Iulia Gensch

Stable Carbon Isotope Ratio Analysis of Anhydrosugars in Biomass Burning Aerosol Particles from Source Samples

A new method for stable carbon isotope ratio analysis of anhydrosugars from biomass burning aerosol particle source filter samples was developed by employing Thermal Desorption--2 Dimensional Gas Chromatography--Isotope Ratio Mass Spectrometry (TD-2DGC-IRMS). Compound specific isotopic measurements of levoglucosan, mannosan, and galactosan performed by TD-2DGC-IRMS in a standard mixture show good agreement with isotopic measurements of the bulk anhydrosugars, carried out by Elemental Analyzer--Isotope Ratio Mass Spectrometry (EA-IRMS). The established method was applied to determine the isotope ratios of levoglucosan, mannosan, and galactosan from source samples collected during combustion of hard wood, softwood, and crop residues. δ(13)C values of levoglucosan were found to vary between -25.6 and -22.2‰, being higher in the case of softwood. Mannosan and galactosan were detected only in the softwood samples showing isotope ratios of -23.5‰ (mannosan) and -25.7‰ (galactosan). The isotopic composition of holocellulose in the plant material used for combustion experiments was determined with δ(13)C values between -28.5 and -23.7‰. The difference in δ(13)C of levoglucosan in biomass burning aerosol particles compared to the parent fuel holocellulose was found to be -1.89 (±0.37)‰ for the investigated biomass fuels. Compound specific δ(13)C measurements of anhydrosugars should contribute to an improved source apportionment.

Tropopause and hygropause variability over the equatorial Indian Ocean during February and March 1999

Measurements of temperature, water vapor, total water, ozone, and cloud properties were made above the western equatorial Indian Ocean in February and March 1999. The cold-point tropopause was at a mean pressure-altitude of 17 km, equivalent to a potential temperature of 380 K, and had a mean temperature of 190 K. Total water mixing ratios at the hygropause varied between 1.4 and 4.1 ppmv. The mean saturation water vapor mixing ratio at the cold point was 3.0 ppmv. This does not accurately represent the mean of the measured total water mixing ratios because the air was unsaturated at the cold point for about 40% of the measurements. As well as unsaturation at the cold point, saturation was observed above the cold point on almost 30% of the profiles. In such profiles the air was saturated with respect to water ice but was free of clouds (i.e., backscatter ratio <2) at potential temperatures more than 5 K above the tropopause and hygropause. Individual profiles show a great deal of variability in the potential temperatures of the cold point and hygropause. We attribute this to short timescale and space-scale perturbations superimposed on the seasonal cycle. There is neither a clear and consistent “setting” of the tropopause and hygropause to the same altitude by dehydration processes nor a clear and consistent separation of tropopause and hygropause by the Brewer-Dobson circulation. Similarly, neither the tropopause nor the hygropause provides a location where conditions consistently approach those implied by a simple “tropopause freeze drying” or “stratospheric fountain” hypothesis.

Temperature dependence of the kinetic isotope effect in β‐pinene ozonolysis

[1]xa0The temperature dependence of the kinetic isotope effect (KIE) of β-pinene ozonolysis was investigated experimentally at 258, 273 and 303 K in the AIDA atmospheric simulation chamber. Compound specific carbon isotopic analysis of gas phase samples was performed off-line with a Thermo Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS) system. From the temporal behavior of the δ13C of β-pinene a KIE of 1.00358 ± 0.00013 was derived at 303 K, in agreement with literature data. Furthermore, KIE values of 1.00380 ± 0.00014 at 273 K and 1.00539 ± 0.00012 at 258 K were determined, showing an increasing KIE with decreasing temperature. A parameterization of the observed KIE temperature dependence was deduced and used in a sensitivity study carried out with the global chemistry transport model MOZART-3. Two scenarios were compared, the first neglecting, the second implementing the KIE temperature dependence in the simulations. β-Pinene stable carbon isotope ratio and concentration were computed, with emphasis on boreal zones. For early spring it is shown that when neglecting the temperature dependence of KIE, the calculated average age of β-pinene in the atmosphere can be up to two times over- or underestimated. The evolution of the isotopic composition of the major β-pinene oxidation product, nopinone, was examined using Master Chemical Mechanism (MCM) simulations. The tested hypothesis that formation of nopinone and its associated KIE are the determining factors for the observed δ13C values of nopinone is supported at high β-pinene conversion levels.

