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1. Surfaces, silica and semivolatile organics—limonene uptake and desorption indoors and outdoors

   https://doi.org/10.1039/D5EM00275C  

   Reynolds, Ryan S; Johnson, Kristen N; Pacaud, Katelyn; Ezell, Michael; Lakey, Pascale_S J; Shiraiwa, Manabu; Finlayson-Pitts, Barbara J (July 2025, Environmental Science: Processes & Impacts)

   Adsorption of organics on surfaces is important in both outdoor and indoor environments. Surfaces can serve as sinks for gas-phase species, act as reservoirs by emitting previously partitioned organics back into the gas phase, and can facilitate heterogeneous chemistry. We report here studies of the uptake and desorption energetics of gas-phase limonene, a volatile and widely-distributed monoterpene, on solid silica nanoparticles using a unique apparatus that allows for temperature programmed desorption (TPD) measurements of surface binding energies as well as Knudsen cell gas uptake measurements. A multiphase kinetic model was applied to these data to provide additional molecular-level understanding of the processes involved. TPD experiments yielded an average desorption energy of 47.5 ± 8.2 kJ mol-1 (±1s, sample standard deviation), the first direct experimental measurement of this parameter over a broad temperature range (150–320 K). Initial net uptake coefficients (0,net) range from (1.7 ± 0.3) ×10-3 (±1s) at 210 K to (2.3 ± 0.4) ×10-4 (±1s) at 250 K, reflecting increased rates of desorption with an increase in temperature combined with increased rates of diffusion and re-adsorption within the pores between adjacent silica nanoparticles. Effective Langmuir constants, which also reflect the effects of pore diffusion and re-adsorption, were determined from the uptake data and vary from (1.8–0.3)×10-13 cm3 molecule-1 over the same temperature range. These results are in excellent agreement with previous studies around room temperature and with theoretical calculations of the energetics of the limonene-silica interaction. The strong attraction between limonene and the polar silica surface shows the importance of including such interactions in models of the atmospheric fates of terpenes both indoors and outdoors. 

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2. Understanding interactions of organic nitrates with the surface and bulk of organic films: implications for particle growth in the atmosphere

   https://doi.org/10.1039/C8EM00348C  

   Vander Wall, A. C.; Lakey, P. S.; Rossich Molina, E.; Perraud, V.; Wingen, L. M.; Xu, J.; Soulsby, D.; Gerber, R. B.; Shiraiwa, M.; Finlayson-Pitts, B. J. (November 2018, Environmental Science: Processes & Impacts)

   Understanding impacts of secondary organic aerosol (SOA) in air requires a molecular-level understanding of particle growth via interactions between gases and particle surfaces. The interactions of three gaseous organic nitrates with selected organic substrates were measured at 296 K using attenuated total reflection Fourier transform infrared spectroscopy. The organic substrates included a long chain alkane (triacontane, TC), a keto-acid (pinonic acid, PA), an amorphous ester oligomer (poly(ethylene adipate) di-hydroxy terminated, PEA), and laboratory-generated SOA from α-pinene ozonolysis. There was no uptake of the organic nitrates on the non-polar TC substrate, but significant uptake occurred on PEA, PA, and α-pinene SOA. Net uptake coefficients ( γ ) at the shortest reaction times accessible in these experiments ranged from 3 × 10 −4 to 9 × 10 −6 and partition coefficients ( K ) from 1 × 10 7 to 9 × 10 4 . Trends in γ did not quantitatively follow trends in K , suggesting that the intermolecular forces involved in gas–surface interactions are not the same as those in the bulk, which is supported by theoretical calculations. Kinetic modeling showed that nitrates diffused throughout the organic films over several minutes, and that the bulk diffusion coefficients evolved as uptake/desorption occurred. A plasticizing effect occurred upon incorporation of the organic nitrates, whereas desorption caused decreases in diffusion coefficients in the upper layers, suggesting a crusting effect. Accurate predictions of particle growth in the atmosphere will require knowledge of uptake coefficients, which are likely to be several orders of magnitude less than one, and of the intermolecular interactions of gases with particle surfaces as well as with the particle bulk. 

