Mary K. Gilles

Bio: Mary K. Gilles is an academic researcher from Lawrence Berkeley National Laboratory. The author has contributed to research in topics: Aerosol & Particle. The author has an hindex of 44, co-authored 105 publications receiving 6974 citations. Previous affiliations of Mary K. Gilles include University of California, San Diego & Cooperative Institute for Research in Environmental Sciences.

Measuring Mass-Based Hygroscopicity of Atmospheric Particles through in Situ Imaging

Abstract: Quantifying how atmospheric particles interact with water vapor is critical for understanding the effects of aerosols on climate. We present a novel method to measure the mass-based hygroscopicity of particles while characterizing their elemental and carbon functional group compositions. Since mass-based hygroscopicity is insensitive to particle geometry, it is advantageous for probing the hygroscopic behavior of atmospheric particles, which can have irregular morphologies. Combining scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX), scanning transmission X-ray microscopy (STXM) analysis, and in situ STXM humidification experiments, this method was validated using laboratory-generated, atmospherically relevant particles. Then, the hygroscopicity and elemental composition of 15 complex atmospheric particles were analyzed by leveraging quantification of C, N, and O from STXM, and complementary elemental quantification from SEM/EDX. We found three types of hygroscopic responses, and correlated high hygroscopicity with Na and Cl content. The mixing state of 158 other particles from the sample broadly agreed with those of the humidified particles, indicating the potential to infer atmospheric hygroscopic behavior from a selected subset of particles. These methods offer unique quantitative capabilities to characterize and correlate the hygroscopicity and chemistry of individual submicrometer atmospheric particles.

Photodissociation of ClONO2: 1. Atomic Resonance Fluorescence Measurements of Product Quantum Yields

Abstract: The quantum yields for the production of Cl, O, and ClO in the photolysis of ClONO2, measured by detecting Cl and O atoms by atomic resonance fluorescence, are reported The resonance fluorescence signals were calibrated by generating known concentrations of Cl and O atoms from the photolysis of Cl2, HCl, O3, or N2O The quantum yields for Cl in the 1932, 2220, 24825, and 30815 nm photolysis of ClONO2 were 053 ± 010, 046 ± 010, 041 ± 013, and 064 ± 020, respectively The yields for O atoms at these wavelengths were, respectively, 037 ± 008, 017 ± 005, <010, and <005 The quoted uncertainties are 2σ precision of the measurements ClO radical was converted to Cl via addition of NO and its signal compared to the Cl atom signal produced by photolysis of ClONO2 The obtained quantum yields for ClO were 029 ± 020, 064 ± 020, 039 ± 019, and 037 ± 019, at 1932, 2220, 24825, and 30815 nm, respectively It appears that Cl + NO3 and ClO + NO2 are the major products in the photodissociat

High spatial resolution Raman thermometry analysis of TiO2 microparticles.

Abstract: A new technique of high-resolution micro-Raman thermometry using anatase TiO2 microparticles (0.5–3 μm) is presented. These very high spatial resolution measurements (280 nm) reveal temperature gradients even within individual microparticles. Potential applications of this technique are demonstrated by probing the temperature distribution of a micro-fabricated heater consisting of a thin silicon nitride (Si-N) membrane with a gold coil on top of the membrane. Using TiO2 microparticle micro-Raman thermometry, the temperature from the outer edge of the coil to the inner portion was measured to increase by ∼40 °C. These high spatial resolution microscopic measurements were also used to measure the temperature gradient within the 20 μm wide Si-N between the gold heating coils. 2D numerical simulations of the micro heater temperature distribution are in excellent agreement with the experimental measurements of the temperatures. These measurements illustrate the potential to extend applications of micro-Raman thermometry to obtain temperature details on a sub-micrometer spatial resolution by employing microparticles.

