Isotopic study of ceria-catalyzed soot oxidation in the presence of NOx

The ceria-catalyzed soot oxidation mechanism has been studied by a pulse technique with labeled O2 in the absence and presence of NO, using ceria–soot mixtures prepared in the loose contact mode. In the absence of soot, the ceria-catalyzed oxidation of NO to NO2 takes place with ceria oxygen and not with gas-phase O2. However, the oxygen exchange process between gas-phase O2 and ceria oxygen (to yield back O2, but with oxygen atoms coming from ceria) prevailed with regard to the ceria-catalyzed oxidation of NO to NO2. Gas-phase O2 did not react directly with soot when pulsed to a soot–ceria loose contact mixture. Instead, ceria oxygen is transferred to soot (this step does not require gas-phase molecular oxygen to be present), and gas-phase O2 fills up the vacancies created on the oxide in a further step. The transfer of oxygen between ceria and soot occurred directly in the absence of NO. However, in the presence of NO, NO2 is expected to be additionally generated by ceria oxygen oxidation, which also reacts with soot. The main reaction products of the ceria-catalyzed soot oxidation reaction with NO/O2 were CO2 and NO. Additionally, evidence of the reduction of NOx to N2 was found.

Reconstituição da paleoprecipitação no sul do Nordeste Brasileiro durante os dois últimos ciclos glaciais a partir da aplicação de registros isotópicos de oxigênio de estalagmites da Chapada Diamantina, Bahia.

Registros isotópicos de oxigênio obtidos em alta resolução das estalagmites CL2 e MAG das cavernas Calixto e Marota, região da Chapada Diamantina (CD) (12ºS), Estado da Bahia, sul do Nordeste brasileiro (sNEB), permitiram reconstituir as mudanças passadas da precipitação entre 165-128 e 59-39 mil anos A.P. Para a reconstituição paleoclimática considerou-se resultados de um estudo de calibração realizado em duas cavernas da CD o qual demonstrou uma relação entre composição isotópica da água meteórica e de gotejamento e sugeriu um ambiente adequado para a deposição do espeleotema em condições equilíbrio e/ou próximas com a água de gotejamento. A interpretação da paleoprecipitação através dos registros isotópicos \'\'delta\' POT.18\'O das estalagmites também foi baseada na relação entre composição isotópica da água da precipitação e a quantidade de chuva obtidos em estações da IAEA-GNIP no Brasil e de simulações das variações do \'\'delta\' POT.18\'O da chuva através do modelo climático ECHAM-4. Esses dados indicaram o efeito quantidade (amount effect) como fator preponderante de controle isotópico da água da chuva que formam os espeleotemas na CD, significando que a diminuição dos valores de \'\'delta\' POT.18\'O está associada ao aumento do volume de chuvas e vice-versa. Os registros de \'\'delta\' POT.18\'O dos espeleotemas permitiram reconstituir a variação da paleoprecipitação na escala orbital e milenar durante o penúltimo glacial bem como correlacionar mudanças na paleoprecipitação no sNEB com eventos milenares registrados na Groelândia no último glacial. Os registros da CD indicaram um aumento (diminuição) da paleoprecipitação na Bahia relacionado a diminuição (aumento) da insolação austral de verão a 10ºS durante o penúltimo glacial, similar ao observado no último ciclo precessional. Na escala orbital os registros da CD estiveram em antifase com os paleoindicadores isotópicos do Sudeste brasileiro e em fase com os valores de\'\'delta\' POT.18\'O dos espeleotemas do leste da China. Esse padrão de precipitação é similar ao observado na última glaciação e sugere que a variação na insolação de verão afetou as monções sul-americanas (MSA) promovendo mudanças na precipitação no sNEB no penúltimo glacial. Condições áridas no sNEB durante o aumento da insolação de verão estariam provavelmente associadas ao aprofundamento da subsidência de ar provocado pelo fortalecimento da circulação leste-oeste da MSA devido ao aumento das atividades convectivas na Amazônia o que teria, favorecido um posicionamento mais a sul da Zona de Convergência do Atlântico Sul (ZCAS). O oposto também ocorreria durante as fases de baixa insolação de verão quando a MSA estaria provavelmente mais desintensificada. Durante o penúltimo glacial (Terminação Glacial II) abruptas oscilações nos registros da CD para valores mais baixos de \'\'delta\' POT.18\'O indicaram um profundo aumento da precipitação coincidente com o evento Heinrich (H11). Nesse período a paleoprecipitação no sNEB esteve correlacionada negativamente com as mudanças climáticas na China e no oeste amazônico (Peru) e positivamente com o Sudeste brasileiro. Interpretou-se que as anomalias positivas da precipitação no sNEB podem ter estado relacionadas ao deslocamento para sul da Zona de Convergência Intertropical (ZCIT) bem como com a intensificação da MSA e ZCAS nesse período. Finalmente, oscilações isotópicas abruptas para valores mais altos observadas durante o estágio marinho isotópico 3 coincidentes com os eventos quentes registrados na Groelândia, denominados de eventos Dansgaard-Oeschger (DO), foram interpretados como a ocorrência de eventos muito secos no sNEB. Essas variações da precipitação na escala milenar, que estão em fase com os registros no Peru, podem ter estado relacionadas ao deslocamento para norte da ZCIT o que teria promovido uma profunda desintensificação da MSA.