MAID: a model to simulate UT/LS aerosols and ice clouds

The comprehensive model MAID (model for aerosol and ice dynamics) was developed to simulate condensation and freezing in aerosol particles residing in the UT/LS (upper troposphere/lower stratosphere). The exact balancing of trace gas components is a particular emphasis of MAID. MAID is applied to and verified by experiments in the aerosol chamber AIDA, and, moreover, it is adapted to Lagrangian atmospheric cirrus cloud simulations. Here, the model is introduced, and as an example for model applications the significant influence of homogeneous or heterogeneous freezing on ice cloud microphysics and the water and nitric acid partitioning in cirrus clouds is shown.

Chemical stability of levoglucosan: An isotopic perspective

The chemical stability of levoglucosan was studied by exploring its isotopic fractionation during the oxidation by hydroxyl radicals. Aqueous solutions as well as mixed (NH4)2SO4-levoglucosan particles were exposed to OH. In both cases, samples experiencing different extents of processing were isotopically analyzed by Thermal Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS). From the dependence of levoglucosan δ13C and concentration on the reaction extent, the kinetic isotope effect (KIE) of the OH oxidation reactions was determined to be 1.00187±0.00027 and 1.00229±0.00018, respectively. Both show good agreement within the uncertainty range. For the heterogeneous oxidation of particulate levoglucosan by gas-phase OH, a reaction rate constant of (2.67±0.03)·10−12 cm3xa0molecule−1S−1 was derived. The laboratory kinetic data, together with isotopic source and ambient observations, give information on the extent of aerosol chemical processing in the atmosphere.

Using δ13C of Levoglucosan As a Chemical Clock

Compound specific carbon isotopic measurements (δ13C) of levoglucosan were carried out for ambient aerosol sampled during an intensive biomass burning period at different sites in Guangdong province, China. The δ13C of ambient levoglucosan was found to be noticeably heavier than the average δ13C of levoglucosan found in source C3-plant-combustion samples. To estimate the photochemical age of sampled ambient levoglucosan, back trajectory analyses were done. The origin and pathways of the probed air masses were determined, using the Lagrangian-particle-dispersion-model FLEXPART and ECMWF meteorological data. On the other hand, the isotopic hydrocarbon clock concept was applied to relate the changes in the field-measured stable carbon isotopic composition to the extent of chemical processing during transport. Comparison of the photochemical age derived using these two independent approaches shows on average good agreement, despite a substantial scatter of the individual data pairs. These analyses demonstrate that the degree of oxidative aging of particulate levoglucosan can be quantified by combining laboratory KIE studies, observed δ13C at the source and in the field, as well as back trajectory analyses. In this study, the chemical loss of levoglucosan was found to exceed 50% in one-fifth of the analyzed samples. Consequently, the use of levoglucosan as a stable molecular tracer may underestimate the contribution of biomass burning to air pollution.

Temperature dependence of stable carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals: Experimental and theoretical studies

The stable carbon kinetic isotope effect (KIE) of ethane photo-oxidation by OH radicals was deduced by employing both laboratory measurements and theoretical calculations. The investigations were designed to elucidate the temperature dependence of KIE within atmospherically relevant temperature range. The experimental KIE were derived from laboratory compound specific isotope analyses of ethane with natural isotopic abundance exposed to OH at constant temperature, showing e values of 7.16 ± 0.54 ‰ (303 K), 7.45 ± 0.48 ‰ (288 K), 7.36 ± 0.28 ‰ (273 K), 7.61 ± 0.28 ‰ (263 K), 8.89 ± 0.90‰ (253 K), and 9.42 ± 2.19% (243 K). Compared to previous studies, a significant improvement of the measurement precision was reached at the high end of the investigated temperature range. The KIE was theoretically determined as well, in the temperature range of 150 K to 400 K, by calculating the reaction rate coefficients of 12C and singly 13C substituted ethane isotopologues applying chemical quantum mechanics together with transition state theory. Tunneling effect and internal rotations were also considered. The agreement between experimental and theoretical results for rate coefficients and KIE in an atmospherically relevant temperature range is discussed. However, both laboratory observations and computational predictions show no significant temperature dependence of the KIE for the ethane oxidation by OH radicals.