C) in subtropical rivers. Annually rivers receive a large amount of terrestrial C, process a portion of this C and return it to the atmosphere as CO2. The rest is transported to the ocean. Land use and human activities can affect the sources and fate of terrestrial C in rivers. However, studies on these effects are limited, especially in the humid subtropics. I combined measurements of the partial pressure of dissolved CO2 (pCO2), C isotopes (13C and 14C) and solid-state 13C nuclear magnetic resonance (NMR) to study C cycling in three subtropical rivers in Texas, two small rivers (Buffalo Bayou and Spring Creek) and a midsized river (the Brazos). My pCO2 data show that small humid subtropical rivers are likely a large source of atmospheric CO2 in the global C cycle. My measurements on pCO2, C isotopic and chemical composition of dissolved inorganic C (DIC) and particulate organic C (POC) revealed four types of effects of land use and human activities on river C cycling. First, oyster shells and crushed carbonate minerals used in road construction are being dissolved and slowly drained into Buffalo Bayou and the lower Brazos and may be a source of river CO2 released to the atmosphere. Second, river damming and nutrient input from urban treated wastewater stimulate algal growth and reduce CO2 evasion of the middle Brazos. Third, urban treated wastewater discharge is adding old POC to the middle Brazos and decomposition of the old POC adds to the old riverine DIC pool. Fourth, agricultural activities coupled with high precipitation enhance loss of old organic C (OC) from deep soils to the lower Brazos, and decomposition of the old soil OC contributes to the old CO2 evaded. I document for the first time the river C cycling effects of the use of carbonate minerals in construction and the riverine discharge of urban wastewater. Results presented here indicate the need to study disturbed river systems to better constrain the global C budget.

The erosion or dissolution of stainless steel grade 304 as base metal by molten brazing fillermetal was investigated using one nickel and two iron based filler metals. The difference betweentwo iron filler metal is 5 % Manganese content in one of the filler metal. The Wettability of fillermetal is effected by oxidation of base or filler metal for which high vacuum or non reacting gasis used as a furnace atmosphere to reduce the partial pressure of oxygen. The furnace parameterseffecting erosion of base metal was observed e.g. peak temperature and brazing time. The effectof filler mass was also observed. The erosion depth was measured by light optical microscope.All the three filler metal shows different erosion behavior in nitrogen atmosphere compare tohigh vacuum. In high vacuum some of the elements evaporates at brazing temperature whichchanges the properties of filler metal. This change of composition in filler metal was observed byEDX analysis. SEM analysis was used to identify different element rich phases.

O ciclo diurno do fluxo de CO2 no oceano Atlântico equatorial para o mês de agosto é estimado utilizando um algoritmo de transferência de gases. O algoritmo é baseado na teoria de similaridade de Monin-Obukhov para fluxos turbulentos na interface ar-mar e na física da transferência de CO2 na camada molecular oceânica. O ciclo diurno do fluxo de CO2, obtido na região, caracteriza o oceano Atlântico equatorial, durante o período, como fonte de CO2 para a atmosfera e seus valores estão entre 0,71 e 0,85 mol CO2 m^-2 ano^-1. / The diurnal cycle of CO2 is estimated for the month of August on the Atlantic Ocean using a gas transfer algorithm. The algorithm is based on the Monin-Obukhov similarity theory for turbulent transfer at the air-sea interface and the physics of the CO2 transfer at the oceanic molecular layer.