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3. Oxidation of solid thin films of neonicotinoid pesticides by gas phase hydroxyl radicals

   https://doi.org/10.1039/d2ea00134a  

   Finlayson-Pitts, B. J.; Anderson, A.; Lakey, P. S.; Wang, W.; Ezell, M. J.; Wang, X.; Wingen, L. M.; Perraud, V.; Shiraiwa, M. (November 2022, Environmental Science: Atmospheres)

   Neonicotinoids (NNs) are commonly found throughout the environment on surfaces such as seeds, soil, vegetation, and blowing dust particles. However, there is a paucity of data on the kinetics and oxidation products formed on contact with the atmosphere which limits understanding of their potentially far-reaching impacts. In this study, in situ attenuated total reflectance (ATR) FTIR spectroscopy was used to investigate the OH oxidation of thin films of three solid NNs, imidacloprid (IMD), dinotefuran (DNF) and clothianidin (CLD) at 295 ± 3 K. The experimentally measured reaction probabilities based on initial rates of NN loss are (1.6 ± 0.8) × 10 −2 for IMD, (1.5 ± 0.6) × 10 −2 for DNF and (0.9 ± 0.2) × 10 −2 for CLD (±1 σ ), suggesting initial NN lifetimes with respect to OH of 10–17 days. The kinetics were interpreted using a multiphase kinetics model, KM-SUB, which showed that the OH uptake and reaction occurred primarily in the surface layer. Products identified by mass spectrometry included carbonyl-, alcohol- and olefin-containing species formed via hydrogen abstraction from aliphatic C–H groups. Additionally, carbonyl-containing desnitro and urea derivative products were observed from secondary reactions of the initially formed photodegradation products. Reaction with OH will contribute to NN loss both during the day as well as at night when there are non-photolytic sources of this radical. Thus, OH reactions with both the parent neonicotinoid and its photodegradation products should be considered in assessing their environmental impacts. 

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4. Buffer gas cooled ice chemistry. II. Ice generation and mm-wave detection of molecules desorbed from an ice

   https://doi.org/10.1063/5.0225903  

   Hager, T J; Moore, B M; Borengasser, Q D; Kanaherarachchi, A C; Renshaw, K T; Radhakrishnan, S; Hall, G E; Broderick, B M (September 2024, The Journal of Chemical Physics)

   This second paper in a series of two describes the chirped-pulse ice apparatus that permits the detection of buffer gas cooled molecules desorbed from an energetically processed ice using broadband mm-wave rotational spectroscopy. Here, we detail the lower ice stage developed to generate ices at 4 K, which can then undergo energetic processing via UV/VUV photons or high-energy electrons and which ultimately enter the gas phase via temperature-programmed desorption (TPD). Over the course of TPD, the lower ice stage is interfaced with a buffer gas cooling cell that allows for sensitive detection via chirped-pulse rotational spectroscopy in the 60–90 GHz regime. In addition to a detailed description of the ice component of this apparatus, we show proof-of-principle experiments demonstrating the detection of H2CO products formed through irradiation of neat methanol ices or 1:1 CO + CH4 mixed ices. 

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5. Knudsen cell studies of the uptake of gaseous ammonia and amines onto C3–C7 solid dicarboxylic acids

   https://doi.org/10.1039/C7CP05252A  

   Fairhurst, Michelle C.; Ezell, Michael J.; Finlayson-Pitts, Barbara J. (January 2017, Phys. Chem. Chem. Phys.)

   While atmospheric particles affect health, visibility and climate, the details governing their formation and growth are poorly understood on a molecular level. A simple model system for understanding the interactions between the gas and particle phases is the reaction of bases with acids, both of which are common constituents of atmospheric particles. In the present study, uptake coefficients for the reactions of gas phase ammonia, methylamine, ethylamine, dimethylamine and trimethylamine with a series of solid dicarboxylic acids (diacids) were measured at 296 ± 1 K using a Knudsen cell interfaced to a quadrupole mass spectrometer. The uptake coefficients ( γ ) for a given amine follow an odd–even trend in carbon number of the diacid, and are larger for the odd carbon diacids. Values range from γ = 0.4 for ethylamine on malonic acid (C3) to less than ∼10 −6 for ammonia and all amines on adipic (C6) and pimelic (C7) acids. Basicity or structure of the amines/ammonia alone do not explain the effect of the base on uptake. The crystal structures of the diacids also play a key role, which is especially evident for malonic acid (C3). Evaporation of aqueous mixtures of amines/ammonia with odd carbon diacids show the formation of ionic liquids (ILs) or in some cases, metastable ILs that revert back to a stable solid salt upon complete evaporation of water. The trends with amine and diacid structure provide insight into the mechanisms of uptake and molecular interactions that control it, including the formation of ionic liquid layers in some cases. The diversity in the kinetics and mechanisms involved in this relatively simple model system illustrate the challenges in accurately representing such processes in atmospheric models. 

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