Rate Coefficients for the OH + CF3I Reaction between 271 and 370 K

Abstract: The rate coefficient, k1, for the reaction OH + CF3I → products was measured under pseudo-first-order conditions in hydroxyl radical, OH. OH temporal profiles were monitored by laser-induced fluorescence (LIF), and CF3I concentrations were determined by UV/Visible absorption. We determined k1 (T) to be (2.10 ± 0.80) × 10-11 exp[−(2000 ± 140)/T] cm3 molecule-1 s-1, over the temperature range 271 to 370 K. The quoted uncertainties are 2σ (95% confidence limits, σA = AσlnA). Previous measurements of k1(T) are compared with our values, and possible reasons for the discrepancies are discussed. The heat of formation of HOI is deduced to be less than −16 kcal mole-1, if the products of reaction 1 are mostly HOI and CF3. These measurements support the earlier conclusion that the reaction of OH with CF3I plays a negligibly small role in the atmospheric removal of CF3I.

Chemical mapping of polymer photoresistsby scanning transmission x-ray microscopy

Abstract: Scanning transmission x-ray microscopy (STXM) is shown to be a powerful imaging technique that provides chemical selectivity and high spatial resolution (∼35nm) for studying chemically amplified photoresists. Samples of poly(4-t-butoxycarbonyloxystyrene) PTBOCST resist, imprinted by deep ultraviolet lithography with a line∕space pattern of 1.10μm∕0.87μm followed by a post-exposure bake, are used to demonstrate STXM imaging capabilities to extract photoresist latent images. Chemical contrast is obtained by measuring the x-ray absorption at an energy of 290.5 eV, corresponding to a carbon K shell electronic transition to the unoccupied π* molecular orbital of the PTBOCST carbonyl group. A quantitative analysis provides the spatial distribution of the fraction of the unexposed and deprotected polymers remaining after the post-exposure bake stage as well as the thickness of both regions. Both chemical and topographical contributions to the total contrast are estimated. Advantages and limitations of STXM in co...

I and i

Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

Bounding the role of black carbon in the climate system: A scientific assessment

Abstract: Black carbon aerosol plays a unique and important role in Earth's climate system. Black carbon is a type of carbonaceous material with a unique combination of physical properties. This assessment provides an evaluation of black-carbon climate forcing that is comprehensive in its inclusion of all known and relevant processes and that is quantitative in providing best estimates and uncertainties of the main forcing terms: direct solar absorption; influence on liquid, mixed phase, and ice clouds; and deposition on snow and ice. These effects are calculated with climate models, but when possible, they are evaluated with both microphysical measurements and field observations. Predominant sources are combustion related, namely, fossil fuels for transportation, solid fuels for industrial and residential uses, and open burning of biomass. Total global emissions of black carbon using bottom-up inventory methods are 7500 Gg yr−1 in the year 2000 with an uncertainty range of 2000 to 29000. However, global atmospheric absorption attributable to black carbon is too low in many models and should be increased by a factor of almost 3. After this scaling, the best estimate for the industrial-era (1750 to 2005) direct radiative forcing of atmospheric black carbon is +0.71 W m−2 with 90% uncertainty bounds of (+0.08, +1.27) W m−2. Total direct forcing by all black carbon sources, without subtracting the preindustrial background, is estimated as +0.88 (+0.17, +1.48) W m−2. Direct radiative forcing alone does not capture important rapid adjustment mechanisms. A framework is described and used for quantifying climate forcings, including rapid adjustments. The best estimate of industrial-era climate forcing of black carbon through all forcing mechanisms, including clouds and cryosphere forcing, is +1.1 W m−2 with 90% uncertainty bounds of +0.17 to +2.1 W m−2. Thus, there is a very high probability that black carbon emissions, independent of co-emitted species, have a positive forcing and warm the climate. We estimate that black carbon, with a total climate forcing of +1.1 W m−2, is the second most important human emission in terms of its climate forcing in the present-day atmosphere; only carbon dioxide is estimated to have a greater forcing. Sources that emit black carbon also emit other short-lived species that may either cool or warm climate. Climate forcings from co-emitted species are estimated and used in the framework described herein. When the principal effects of short-lived co-emissions, including cooling agents such as sulfur dioxide, are included in net forcing, energy-related sources (fossil fuel and biofuel) have an industrial-era climate forcing of +0.22 (−0.50 to +1.08) W m−2 during the first year after emission. For a few of these sources, such as diesel engines and possibly residential biofuels, warming is strong enough that eliminating all short-lived emissions from these sources would reduce net climate forcing (i.e., produce cooling). When open burning emissions, which emit high levels of organic matter, are included in the total, the best estimate of net industrial-era climate forcing by all short-lived species from black-carbon-rich sources becomes slightly negative (−0.06 W m−2 with 90% uncertainty bounds of −1.45 to +1.29 W m−2). The uncertainties in net climate forcing from black-carbon-rich sources are substantial, largely due to lack of knowledge about cloud interactions with both black carbon and co-emitted organic carbon. In prioritizing potential black-carbon mitigation actions, non-science factors, such as technical feasibility, costs, policy design, and implementation feasibility play important roles. The major sources of black carbon are presently in different stages with regard to the feasibility for near-term mitigation. This assessment, by evaluating the large number and complexity of the associated physical and radiative processes in black-carbon climate forcing, sets a baseline from which to improve future climate forcing estimates.