La température et la pression partielle d’oxygène (PO2) constituent les paramètres majeurs contrôlantles évolutions thermochimiques en réacteur des combustibles nucléaires de type oxyde, et notammentla spéciation des produits de fission potentiellement corrosifs (Cs, I, Te). Pour limiter les risques derupture de la gaine en Zr par corrosion, une solution innovante consiste à imposer au combustible defonctionner dans un domaine de PO2 où les espèces chimiques des gaz de fission sont inoffensives, pardopage in-situ avec un tampon oxydo-réducteur solide. Le niobium, avec ses couples redoxNbO2/NbO et Nb2O5/NbO2, a été identifié comme le candidat le plus prometteur. Un procédé defabrication d’un combustible dopé niobium répondant à cet objectif et conforme aux spécificationsd’usage (densité, microstructure) a été optimisé. L’étude expérimentale du système UO2-NbOx a révélél’existence à 810°C d’une phase liquide entre UO2 et NbO2, non identifiée à ce jour. La caractérisationdes phases solides et en solution du niobium nous a conduit à proposer un modèle thermodynamiquede solubilité du dopant dans UO2 à 1700°C. Une étude approfondie de la spéciation du niobiumprécipité a permis d’identifier la présence simultanée dans le matériau des phases majeures NbO2 etNbO, ainsi que Nb en moindre teneur. La coexistence du niobium sous deux degrés d’oxydationdifférents constitue un élément-clé de démonstration d’un possible effet tampon in-situ, dont l’impactest observé sur certaines propriétés du combustible dépendantes de la PO2, la densification notamment.Les résultats confirment le potentiel prometteur des combustibles tamponnés en PO2 au regard de sesperformances en réacteur. / Temperature and oxygen partial pressure (PO2) of nuclear oxide fuels are the main parametersgoverning both their thermochemical evolution in reactor and the speciation of volatile fissionproducts such as Cs, I or Te. An innovative way to limit the risk of cladding rupture by corrosionunder irradiation consists in buffering the oxygen partial pressure of the fuel under operation in a PO2domain where the fission gas are harmless towards Zr clad, by using solid redox buffers as additives.Niobium, with its NbO2/NbO and Nb2O5/NbO2 redox couples has been found to be a promisingcandidate to this end. A manufacturing process of a buffered UO2 fuel, doped with niobium has beenoptimized, in order to fulfill usual specifications (density, microstructure). The experimental study ofthe UO2-NbOx system has shown the existence of a liquid phase between UO2 and NbOx at 810°C,which was not reported in the literature. The characterization of Nb containing phases present in UO2both in solid solution and as precipitates has lead us to propose a solubility thermodynamic model ofniobium in UO2 at 1700°C. An extensive study of the niobium precipitates shows the co-existence inthe fuel of NbO2 and NbO as major phases, together with small amounts of metallic Nb. The coexistenceof niobium under two oxidation states inside the fuel is a key element of demonstration of apossible in-situ buffering effect, which is likely to impact some properties of the material that aredependent upon PO2, such as densification. These results confirm the promising potential of oxygenbuffered fuels as regard to their performance in reactor.

Thesis (M.S.); Submitted to the University of California, Berkeley, 210 Hearst Mining Memorial Bldg., Berkeley, CA 94720 (US); 15 Dec 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "LBNL--54116" Li, Sonny X. USDOE Director. Office of Science. Basic Energy Sciences (US) 12/15/2003. Report is also available in paper and microfiche from NTIS.

O ciclo diurno do fluxo de CO2 no oceano Atlântico equatorial para o mês de agosto é estimado utilizando um algoritmo de transferência de gases. O algoritmo é baseado na teoria de similaridade de Monin-Obukhov para fluxos turbulentos na interface ar-mar e na física da transferência de CO2 na camada molecular oceânica. O ciclo diurno do fluxo de CO2, obtido na região, caracteriza o oceano Atlântico equatorial, durante o período, como fonte de CO2 para a atmosfera e seus valores estão entre 0,71 e 0,85 mol CO2 m^-2 ano^-1. / The diurnal cycle of CO2 is estimated for the month of August on the Atlantic Ocean using a gas transfer algorithm. The algorithm is based on the Monin-Obukhov similarity theory for turbulent transfer at the air-sea interface and the physics of the CO2 transfer at the oceanic molecular layer.

An induction setup for levitation studies of molten metals was built. The setup was used to levitate and heat stainless steel samples of 2.00 g to 1600 °C and subject them to different atmospheres. Changes in shape and temperature were recorded by video and infrared thermocouple. Oxide films forming on the droplets during levitation were observed. It was possible to notice an immediate surface reaction when the reaction gas was introduced. This reaction is concluded to influence the surface and bulk composition, and therefore have an effect on the shape evolution of the droplet. A more oxidizing atmosphere resulted in a more conical droplet shape; this is thought to be an effect of lowered surface tension and the conically shaped volumetric force caused by the magnetic field. Changes in temperature after the sample is molten are thought to be an effect of changes in emissivity, caused by surface oxidization. Post mortem analysis show a difference in surface morphology for samples subjected to different gases, as well as a difference in amount of oxidization.

