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Organic reactions in atmospheric particles impact human health and climate, such as by the production of brown carbon. Previous work suggests that reactions are faster in particles than in bulk solutions because of higher reactant concentrations and pronounced surface-mediated processes. Additionally, dialdehydes may have accelerated reactions in particles, as has been shown for the glyoxal reaction with ammonium sulfate (AS). Here, we examine the competition between evaporation and reaction of butenedial, a semivolatile dialdehyde, and reduced nitrogen (NH X ) in bulk solutions and levitated particles with mass spectrometry (MS). Pyrrolinone is the major product of butenedial/AS bulk solutions, indicating brown carbon formation via accretion reactions. By contrast, pyrrolinone is completely absent in all MS measurements of comparable levitated particles suspended in a pure N 2 stream. Pyrrolinone is only produced in levitated butenedial particles exposed to gas-phase ammonia, without enhanced reaction kinetics previously observed for glyoxal and other systems. Despite butenedial's large Henry's law constant and fast reaction with NH X compared to glyoxal, the brown carbon pathway competes with evaporation only in polluted regions with extreme NH X . Therefore, accurate knowledge of effective volatilities or Henry's law constants for complex aerosol matrices is required when chemistry studied in bulk solutions is extrapolated to atmospheric particles.

The uptake of medium-sized levoglucosan and 2,4-dinitrophenol to organic particles produced by α-pinene ozonolysis and to ammonium sulfate particles was studied from 10% to >95% relative humidity (RH). For aqueous sulfate particles, the water-normalized gas-particle partitioning coefficient of levoglucosan decreased from (1.0 ± 0.1) × 10 -3 to (0.2 ± 0.1) × 10 -3 (ng μg -1 ) particle /(ng m -3 ) gas from 40% to >95% RH, suggestive of a salting-in mechanism between levoglucosan and ionic ammonium sulfate solutions. For the organic particles, the levoglucosan partitioning coefficient increased from 10% to 40% RH and became invariant at (2.0 ± 0.4) × 10 -3 (ng μg -1 )/(ng m -3 ) above 40% RH. A kinetic limitation on uptake below 40% RH was implied, compared to a thermodynamic regime above 40% RH. The estimated diffusivity was 10 -19±0.05 m 2 s -1 at 40% RH. By comparison, the uptake of 2,4-dinitrophenol onto the organic particles was below detection limit, implying an upper limit on the partitioning coefficient of 6.8 × 10 -6 (ng μg -1 )/(ng m -3 ) at 80% RH. The results highlight that the molecular uptake of gases onto particles can be regulated by both kinetic and thermodynamic factors, either of which can limit the uptake of medium-sized organic molecules by atmospherically relevant particles.

Aerosol liquid water (ALW) influences aerosol radiative properties and the partitioning of gas-phase water-soluble organic compounds (WSOCg) to the condensed phase. A recent modeling study drew attention to the anthropogenic nature of ALW in the southeastern United States, where predicted ALW is driven by regional sulfate. Herein, we demonstrate that ALW in the Po Valley, Italy, is also anthropogenic but is driven by locally formed nitrate, illustrating regional differences in the aerosol components responsible for ALW. We present field evidence for the influence of controllable ALW on the lifetimes and atmospheric budgets of reactive organic gases and note the role of ALW in the formation of secondary organic aerosol (SOA). Nitrate is expected to increase in importance due to increased emissions of nitrate precursors, as well as policies aimed at reducing sulfur emissions. We argue that the impacts of increased particulate nitrate in future climate and air quality scenarios may be under predicted because they do not account for the increased potential for SOA formation in nitrate-derived ALW, nor do they account for the impacts of this ALW on reactive gas budgets and gas-phase photochemistry.

Reactions and interactions between glyoxal and salts in aqueous solution were studied. Glyoxal was found to react with ammonium to form imidazole, imidazole-2-carboxaldehyde, formic acid, N-glyoxal substituted imidazole, and minor products at very low concentrations. Overall reaction orders and rates for each major product were measured. Sulfate ions have a strong and specific interaction with glyoxal in aqueous solution, which shifts the hydration equilibria of glyoxal from the unhydrated carbonyl form to the hydrated form. This ion-specific effect contributes to the observed enhancement of the effective Henry's law coefficient for glyoxal in sulfate-containing solutions. The results of UV-vis absorption and NMR spectroscopy studies of solutions of glyoxal with ammonium, methylamine, and dimethylamine salts reveal that light absorbing compounds require the formation of nitrogen containing molecules. These findings have implications on the role of glyoxal in the atmosphere, both in models of the contribution of glyoxal to form secondary organic aerosol (SOA), the role of nitrogen containing species for aerosol optical properties and in predictions of the behavior of other carbonyls or dicarbonyls in the atmosphere.

We present the measurement and analysis of five new (D2O)5 bands via vibration-rotation-tunneling (VRT) spectroscopy as well as a preliminary description of a second (H2O)5 band. The vibrationally averaged rotational constants of all five fitted bands agree well with those from the two previously observed (D2O)5 bands and confirm that the pentamer averages to a symmetric, quasi-planar structure on the time scale of our experiment. While the spectrum of the first two bands, located at 50.7 cm(-1) (1.52 THz) and 27.3 cm(-1) (0.82 THz) are indicative of unperturbed oblate rotors, the three remaining (D2O)5 bands centered at 47.7 cm(-1) (1.43 THz), 45.4 cm(-1) (1.36 THz), and 45.0 cm(-1) (1.35 THz) are severely perturbed by first-order Coriolis coupling. This represents the first observation of this perturbation in the perdeuterated water pentamer, as well as the first observation of transitions between degenerate states of the torsional-puckering manifold. Unlike transitions from the (H2O)5 band observed by Brown et al. at 89.0 cm(-1) and the 103.8 cm(-1) band that we report here, none of the individual rovibrational transitions of any of the five (D2O)5 bands demonstrate spectral splittings due to bifurcation tunneling. We conclude, through careful analysis of these water pentamer bands, that at least three torsional-puckering manifolds have been probed and that the lowest-energy manifold is highly compacted. A plausible water pentamer torsional-puckering correlation diagram is proposed, though additional experimental data are required to unambiguously establish the energies of the torsional-puckering levels.

Extensive terahertz laser vibration-rotation-tunneling spectra and mid-IR laser spectra have been compiled for several isotopomers of small (dimer through hexamer) water clusters. These data, in conjunction with new theoretical advances, quantify the structures, force fields, dipole moments, and hydrogen bond rearrangement dynamics in these clusters. This new information permits us to systematically untangle the intricacies associated with cooperative hydrogen bonding and promises to lead to a more complete molecular description of the liquid and solid phases of water, including an accurate universal force field.

The effect of exciting each of the three classes of intermolecular vibrations on the hydrogen bond lifetime (tau(H)) of the isolated water trimer is investigated by far-infrared laser spectroscopy. Single excitation of a librational vibration decreases tau(H) by 3 orders of magnitude to tau(H) = 1-6 ps, comparable to the time scale of a number of important bulk water dynamical relaxation processes. In contrast, excitation of translational or torsional vibrations has no significant effect (tau(H) = 1-2 ns). Although such a dependence of tau(H) on intermolecular motions has also been proposed for liquid water via computer simulations, these are the first experiments that provide a detailed molecular picture of the respective motions without extensive interpretation.