P-T-Fluid evolution and graphite deposition during retrograde metamorphism in Ribeira Fold Belt, SE Brazil: Oxygen fugacity, fluid inclusions and C-O-H isotopic evidence

Combined fluid inclusion (FI) microthermometry, Raman spectroscopy, X-ray diffraction, C-O-H isotopes and oxygen fugacities of granulites from central Ribeira Fold Belt, SE Brazil, provided the following results: i) Magnetite-Hematite fO(2) estimates range from 10(-11.5) bar (QFM + 1) to 10(-18.3) bar (QFM - 1) for the temperature range of 896 degrees C-656 degrees C, implying fO(2) decrease from metamorphic peak temperatures to retrograde conditions; ii) 5 main types of fluid inclusions were observed: a) CO(2) and CO(2)-N(2) (0-11 mol%) high to medium density (1.01-0.59 g/cm(3)) FI; b) CO(2) and CO(2)-N(2) (0-36 mol%) low density (0.19-0.29 g/cm(3)) FI; c) CO(2) (94-95 mol%)-N(2) (3 mol%)-CH(4) (2-3 mol%)-H(2)O (water phi(v) (25 degrees C) = 0.1) FI; d) low-salinity H(2)O-CO(2) FI; and e) late low-salinity H(2)O FI; iii) Raman analyses evidence two graphite types in khondalites: an early highly ordered graphite (T similar to 450 degrees C) overgrown by a disordered kind (T similar to 330 degrees C); iv) delta(18)O quartz results of 10.3-10.7 parts per thousand, imply high-temperature CO(2) delta(18)O values of 14.4-14.8 parts per thousand, suggesting the involvement of a metamorphic fluid, whereas lower temperature biotite delta(18)O and delta D results of 7.5-8.5 parts per thousand and -54 to -67 parts per thousand respectively imply H(2)O delta(18)O values of 10-11 parts per thousand and delta D(H2O) of -23 to -36 parts per thousand suggesting delta(18)O depletion and increasing fluid/rock ratio from metamorphic peak to retrograde conditions. Isotopic results are compatible with low-temperature H(2)O influx and fO(2) decrease that promoted graphite deposition in retrograde granulites, simultaneous with low density CO(2), CO(2)-N(2) and CO(2)-N(2)-CH(4)-H(2)O fluid inclusions at T = 450-330 degrees C. Graphite delta(13)C results of -10.9 to -11.4 parts per thousand imply CO(2) delta(13)C values of -0.8 to -1.3 parts per thousand suggesting decarbonation of Cambrian marine carbonates with small admixture of lighter biogenic or mantle derived fluids. Based on these results, it is suggested that metamorphic fluids from the central segment of Ribeira Fold Belt evolved to CO(2)-N(2) fluids during granulitic metamorphism at high fO(2), followed by rapid pressure drop at T similar to 400-450 degrees C during late exhumation that caused fO(2) reduction induced by temperature decrease and water influx, turning carbonic fluids into CO(2)-H(2)O (depleting biotite delta(18)O and delta D values), and progressively into H(2)O. When fO(2) decreased substantially by mixture of carbonic and aqueous fluids, graphite deposited forming khondalites. (C) 2010 Elsevier Ltd. All rights reserved.