VILLELA, FRANCO N. J. Análise decadal do fluxo de CO2 entre o oceano e a atmosfera na passagem de Drake, Oceano Austral. 2011. 148 f. Dissertação (mestrado) Programa de Pós-Graduação em Ciência Ambiental (PROCAM), Universidade de São Paulo, São Paulo, 2011. Para a área delimitada pelos paralelos 60ºS e 62,5ºS e pelos meridianos 60ºW e 65ºW, localizada no sul da Passagem de Drake, no Oceano Austral, próximo à Península Antártica, foram calculadas as distribuições médias de 2000 a 2009, sazonais e anual, do fluxo de CO2 na interface oceano-atmosfera e de suas variáveis associadas: a pressão parcial de CO2 na superfície marinha (PCO2sw), a pressão parcial de CO2 na atmosfera (PCO2ar), a diferença da pressão parcial de CO2 entre o oceano e a atmosfera (PCO2) e a taxa de transferência gasosa (TR), que é produto do coeficiente solubilidade do CO2 na água do mar pela velocidade de transferência gasosa. A parametrização utilizada no cálculo dos fluxos foi a de Takahashi et al. (2009) com TR dependente da velocidade do vento ao quadrado multiplicada por um fator de escala 0,26. A área de estudo tem cerca de 75 mil km2 e foi dividida em uma grade espacial de 0,5º x 0,5º, resultando em 50 quadrículas. Foram utilizados mais de 46 mil medições de PCO2sw, que na média espacial variou de 362,7 ±11,2 a 371,9 ±17,5 µatm, no verão e primavera respectivamente. A PCO2 variou de -0,4 a 5,7 µatm no outono e primavera, respectivamente. A TR variou de 0,065 ±0,04 a 0,088 ±0,002 gC.mês-1.m-2.µatm-1, no verão e inverno, respectivamente. O fluxo líquido, se tomando a concentração de gelo como negligenciável, variou de -0,039 ±0,865 a 0,456 ±1,221 gC.m-2.mês-1, no outono e inverno, respectivamente. O fluxo total anual de carbono, estimado através da média espacial por quadrícula, foi de 95 GgC.ano-1. Dessa maneira, na estimativa anual, a superfície do mar se comporta como fonte de CO2 para a atmosfera, principalmente devido à região da plataforma continental com PCO2sw consideravelmente maior que o da atmosfera. Sazonalmente sugere-se que no verão a maior disponibilidade de radiação solar, a temperatura da superfície do mar (TSM) mais elevada e os ventos mais fracos favorecem a produção de biomassa fitoplanctônica, fazendo com que a bomba biológica seja o processo dominante na diminuição da PCO2sw e na absorção de CO2 atmosférico pela superfície marinha. Já no inverno, os ventos se intensificam e, associados com o forte resfriamento da TSM, promovem a mistura com águas profundas ricas em carbono inorgânico dissolvido, levando a superfície marinha a um estado de supersaturação de CO2 em relação à atmosfera. Ventos circumpolares de oeste mais intensos e deslocados para sul tem sido apontados como a causa do aumento da PCO2sw em igual ou maior taxa do que ocorre na atmosfera. Na área de estudo foi levantada uma tendência média da intensidade do vento de 0,23 ±0,03 m.s-1.década-1 e um aumento na freqüência da componente zonal de oeste (positiva) de 1,47 ± 1,13 % .década-1. Sugere-se que estas tendências estejam relacionadas com o Modo Anular Austral (SAM). Entretanto, a tendência decadal estimada para a PCO2sw foi menor que para a atmosfera, apesar de ambas indicarem tendência de aumento. Acredita-se que a grande variabilidade e distribuição esparsa de dados tenham mascarado a magnitude da estimativa da tendência de PCO2sw. / VILLELA, FRANCO N. J. Decadal analysis of the CO2 sea-air flux in the Drake Passage, Southern Ocean 2011. 148 f. Dissertação (mestrado) Programa de Pós-Graduação em Ciência Ambiental (PROCAM), Universidade de São Paulo, São Paulo, 2011. For the area bounded by parallels 60°S and 62.5°S and meridians 60°W and 65°W, located in the southern Drake Passage in the Southern Ocean, near the Antarctic Peninsula, mean seasonal and annual distributions of CO2 flux at the ocean-atmosphere interface, from 2000 to 2009, have been computed, as well as their associated variables: the CO2 partial pressure at sea surface (PCO2sw), the CO2 partial pressure in atmosphere (PCO2ar), the CO2 pressure difference between ocean and atmosphere (PCO2), and the gas transfer rate (TR), which is the product of the CO2 solubility coefficient in sea water by the gas transfer velocity. The parameterization used to calculate fluxes was that of Takahashi et al. (2009) with TR depending on the squared wind speed multiplied by a scale factor 0.26. The study area has about 75,000 km2 and was divided into a grid of 0.5° x 0.5°, resulting in 50 area boxes. Over 46,000 PCO2sw measurements were used, which in the spatial mean varied from 362.7±11.2 to 371.9±17.5 µatm, in summer and spring, respectively. The PCO2 varied from 0.4 to 5.7 µatm in autumn and spring, respectively. TR varied from 0.065±0.04 to 0,088±0.002 gC.month-1.m-2.µatm-1, in summer and winter, respectively. The net flux, taking ice concentration as negligible, varied from 0.039±0.865 to 0.456±1.221 gC.month-1.m-2, in autumn and winter, respectively. The total annual carbon flux, estimated through the spatial mean per square, was 95 GgC.y-1. Thus, in the annual estimate the region acts as a source to the atmosphere, mainly due to the continental shelf having PCO2sw considerably greater than that of the atmosphere. Seasonally, it is suggested that in summer the greater availability of solar radiation, warmer sea surface temperature (SST), and weaker winds favor the production of phytoplanktonic mass, making the biological pump the dominating process in lowering the PCO2sw and the absorption of atmospheric CO2 by the sea surface. On the other hand, in winter winds intensify and, in association with the strong cooling of the SST, promote mixing with deep waters rich in dissolved inorganic carbon, leading the sea surface to a state of supersaturation in CO2 relative to the atmosphere. Stronger circumpolar west winds and displaced to the south have been pointed as the cause for the increase of PCO2sw at a rate equal to or greater than that occurring in the atmosphere. In the study area it has been detected a mean trend of wind intensity 0.23±0.03 m.s-1.decade-1 and an increase in the western zonal component of 1.47±1.3%.decade-1. It is suggested that these trends are related to the Southern Annular Mode (SAM). However, the decadal trend estimated for the PCO2sw was smaller than for the atmosphere, in spite of both indicating increasing tendencies. It is believed that the great variability and scatter distribution of the data have masked the magnitude of the PCO2SW trend estimate.

