Impact of Preindustrial Biomass-Burning Emissions on the Oxidation Pathways of Tropospheric Sulfur and Nitrogen

Ice core measurements (H2O2 and CH4/HCHO) and modeling studies indicate a change in the oxidation capacity of the atmosphere since the onset of the Industrial Revolution due to increases in fossil fuel burning emissions [e. g., Lelieveld et al., 2002; Hauglustaine and Brasseur, 2001; Wang and Jacob, 1998; Staffelbach et al., 1991]. The mass-independent fractionation (MIF) in the oxygen isotopes of sulfate and nitrate from a Greenland ice core reveal that biomass-burning events in North America just prior to the Industrial Revolution significantly impacted the oxidation pathways of sulfur and nitrogen species deposited in Greenland ice. This finding highlights the importance of biomass-burning emissions for atmospheric chemistry in preindustrial North America and warrants the inclusion of this impact in modeling studies estimating changes in atmospheric oxidant chemistry since the Industrial Revolution, particularly when using paleo-oxidant data as a reference for model evaluation

Nitrogen and oxygen isotope constraints on the origin of atmospheric nitrate in coastal Antarctica

Throughout the year 2001, aerosol samples were collected continuously for 10 to 15 days at the French Antarctic Station Dumont d'Urville (DDU) (66°40' S, l40°0' E, 40 m above mean sea level). The nitrogen and oxygen isotopic ratios of particulate nitrate at DDU exhibit seasonal variations that are among the most extreme observed for nitrate on Earth. In association with concentration measurements, the isotope ratios delineate four distinct periods, broadly consistent with previous studies on Antarctic coastal areas. During austral autumn and early winter (March to mid-July), nitrate concentrations attain a minimum between 10 and 30 ng m^−3 (referred to as Period 2). Two local maxima in August (55 ng m^−3) and November/December (165 ng m^−3) are used to assign Period 3 (mid-July to September) and Period 4 (October to December). Period 1 (January to March) is a transition period between the maximum concentration of Period 4 and the background concentration of Period 2. These seasonal changes are reflected in changes of the nitrogen and oxygen isotope ratios. During Period 2, which is characterized by background concentrations, the isotope ratios are in the range of previous measurements at mid-latitudes: δ¹⁸O_vsmow=(77.2±8.6)‰; Δ¹⁷O=(29.8±4.4)‰; δ¹⁵N_air=(−4.4±5.4)‰ (mean ± one standard deviation). Period 3 is accompanied by a significant increase of the oxygen isotope ratios and a small increase of the nitrogen isotope ratio to δ¹⁸O_vsmow=(98.8±13.9)‰; Δ¹⁷O=(38.8±4.7)‰ and δ¹⁵N_air=(4.3±8.20‰). Period 4 is characterized by a minimum ¹⁵N/¹⁴N ratio, only matched by one prior study of Antarctic aerosols, and oxygen isotope ratios similar to Period 2: δ¹⁸O_vsmow=(77.2±7.7)‰; Δ¹⁷O=(31.1±3.2)‰; δ¹⁵N_air=(−32.7±8.4)‰. Finally, during Period 1, isotope ratios reach minimum values for oxygen and intermediate values for nitrogen: δ¹⁸O_vsmow=63.2±2.5‰; Δ¹⁷O=24.0±1.1‰; δ¹⁵N_air=−17.9±4.0‰). Based on the measured isotopic composition, known atmospheric transport patterns and the current understanding of kinetics and isotope effects of relevant atmospheric chemical processes, we suggest that elevated tropospheric nitrate levels during Period 3 are most likely the result of nitrate sedimentation from polar stratospheric clouds (PSCs), whereas elevated nitrate levels during Period 4 are likely to result from snow re-emission of nitrogen oxide species. We are unable to attribute the source of the nitrate during periods 1 and 2 to local production or long-range transport, but note that the oxygen isotopic composition is in agreement with day and night time nitrate chemistry driven by the diurnal solar cycle. A precise quantification is difficult, due to our insufficient knowledge of isotope fractionation during the reactions leading to nitrate formation, among other reasons

First observation of a mass independent isotopic fractionation in a condensation reaction

Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments

Sulfate Formation in Sea-Salt Aerosols: Constraints from Oxygen Isotopes

We use observations of the mass-independent oxygen isotopic composition (Δ17O) of sulfate in the marine boundary layer (MBL) to quantify the sulfate source from aqueous SO2 (S(IV)) oxidation by O3 in alkaline sea-salt aerosols. Oxidation by O3 imparts a large Δ17O signature to the resulting sulfate (8.8‰) relative to oxidation by H2O2 (0.9‰) or by OH or O2 (0‰). Ship data from two Indian Ocean Experiment (INDOEX) cruises in the Indian Ocean indicate Δ17O values usually 70%) and increases MBL sulfate concentrations by typically >10% (up to 30%). Globally, this mechanism contributes 9% of atmospheric sulfate production and 1% of the sulfate burden. The impact on H2SO4 (g) formation and implications for the potential formation of new particles in the MBL warrants inclusion in models examining the radiative effects of sulfate aerosols.Earth and Planetary SciencesEngineering and Applied Science

