Simultaneous Determination of Stable Carbon, Oxygen, and Hydrogen Isotopes in Cellulose

A technological development is described through which the stable carbon-, oxygen-, and nonexchangeable hydrogen-isotopic ratios (δ13C,δ18O,δ2H) are determined on a single carbohydrate (cellulose) sample with precision equivalent to conventional techniques (δ13 C 0.15‰,δ18O 0.30‰,δ2H 3.0‰). This triple-isotope approach offers significant new research opportunities, most notably in physiology and medicine, isotope biogeochem- istry, forensic science, and palaeoclimatology, when isotopic analysis of a common sample is desirable or when sample material is limited.

(Table 2) Mineralogy and carbon, oxygen, and hydrogen isotope ratios for secondary mineral samples from igneous rocks from ODP Hole 128-794D

The basaltic rocks of Hole 794D drilled during Leg 128 are strongly altered. Microprobe analyses and XRD spectra on small quantities of matter extracted from thin sections show that primary minerals and glassy zones of the groundmass are totally or partially replaced by clay minerals with chlorite/saponite mixed-layer composition whatever the rock sample considered. This mixed-layer was also identified in veins and vesicles where it crystallizes in spheroidal aggregates. The largest veins and vesicles are filled by a zoned deposit: the chlorite/saponite mixed-layer always occupies the central part and is rimmed by pure saponite. Calcite crystallizes in secondary fractures which crosscut the clayey veins and vesicles. Chemographic analysis based on the M+-4Si-3R2+ projection shows that the chemical composition of the saponite component in the mixed-layer is identical to that of the free saponite. This indicates that the clay mineral crystallization was controlled by the chemical composition of the alteration fluids. From petrographic evidence, it is suggested that both chlorite/saponite mixed-layer and free saponite belong to the same hydrothermal event and are produced by a temperature decrease. This is supported by the stable isotopic data. The isotopic data show very little variation: d18O saponite ranges from 13.1 per mil to 13.5 per mil, and dD saponite from -73.6 per mil to -70.0 per mil. d18O calcite varies from +19.7 per mil to +21.9 per mil vs SMOW and d13C from -3.2 per mil to +0.4 per mil vs. PDB. These values are consistent with seawater alteration of the basalt. The formation of saponite took place at 150°-180°C and the formation of calcite at about 65°C.

Carbon/oxygen ratios, clay composition and gas-hydrate saturation of ODP Leg 164 sites

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Porosity, permeability, trace elements, and carbon-oxygen isotopes at DSDP Hole 77-536

Talus deposits recovered from Site 536 show evidence of aragonite dissolution, secondary porosity development, and calcite cementation. Although freshwater diagenesis could account for the petrographic features of the altered talus deposits, it does not uniquely account for isotopic or trace-element characteristics. Also, the hydrologic setting required for freshwater alteration is not easily demonstrated for the Campeche Bank. A mixing-zone model does not account for the available trace-element data, but does require somewhat less drastic assumptions about the size of the freshwater lens. Although a seawater (bottom-water) alteration model requires no hydrologic difficulties, unusual circumstances are required to account for the geochemical characteristics of the talus deposits using this model.

Type Ia supernovae from violent mergers of carbon-oxygen white dwarfs: polarization signatures

The violent merger of two carbon-oxygen white dwarfs has been proposed as a viable progenitor for some Type Ia supernovae. However, it has been argued that the strong ejecta asymmetries produced by this model might be inconsistent with the low degree of polarization typically observed in Type Ia supernova explosions. Here, we test this claim by carrying out a spectropolarimetric analysis for the model proposed by Pakmor et al. for an explosion triggered during the merger of a 1.1 and 0.9 M⊙ carbon-oxygen white dwarf binary system. Owing to the asymmetries of the ejecta, the polarization signal varies significantly with viewing angle. We find that polarization levels for observers in the equatorial plane are modest (≲1 per cent) and show clear evidence for a dominant axis, as a consequence of the ejecta symmetry about the orbital plane. In contrast, orientations out of the plane are associated with higher degrees of polarization and departures from a dominant axis. While the particular model studied here gives a good match to highly polarized events such as SN 2004dt, it has difficulties in reproducing the low polarization levels commonly observed in normal Type Ia supernovae. Specifically, we find that significant asymmetries in the element distribution result in a wealth of strong polarization features that are not observed in the majority of currently available spectropolarimetric data of Type Ia supernovae. Future studies will map out the parameter space of the merger scenario to investigate if alternative models can provide better agreement with observations.

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

Characterization of molecular damage induced by UV photons and carbon ions on biomimetic heterostructures

The study of the effect of radiation on living tissues is a rather complex task to address mainly because they are made of a set of complex functional biological structures and interfaces. Particularly if one is looking for where damage is taking place in a first stage and what are the underlying reaction mechanisms. In this work a new approach is addressed to study the effect of radiation by making use of well identified molecular hetero-structures samples which mimic the biological environment. These were obtained by assembling onto a solid support deoxyribonucleic acid (DNA) and phospholipids together with a soft water-containing polyelectrolyte precursor in layered structures and by producing lipid layers at liquid/air interface with DNA as subphase. The effects of both ultraviolet (UV) radiation and carbon ions beams were systematically investigated in these heterostructures, namely damage on DNA by means vacuum ultraviolet (VUV), infrared (IR), X-Ray Photoelectron (XPS) and impedance spectroscopy. Experimental results revealed that UV affects furanose, PO2-, thymines, cytosines and adenines groups. The XPS spectrometry carried out on the samples allowed validate the VUV and IR results and to conclude that ionized phosphate groups, surrounded by the sodium counterions, congregate hydration water molecules which play a role of UV protection. The ac electrical conductivity measurements revealed that the DNA electrical conduction is arising from DNA chain electron hopping between base-pairs and phosphate groups, with the hopping distance equal to the distance between DNA base-pairs and is strongly dependent on UV radiation exposure, due loss of phosphate groups. Characterization of DNA samples exposed to a 4 keV C3+ ions beam revealed also carbon-oxygen bonds break, phosphate groups damage and formation of new species. Results from radiation induced damage carried out on biomimetic heterostructures having different compositions revealed that damage is dependent on sample composition, with respect to functional targeted groups and extent of damage. Conversely, LbL films of 1,2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (Sodium Salt) (DPPG) liposomes, alternated with poly(allylamine hydrochloride) (PAH) revealed to be unaffected, even by prolonged UV irradiation exposure, in the absence of water molecules. However, DPPG molecules were damaged by the UV radiation in presence of water with cleavage of C-O, C=O and –PO2- bonds. Finally, the study of DNA interaction with the ionic lipids at liquid/air interfaces revealed that electrical charge of the lipid influences the interaction of phospholipid with DNA. In the presence of DNA in the subphase, the effects from UV irrladiation were seen to be smaller, which means that ionic products from biomolecules degradation stabilize the intact DPPG molecules. This mechanism may explain why UV irradiation does not cause immediate cell collapse, thus providing time for the cellular machinery to repair elements damaged by UV.