Climate Change 2007: Impacts, Adaptation and Vulnerability.

Abstract: Impatti, adattamento e vulnerabilita Le cause e le responsabilita dei cambiamenti climatici sono state trattate sul numero di ottobre della rivista Cda. Approfondiamo l’argomento presentando il documento: “Cambiamenti climatici 2007: impatti, adattamento e vulnerabilita” votato ad aprile 2007 dal secondo gruppo di lavoro del Comitato Intergovernativo sui Cambiamenti Climatici (Intergovernmental Panel on Climate Change). Si tratta del secondo di tre documenti che compongono il quarto rapporto sui cambiamenti climatici.

Gaussian-2 theory for molecular energies of first- and second-row compounds

Abstract: The Gaussian‐2 theoretical procedure (G2 theory), based on a b i n i t i o molecular orbital theory, for calculation of molecular energies (atomization energies, ionization potentials,electron affinities, and proton affinities) of compounds containing first‐ (Li–F) and second‐row atoms (Na–Cl) is presented. This new theoretical procedure adds three features to G1 theory [J. Chem. Phys. 9 0, 5622 (1989)] including a correction for nonadditivity of diffuse‐s p and 2d f basis set extensions, a basis set extension containing a third d function on nonhydrogen and a second p function on hydrogen atoms, and a modification of the higher level correction. G2 theory is a significant improvement over G1 theory because it eliminates a number of deficiencies present in G1 theory. Of particular importance is the improvement in atomization energies of ionic molecules such as LiF and hydrides such as C2H6, NH3, N2H4, H2O2, and CH3SH. The average absolute deviation from experiment of atomization energies of 39 first‐row compounds is reduced from 1.42 to 0.92 kcal/mol. In addition, G2 theory gives improved performance for hypervalent species and electron affinities of second‐row species (the average deviation from experiment of electron affinities of second‐row species is reduced from 1.94 to 1.08 kcal/mol). Finally, G2 atomization energies for another 43 molecules, not previously studied with G1 theory, many of which have uncertain experimental data, are presented and differences with experiment are assessed.

Organic aerosol and global climate modelling: a review

Abstract: The present paper reviews existing knowledge with regard to Organic Aerosol (OA) of importance for global climate modelling and defines critical gaps needed to reduce the involved uncertainties. All pieces required for the representation of OA in a global climate model are sketched out with special attention to Secondary Organic Aerosol (SOA): The emission estimates of primary carbonaceous particles and SOA precursor gases are summarized. The up-to-date understanding of the chemical formation and transformation of condensable organic material is outlined. Knowledge on the hygroscopicity of OA and measurements of optical properties of the organic aerosol constituents are summarized. The mechanisms of interactions of OA with clouds and dry and wet removal processes parameterisations in global models are outlined. This information is synthesized to provide a continuous analysis of the flow from the emitted material to the atmosphere up to the point of the climate impact of the produced organic aerosol. The sources of uncertainties at each step of this process are highlighted as areas that require further studies.