Oxygen isotopic fractionation in the photochemistry of nitrate in water and ice

We recently reported the first multiple oxygen isotope composition of nitrate (NO_3^−) in ice cores (Alexander et al., 2004). Postdepositional photolysis and volatilization may alter the isotopic signatures of snowpack nitrate. Therefore the precise assessment of the geochemical/atmospheric significance of O-isotopic signatures requires information on the relative rates of photolysis (λ > 300 nm) of N^(16)O_3^−, N^(16)O_2^(17)O^−, and N^(16)O_2^(18)O^− in ice. Here we report on ^(17)O^- and ^(18)O^-fractionation in the 313-nm photolysis of 10-mM aqueous solutions of normal Fisher KNO3 (i.e., Δ17O = −0.2 ± 0.2‰) and 17O-enriched USGS-35 NaNO_3 (Δ^(17)O = 21.0 ± 0.4‰) between −30° and 25°C. We found that Fisher KNO_3 undergoes mass-dependent O-fractionation, i.e., a process that preserves Δ^(17)O = 0. In contrast, Δ^(17)O in USGS-35 NaNO_3 decreased by 1.6 ± 0.4‰ and 2.0 ± 0.4‰ at 25°C, 1.2 ± 0.4‰ and 1.3 ± 0.4‰ at −5°C, and 0.2 ± 0.4‰ and 1.1 ± 0.4‰ at −30°C, after 12 and 24 hours, respectively. Since the small quantum yield (∼0.2%) of NO_3^− photodecomposition into (NO_2 + OH) is due to extensive cage recombination of the primary photofragments rather than to intramolecular processes, the observed Δ^(17)O decreases likely reflect competitive O-isotope exchange of geminate OH-radicals with H_2O (Δ^(17)O = 0) and escape from the solvent cage, in addition to residual O-isotope mixing of the final photoproducts NO, NO_2, NO_2^−, with H_2O. At the prevailing low temperatures, photochemical processing will not impair the diagnostic value of O-isotopic signatures in tracing the chemical ancestry of nitrate in polar ice

Near-field spectroscopy of silicon dioxide thin films

We analyze the results of scanning near-field infrared spectroscopy performed on thin films of a-SiO2 on Si substrate. The measured near-field signal exhibits surface-phonon resonances whose strength has a strong thickness dependence in the range from 2 to 300 {nm}. These observations are compared with calculations in which the tip of the near-field infrared spectrometer is modeled either as a point dipole or an elongated spheroid. The latter model accounts for the antenna effect of the tip and gives a better agreement with the experiment. Possible applications of the near-field technique for depth profiling of layered nanostructures are discussed.Comment: 8 pages, 6 figure

Infrared nanoscopy of Dirac plasmons at the graphene-SiO2 interface

We report on infrared (IR) nanoscopy of 2D plasmon excitations of Dirac fermions in graphene. This is achieved by confining mid-IR radiation at the apex of a nanoscale tip: an approach yielding two orders of magnitude increase in the value of in-plane component of incident wavevector q compared to free space propagation. At these high wavevectors, the Dirac plasmon is found to dramatically enhance the near-field interaction with mid-IR surface phonons of SiO2 substrate. Our data augmented by detailed modeling establish graphene as a new medium supporting plasmonic effects that can be controlled by gate voltage.Comment: 12 pages, 4 figure

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

Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasing synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process

Molybdenum Evidence for Inherited Planetary Scale Isotope Heterogeneity of the Protosolar Nebula

Isotope anomalies provide important information about early solar system evolution. Here we report molybdenum isotope abundances determined in samples of various meteorite classes. There is no fractionation of molybdenum isotopes in our sample set within 0.1 permil and no contribution from the extinct radionuclide 97Tc at mass 97 (97Tc/92Mo<3E-6). Instead, we observe clear anomalies in bulk iron meteorites, mesosiderites, pallasites, and chondrites characterized by a coupled excess in p- and r- or a mirror deficit in s-process nuclides (Mo-HL). This large scale isotope heterogeneity of the solar system observed for molybdenum must have been inherited from the interstellar environment where the sun was born, illustrating the concept of ``cosmic chemical memory''. The presence of molybdenum anomalies is used to discuss the filiation between planetesimals.Comment: 7 pages, 2 figures, 1 table, accepted in Ap