Oxygen Isotopic and Soluble Ionic Composition of a Shallow Firn Core, Inilchek Glacier, Central Tien Shan

Oxygen isotopic and soluble ionic measurements made on snow-pit (2 in depth) and firn-core (12.4 m depth samples recovered from the accumulation zone 5100 m) of Inilchek glacier 43degrees N, 79degrees E) provide information on recent (1992-98) climatic and environmental conditions in the central Tien Shan region of central Asia. The combined 14.4 m snow-pit/firn-core profile lies within the firn zone, arid contains only one observed melt feature (10 m temperature = - 12 degreesC), Although some post-depositional attenuation of the sub-seasonal delta(18)O record is possible, annual cycles are apparent throughout the isotope profile. We therefore use the preserved delta(18)O record to establish a depth/age scale for the core. Mean delta(18)O values for the entire core and for summer periods are consistent with delta(18)O/temperature observations, and suggest the delta(18)O record provides a means to reconstruct past changes in summer surface temperature at the site. Major-ion (Na(+), K(+), Mg(2+), Ca(2+), NH(4)(+), Cl(-), NO(3)(-), SO(4)(2-)) data from the core demonstrate the dominant influence of dust deposition on the soluble chemistry at the site, arid indicate significant interannual variability in atmospheric-dust loading during the 1900s. Anthropogenic impacts oil NH(4)(+) concentrations are observed at the site, and suggest a summer increase in atmospheric NH(4)(+) that may be related to regional agricultural (nitrogen-rich fertilizer use activities.

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ18O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in 18O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO32−] (∼50 μmol/l) in the surface waters. The resulting weighted average δ18O value for the studied period is −9.6‰, compared with a calculated equilibrium δ18O value of −9.4‰. These data convincingly demonstrate that δ18O of calcite are, for the most part, a very reliable proxy for temperature and δ18O of the water.

Carbon and oxygen isotopic compositions of Cibicidoides spp. and fine fraction separates (<10 µm) from ODP Holes 113-689B, 119-738B, and 120-748B

A prominent middle Eocene warming event is identified in Southern Ocean deep-sea cores, indicating that long-term cooling through the middle and late Eocene was not monotonic. At sites on Maud Rise and the Kerguelen Plateau, a distinct negative shift in d18O values (~1.0 per mil) is observed ca. 41.5 Ma. This excursion is interpreted as primarily a temperature signal, with a transient warming of 4°C over 600 k.y. affecting both surface and middle-bathyal deep waters in the Indian-Atlantic region of the Southern Ocean. This isotopic event is designated as the middle Eocene climatic optimum, and is interpreted to represent a significant climatic reversal in the midst of middle to late Eocene deep-sea cooling. The lack of a significant negative carbon isotope excursion, as observed during the Paleocene-Eocene thermal maximum, and the gradual rate of high-latitude warming suggest that this event was not triggered by methane hydrate dissociation. Rather, a transient rise in pCO2 levels is suspected, possibly as a result of metamorphic decarbonation in the Himalayan orogen or increased ridge/arc volcanism during the late middle Eocene.

Oxygen and carbon isotopic composition of shells from Radix sp. in lakes across the Tibetan Plateau

The Tibetan Plateau (TP), including its surrounding mountain ranges, represents the largest store of ice outside the polar regions. It hosts numerous lakes as well as the head waters of major Asian rivers, on which billions of people depend, and it is particularly sensitive to climate change. The moisture transport to the TP is controlled by the Indian and Pacific monsoon and the Westerlies. Understanding the evolution of the interaction of these circulation systems requires studies on climate archives in different spatial and temporal contexts. The objective of this study is to learn more about the interannual variability of precipitation patterns across the TP and how different hydrologic systems react to different climatic factors. Aragonite shells of the aquatic gastropod Radix, which is widely distributed in the region, may represent suitable archives for inferring hydrologic and climatic signals in particularly high resolution. Therefore, sclerochronological studies of d18O and d13C ratios in Radix shells from seven lakes were conducted, each representing a different hydrologic and climatic setting, on a transect from the Pamirs across the TP. The shell patterns exhibit an increasing influence of precipitation and a decreasing influence of evaporation on the isotope compositions from west to east. d18O values of shells from lakes on the eastern and central TP (Donggi Cona, Yamdrok Yumco, Tarab Co) mirror monsoon signals, indicated by more negative values and higher variabilities compared to the more western lakes (Karakul, Bangong/Nyak, Manasarovar). In Yadang Co, located on the central southern TP, the monsoon rains did not reach the lake in the sampling year, although it is located in a region which is usually affected by monsoon circulation. The d18O values are used to differentiate the annual hydrological cycle into ice cover period, melt water period, precipitation period and evaporation period. d13C compositions in the shells particularly depend on specific habitats, which vary in biological productivity and in carbon sources. d18O and d13C patterns show a positive covariance in shells originating from large closed basins. The results show that Radix shells mirror general climatic differences between the seven lake regions. These differences reflect both regional and local climate signals in sub-seasonal resolution, without noticeable dependence on the particular lake system.

Isotopic composition of oxygen, carbon, and sulfur in interstitial water and cores at DSDP Leg 59 Holes

Comprehensive isotopic studies based on data from the Deep Sea Drilling Project have elucidated numerous details of the low- and high-temperature mechanisms of interaction between water and rocks of ocean crustal seismic Layers 1 and 2. These isotopic studies have also identified climatic changes during the Meso-Cenozoic history of oceans. Data on the abundance and isotopic composition of sulfur in the sedimentary layer as well as in rocks of the volcanic basement are more fragmentary than are oxygen and carbon data. In this chapter we specifically concentrate upon isotopic data related to specific features of the mechanisms of low-temperature interaction of water with sedimentary and volcanogenic rocks. The Leg 59 data provide a good opportunity for such lithologic and isotopic studies, because almost 600 meters of basalt flows and sills interbedded with tuffs and volcaniclastic breccias were cored during the drilling of Hole 448A. Moreover, rocks supposedly exposed to hydrothermal alteration play an important role at the deepest horizons of that mass. Sulfur isotopic studies of the character of possible biogenic processes of sulfate reduction in sediments are another focus, as well as the nature and origin of sulfide mineralization in Layer-2 rocks of remnant island arcs. Finally, oxygen and carbon istopic analyses of biogenic carbonates in the cores also enabled us to investigate the effects of changing climatic conditions during the Cenozoic. These results are compared with previous data from adjacent regions of the Pacific Ocean. Thus this chapter describes results of isotopic analyses of: oxygen and sulfur of interstitial water; oxygen and carbon of sedimentary carbonates and of calcite intercalations and inclusions in tuffs and volcaniclastic breccias interbedded with basalt flows; and sulfur of sulfides in these rocks.

Surface sediment samples from several fore-arc basins west and southwest of the Indonesian Archipelago, analyzed by planktonic foraminifera, stable oxygen and carbon isotopic signals and opal and CaCO3 contents in bulk sediment

A total of 69 surface sediment samples from several fore-arc basins located west and southwest of the Indonesian Archipelago was analyzed with respect to the faunal composition of planktonic foraminifera, the stable oxygen and carbon isotopic signal of a surface-dwelling (Globigerinoides ruber) and a thermocline-dwelling (Neogloboquadrina dutertrei) species, and the opal and CaCO3 contents in bulk sediment. Our results show that the distribution pattern of opal in surface sediments corresponds well to the upwelling-induced chlorophyll concentration in the upper water column and thus, represents a reliable proxy for marine productivity in the coastal upwelling area off S and SW Indonesia. Present-day oceanography and marine productivity are also reflected in the tropical to subtropical and upwelling assemblages of planktonic foraminifera in the surface sediments, which in part differ from previous studies in this region probably due to different coring methods and dissolution effects. The average stable oxygen isotopic values (d18O) of G. ruber in surface sediments vary between 2.9 per mill and 3.2 per mill from basin to basin and correspond to the oceanographic settings during the SE monsoon (July-October) off west Sumatra, whereas off southern Indonesia, they reflect the NW monsoon (December-March) or annual average conditions. The d18O values of N. dutertrei show a stronger interbasinal variation between 1.6 per mill and 2.2 per mill and correspond to the upper thermocline hydrology in July-October. In addition, the difference between the shell carbon isotopic values (d13C) of G. ruber and N. dutertrei (Delta d13C) appears to be an appropriate productivity recorder only in the non-upwelling areas off west Sumatra. Consequently, joint interpretation of the isotopic values of these species is distinctive for different fore-arc basins W and SW of Indonesia and should be considered in paleoceanographic studies.