Chromium is an important alloying element in stainless steel but also environmentally harmful element. A number of mineralogical phases present in the slag matrix can contain chromium and lead to chromium leaching. Chromium in slag if not stabilized, could oxidize to the cancerogenic hexavalent state, and leach out if exposed to acidic and oxygen rich environment. Other environmental concerns are slag dusting and chromium escape to the atmosphere. Despite the fact that there is a certain risk of Cr-emission from slags at operating conditions, still very little is known regarding the emission of the oxides of chromium during the slag tapping. Spinel phase is known to be important for controlling the leaching properties of chromium from the slag. The objective of the present study was to get an understanding of the phase relationships and chromium partition in the chromium-containing industrial slags and synthetic slags with a view to control the chromium stabilization in spinel phase. The impact of slag basicity, heat treatment, oxygen partial pressure and Al2O3 addition, on the phase relationships and chromium partition has been determined. The experimental results were compared with the phase equilibrium calculations. It was found that the oxygen partial pressure in the gas phase had a strong impact on chromium partition. The experimental results show that the impact of the slag basicity on chromium partition at lower oxygen partial pressures was negligible in contrast to that in air. The amount of spinel phase was found to increase with increased Al2O3 content. Slow cooling of slag and soaking at low oxygen partial pressure would improve the spinel phase precipitation. This treatment will also lead to less Cr dissolved in the unstable matrix phases. Chromium oxide was found to be emitted when chromium containing slags were exposed to oxidizing atmosphere. The results indicate that chromium oxide evaporation increases with increase in temperature and oxygen partial pressure, but decreases with slag basicity and sample thickness. / <p>QC 20131114</p> / Steel Eco-Cycle