Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data.

Nitrogen isotopic distributions in the solar system extend across an enormous range, from -400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ(15)N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ(15)N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula.

Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.

Tales of volcanoes and El-Nino southern oscillations with the oxygen isotope anomaly of sulfate aerosol.

The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth's system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980-2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher (17)O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and (17)O = 3.3‰, OEI = 11 and (17)O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that (17)O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations.

Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis.

Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models.

Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: wavelength, pressure, and temperature dependency.

Several absorption bands exist in the vacuum ultraviolet (VUV) region of carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. Experimental results of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ∼13 to 11 eV) from the Advanced Light Source synchrotron by measurement of the oxygen isotopic composition of the products are presented here. A large (few hundred per mil) range of oxygen isotopic compositions are observed in the CO photodissociation product and are wavelength dependent. Slope values (δ('17)O/δ('18)O) ranging from 0.72 to 1.36 were observed in the oxygen three-isotope space (δ('18)O vs. δ('17)O), which anti-correlated with increasing synchrotron photon energy, and indicates a dependency on the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope fractionation was observed for photodissociation at 105 and 107 nm and is found to be associated with accidental predissociation of the vibrational states (ν = 0 and 1) for the upper electronic state E(1)Π. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.

Experimental test of self-shielding in vacuum ultraviolet photodissociation of CO.

Self-shielding of carbon monoxide (CO) within the nebular disk has been proposed as the source of isotopically anomalous oxygen in the solar reservoir and the source of meteoritic oxygen isotopic compositions. A series of CO photodissociation experiments at the Advanced Light Source show that vacuum ultraviolet (VUV) photodissociation of CO produces large wavelength-dependent isotopic fractionation. An anomalously enriched atomic oxygen reservoir can thus be generated through CO photodissociation without self-shielding. In the presence of optical self-shielding of VUV light, the fractionation associated with CO dissociation dominates over self-shielding. These results indicate the potential role of photochemistry in early solar system formation and may help in the understanding of oxygen isotopic variations in Genesis solar-wind samples.

Photochemical mass-independent sulfur isotopes in achondritic meteorites.

Sulfides from four achondrite meteorite groups are enriched in 33S (up to 0.040 per mil) as compared with primitive chondrites and terrestrial standards. Stellar nucleosynthesis and cosmic ray spallation are ruled out as causes of the anomaly, but photochemical reactions in the early solar nebula could produce the isotopic composition. The large 33S excess present in oldhamite from the Norton County aubrite (0.161 per mil) suggests that refractory sulfide minerals condensed from a nebular gas with an enhanced carbon-oxygen ratio, but otherwise solar composition is the carrier. The presence of a mass-independent sulfur effect in meteorites argues for a similar process that could account for oxygen isotopic anomalies observed in refractory inclusions in primitive chondrites.

Localization in membrane microdomains of the Ig-alpha/beta component of the BCR expressed by a B lymphoma variant.

The B cell antigen receptor (BCR) composed of the ligand-binding membrane IgM (mIgM) and the signaling component, Ig-alpha/beta, is known to inducibly associate with membrane microdomains rich in cholesterol and sphingolipids, termed lipid rafts. In this study we tested whether the Ig-alpha/beta portion of the BCR has targeting information that allows it to be localized in lipid rafts. In order to do this, we cross-linked the Ig-alpha/beta on the cell surface of the variant B cell line, WEHI 303.1.5, a derivative of the immature murine B cell line WEHI 231 that lacks mu heavy chain and expresses the Ig-alpha/beta on the cell surface by itself. Using two methods to isolate detergent-insoluble, lipid raft-like fractions, we found that Ig-alpha/beta without accompanying mIgM was constitutively located in these raft-like fractions and that the amount was marginally increased after Ig-alpha/beta cross-linking. These results suggest that the Ig-alpha/beta portion of the BCR has the ability to be compartmentalized into raft-like membrane domains even when not associated with mIgM and perhaps this targeting information is normally regulated by the presence of the mIgM portion of the receptor.

Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates.

Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (delta17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 +/- 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by -0.241 +/- 0.042 per thousand. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 +/- 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation.