Spontaneous Production of I2 at the Surface of Aqueous Iodide Solutions.

Several groups have recently reported spontaneous production of atmospherically reactive species, including molecular iodine (I2) at the air-water interface of droplets. In this study, glancing angle laser-induced fluorescence spectroscopy was used to track the luminol fluorescence at the surface of sodium iodide (NaI) and sodium chloride (NaCl) solutions. Although luminol fluorescence is hardly quenched by halide anions, even up to fairly high concentrations, it is effectively quenched by I2. We observe luminol fluorescence quenching at the surface of NaI solutions but not at the surface of NaCl solutions, pointing to the formation of I2 at the surface of NaI solutions. This provides further support for the proposal that the strong electric field or the reduction solvation present at the air-water interface can initiate spontaneous iodide activation and other chemistry there. The spontaneous production of I2 at the surface of aqueous iodide solutions presents a previously unconsidered source of iodine in the atmosphere.

Spontaneous Iodide Activation at the Air-Water Interface of Aqueous Droplets.

We present experimental evidence that atomic and molecular iodine, I and I2, are produced spontaneously in the dark at the air-water interface of iodide-containing droplets without any added catalysts, oxidants, or irradiation. Specifically, we observe I3- formation within droplets, and I2 emission into the gas phase from NaI-containing droplets over a range of droplet sizes. The formation of both products is enhanced in the presence of electron scavengers, either in the gas phase or in solution, and it clearly follows a Langmuir-Hinshelwood mechanism, suggesting an interfacial process. These observations are consistent with iodide oxidation at the interface, possibly initiated by the strong intrinsic electric field present there, followed by well-known solution-phase reactions of the iodine atom. This interfacial chemistry could be important in many contexts, including atmospheric aerosols.

Uptake of Hydrogen Peroxide from the Gas Phase to Grain Boundaries: A Source in Snow and Ice.

Hydrogen peroxide is a primary atmospheric oxidant significant in terminating gas-phase chemistry and sulfate formation in the condensed phase. Laboratory experiments have shown an unexpected oxidation acceleration by hydrogen peroxide in grain boundaries. While grain boundaries are frequent in natural snow and ice and are known to host impurities, it remains unclear how and to which extent hydrogen peroxide enters this reservoir. We present the first experimental evidence for the diffusive uptake of hydrogen peroxide into grain boundaries directly from the gas phase. We have machined a novel flow reactor system featuring a drilled ice flow tube that allows us to discern the effect of the ice grain boundary content on the uptake. Further, adsorption to the ice surface for temperatures from 235 to 258 K was quantified. Disentangling the contribution of these two uptake processes shows that the transfer of hydrogen peroxide from the atmosphere to snow at temperatures relevant to polar environments is considerably more pronounced than previously thought. Further, diffusive uptake to grain boundaries appears to be a novel mechanism for non-acidic trace gases to fill the highly reactive impurity reservoirs in snow's grain boundaries.

Experimental Confirmation of H2O2 Adsorption at the Water-Air Interface.

Recent work has reported that hydrogen peroxide is formed at the air-water interface. Given the reduced solvation environment there, this process could give rise to enhanced production of OH from H2O2 photolysis at the interface. These considerations give some importance to understanding the adsorption thermochemistry of hydrogen peroxide. Although there are two molecular dynamics studies that provide the adsorption free energy, to date there is no experimental verification that H2O2 adsorbs at the air-water interface. Here we use glancing-angle Raman spectroscopy to follow the surface adsorption behavior of this molecule. Using standard states of 1 mol L-1 for each of the bulk and surface phases yields a ΔG° of -5 kJ mol-1 at 293 K, comparable to that obtained for DMSO.

Modeling the Removal of Water-Soluble Trace Gases from Indoor Air via Air Conditioner Condensate.

Water-soluble trace gas (WSTG) loss from indoor air via air conditioning (AC) units has been observed in several studies, but these results have been difficult to generalize. In the present study, we designed a box model that can be used to investigate and estimate WSTG removal due to partitioning to AC coil condensate. We compared the model output to measurements of a suite of organic acids cycling in an indoor environment and tested the model by varying the input AC parameters. These tests showed that WSTG loss via AC cycling is influenced by Henry's law constant of the compound in question, which is controlled by air and water temperatures and the condensate pH. Air conditioning unit specifications also impact WSTG loss through variations in the sensible heat ratio, the effective recirculation rate of air through the unit, and the timing of coil and fan operation. These findings have significant implications for indoor modeling. To accurately model the fate of indoor WSTGs, researchers must either measure or otherwise account for these unique environmental and operational characteristics.

Chemical Morphology Controls Reactivity of OH Radicals at the Air-Ice Interface.

At the air-ice interface, some aromatic compounds such as benzene and anthracene are surprisingly unreactive toward OH. This may be a consequence of the poor solvation of these compounds at the interface, resulting in clustering there. We test this hypothesis by comparing the reaction of OH with pyrene, a 4-ring polyaromatic hydrocarbon (PAH), to reactions of OH with the more water-soluble compounds coumarin and 7-hydroxycoumarin (7OHC). We observe that OH reacts readily with coumarin and 7OHC at both liquid and frozen air-water interfaces. Pyrene, a much less soluble compound, reacts with OH at the liquid surface but not at the air-ice interface. We report evidence of pyrene aggregation at the ice surface based on its broadened and red-shifted emission spectrum alongside fluorescence mapping of anthracene, a closely related 3-ring PAH, which shows bunching at the ice surface. By contrast, fluorescence mapping shows that coumarin is fairly homogeneously distributed at the air-ice interface. Together, these results suggest that the limited reactivity of some compounds toward OH at the ice surface may be a consequence of their propensity to self-aggregate, demonstrating that chemical morphology can play an important role in reactions at the ice surface.

Loss of NO(g) to painted surfaces and its re-emission with indoor illumination.

Heterogeneous surface reactions play a key role in the chemistry of the indoor environment because of the large indoor surface-to-volume ratio. The presence of photocatalytic material in indoor paints may allow photochemical reactions to occur at wavelengths of light that are present indoors. One such potential reaction is the heterogeneous photooxidation of NO to HONO. NO(g) is commonly found indoors, originating from combustion sources, ventilation and infiltration of outdoor air. We studied the interaction of NO(g) with painted surfaces illuminated with indoor fluorescent and incandescent lighting. There is a loss of NO(g) to painted surfaces in the dark at both 0 and 50% RH. At 50% RH, there is a re-release of some of that NO(g) under illumination. The same behavior is observed for illumination of different colored paints. This is in contrast to what is seen with TiO2 as the substrate, where photoenhanced uptake of NO(g) and formation of NO2 (g) are observed. We hypothesize that the loss of NO(g) is due to adsorption and diffusion into the paint. The re-release of NO under illumination is thought to be due to photooxidation of NO to HONO on the painted surface at higher relative humidities and subsequent HONO photolysis.

Seasonality of the Water-Soluble Inorganic Ion Composition and Water Uptake Behavior of Urban Grime.

Impervious surfaces, especially in urban environments, are coated with a film composed of a complex mixture of substances, referred to as urban grime. Despite its ubiquity, the factors that dictate urban grime composition are still not well understood. Here, we present the first study of the seasonal variation in composition of water-soluble inorganic ions present in urban grime, performed by analyzing samples collected in Toronto for 4-week intervals over the course of a year. A clear seasonality in the composition is evident, with NaCl dominating in the winter months and Ca2+ and NO3- dominant in the summer. We compare the grime composition to the water-soluble ion composition of PM2.5 and PM10 in order to infer chemistry occurring within the grime and find evidence that chemistry occurring within the urban grime matrix could provide a source of ClNO2 and NH3 to the urban atmosphere. The uptake of water by urban grime also shows a clear seasonality, which may be driven by the changing proportions of nitrate salts and/or oxidized organic compounds over the year.

Water Evaporation from Acoustically Levitated Aqueous Solution Droplets.

We present a systematic study of the effect of solutes on the evaporation rate of acoustically levitated aqueous solution droplets by suspending individual droplets in a zero-relative humidity environment and measuring their size as a function of time. The ratios of the early time evaporation rates of six simple salts (NaCl, NaBr, NaNO3, KCl, MgCl2, CaCl2) and malonic acid to that of water are in excellent agreement with predictions made by modifying the Maxwell equation to include the time-dependent water activity of the evaporating aqueous salt solution droplets. However, the early time evaporation rates of three ammonium salt solutions (NH4Cl, NH4NO3, (NH4)2SO4) are not significantly different from the evaporation rate of pure water. This finding is in accord with a previous report that ammonium sulfate does not depress the evaporation rate of its solutions, despite reducing its water vapor pressure, perhaps due to specific surface effects. At longer evaporation times, as the droplets approach crystallization, all but one (MgCl2) of the solution evaporation rates are well described by the modified Maxwell equation.

Chemical Morphology of Frozen Mixed Nitrate-Salt Solutions.

Surface chemistry on ice can play an important role in atmospheric composition, but uncertainties in the chemical partitioning within ice samples has hindered the development of accurate models of these systems. Using Raman microscopy, we examine the nitrate distribution in ice and liquid samples containing environmentally relevant concentrations of sodium chloride, sodium bromide, and sea salt analogue Instant Ocean. Nitrate is enhanced at the surface compared to in the bulk in all frozen samples but to different degrees depending on the added salt. A large variation of nitrate in the horizontal dimension of frozen samples provides direct evidence that it congregates in pockets or grain boundaries within the crystal. In these pockets, nitrate experiences a solution-like environment, whereas at the surface nitrate sometimes forms solid crystals.

Mechanistic Insights on the Photosensitized Chemistry of a Fatty Acid at the Air/Water Interface.

Interfaces are ubiquitous in the environment and many atmospheric key processes, such as gas deposition, aerosol, and cloud formation are, at one stage or another, strongly impacted by physical and chemical processes occurring at interfaces. Here, the photoinduced chemistry of an air/water interface coated with nonanoic acid-a fatty acid surfactant we use as a proxy for chemically complex natural aqueous surface microlayers-was investigated as a source of volatile and semivolatile reactive organic species. The carboxylic acid coating significantly increased the propensity of photosensitizers, chosen to mimic those observed in real environmental waters, to partition to the interface and enhance reactivity there. Photochemical formation of functionalized and unsaturated compounds was systematically observed upon irradiation of these coated surfaces. The role of a coated interface appears to be critical in providing a concentrated medium allowing radical-radical reactions to occur in parallel with molecular oxygen additions. Mechanistic insights are provided from extensive analysis of products observed in both gas and aqueous phases by online switchable reagent ion-time of flight-mass spectrometry and by off-line ultraperformance liquid chromatography coupled to a Q Exactive high resolution mass spectrometer through heated electrospray ionization, respectively.

Nitrate Photolysis in Salty Snow.

Nitrate photolysis from snow can have a significant impact on the oxidative capacity of the local atmosphere, but the factors affecting the release of gas-phase products are not well understood. Here, we report a systematic study of the amounts of NO, NO2, and total nitrogen oxides (NOy) emitted from illuminated snow samples as a function of both nitrate and total salt (NaCl and Instant Ocean) concentration. The results provide experimental evidence that the release of nitrogen oxides to the gas phase is directly related to the expected nitrate concentration in the brine at the surface of the snow crystals. With no added salts, steady-state release of gas-phase products increases to a plateau value with increasing prefreezing nitrate concentration; with the addition of salts, the steady-state gas-phase nitrogen oxides generally decrease with increasing prefreezing NaCl or Instant Ocean concentration. In addition, for these frozen mixed nitrate (25 mM)-salt (0-500 mM) solutions, there is an increase in gas-phase NO2 seen at low added salt amounts, with NO2 production enhanced by up to 42% at low prefreezing [NaCl] (≤25 mM) and by up to 89% at prefreezing Instant Ocean concentrations lower than 200 mM [Cl-]. This enhancement may be important to the atmospheric oxidative capacity in polar regions.

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes.

The heterogeneous reaction between SO2 and unsaturated compounds results in the efficient production of organosulfates for several fatty acids and long-chain alkenes. The presence of an acid group, the physical state of the reactants (solid or liquid), the nature of the double bond (cis, trans, terminal), and the use of light irradiation all have an impact on the reaction rate. The reaction was investigated using different set-ups (coated flow tube, aerosol flow tube, and diffuse reflectance infrared Fourier transform cell). The reaction products were identified by high-resolution mass spectrometry and the impact of this reaction on organosulfate formation in the atmosphere is discussed.

Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface.

We report on experiments that probe photosensitized chemistry at the air/water interface, a region that does not just connect the two phases but displays its own specific chemistry. Here, we follow reactions of octanol, a proxy for environmentally relevant soluble surfactants, initiated by an attack by triplet-state carbonyl compounds, which are themselves concentrated at the interface by the presence of this surfactant. Gas-phase products are determined using PTR-ToF-MS, and those remaining in the organic layer are determined by ATR-FTIR spectroscopy and HPLC-HRMS. We observe the photosensitized production of carboxylic acids as well as unsaturated and branched-chain oxygenated products, compounds that act as organic aerosol precursors and had been thought to be produced solely by biological activity. A mechanism that is consistent with the observations is detailed here, and the energetics of several key reactions are calculated using quantum chemical methods. The results suggest that the concentrating nature of the interface leads to its being a favorable venue for radical reactions yielding complex and functionalized products that themselves could initiate further secondary chemistry and new particle formation in the atmospheric environment.

A pinch of salt is all it takes: chemistry at the frozen water surface.

Chemical interactions at the air-ice interface are of great importance to local atmospheric chemistry but also to the concentrations of pollutants deposited onto natural snow and ice. However, the study of such processes has been hampered by the lack of general, surface-specific probes. Even seemingly basic chemical properties, such as the local concentration of chemical compounds, or the pH at the interface, have required the application of assumptions about solute distributions in frozen media. The measurements that have been reported have tended for the most part to focus on entire ice or snow samples, rather than strictly the frozen interface with the atmosphere. We have used glancing-angle laser spectroscopy to interrogate the air-ice interface; this has yielded several insights into the chemical interactions there. The linear fluorescence and Raman spectra thus measured have the advantage of easy interpretability; careful experimentation can limit their probe depth to that which is relevant to atmospheric heterogeneous processes. We have used these techniques to show that the environment at the interface between air and freshwater ice surfaces is distinct from that at the interface between air and liquid water. Acids such as HCl that adsorb to ice surfaces from the gas phase result in significantly different pH responses than those at liquid water surfaces. Further, the solvation of aromatic species is suppressed at freshwater ice surfaces compared with that at liquid water surfaces, leading to extensive self-association of aromatics at ice surfaces. Photolysis kinetics of these species are much faster than at liquid water surfaces; this can sometimes (but not always) be explained by red shifts in the absorption spectra of self-associated aromatics increasing the extent to which solar radiation is absorbed. The environment presented by frozen saltwater surfaces, in contrast, appears to be reasonably well-described by liquid water. The extent of hydrogen bonding and the solvation of adsorbed species are similar at liquid water surfaces and at frozen saltwater surfaces. Adsorbed acids and bases evoke similar pH responses at frozen saltwater ice surfaces and liquid water surfaces, and photochemical kinetics of at least some aromatic compounds at frozen saltwater ice surfaces are well-described by kinetics in liquid water. These differences are not observed in experiments that interrogate the entire ice sample (i.e., that do not distinguish between processes occurring in liquid regions within bulk ice and those at the air-ice interface). Our work has shown that in general, the chemistry occurring at salty frozen interfaces is well described as being cold aqueous chemistry, whereas that seen at the pure ice interface is not. These findings have significant implications for heterogeneous atmospheric processes in ice-covered environments.

Chemistry of Urban Grime: Inorganic Ion Composition of Grime vs Particles in Leipzig, Germany.

Deposition of atmospheric constituents--either gas phase or particulate--onto urban impervious surfaces gives rise to a thin "urban grime" film. The area exposed by these impervious surfaces in a typical urban environment is comparable to, or greater than, that of particles present in the urban boundary layer; however, it is largely overlooked as a site for heterogeneous reactions. Here we present the results of a field campaign to determine and compare the chemical composition of urban grime and of particles collected simultaneously during the autumn of 2014 at an urban site in central Leipzig, Germany. We see dramatically reduced ammonium and nitrate levels in the film as compared to particles, suggesting a significant loss of ammonium nitrate, thus enhancing the mobility of these species in the environment. Nitrate levels are 10% lower for films exposed to sunlight compared to those that were shielded from direct sun, indicating a possible mechanism for recycling nitrate anion to reactive nitrogen species. Finally, chloride levels in the film suggest that urban grime could represent an unrecognized source of continental chloride available for ClNO2 production even in times of low particulate chloride. Such source and recycling processes could prove to be important to local and regional air quality.

Experimental determination of the partitioning of representative organic pollutants to the air-water interface.

Using glancing-angle laser-induced fluorescence (GALIF) spectroscopy as a probe, the partitioning of naphthalene, fluoranthene, pyrene, umbelliferone, phenol red, and bisphenol A from bulk solution to the air-water interface was examined in both pure water and aqueous solutions of 6 mM octanol. Previous studies provided similar Langmuir adsorption isotherms for anthracene and imidazole 2-carboxaldehyde. The surface partitioning behaviour of each compound in both environments was well described using a Langmuir adsorption model; partitioning coefficients were derived from the fits to such isotherms. Only the PAH molecules, naphthalene, fluoranthene and pyrene, saw an enhancement in the surface partitioning in octanol solution compared to pure water. The surface partitioning to pure water surfaces could be fairly well described using a one parameter linear free energy relationship based on either solubility or KOW.

Ionic Composition of Particulate Matter across Canada Shows Evidence for Near-Ubiquitous Chloride Activation and Sulfate Neutralization.

Using publicly available data from the National Air Pollution Surveillance Program, water-soluble ion mole fractions in PM2.5 and PM2.5-10 were extracted for 2010, 2012, 2013, and 2015 at six locations across Canada. Fine particle ion content was dominated by ammonium sulfate, with ammonium to sulfate ratios largely approaching 2 and no seasonal or geographic trends. Sulfate and nitrate mole fractions were negatively correlated in the fine particles, consistent with their expected pathways of entry into PM2.5. Coarse particle composition varied depending on location and season. Coastal stations were dominated by sodium and chloride year-round while inland stations showed high amounts of these ions only during the colder months, where road salt is often applied. A negative correlation between nitrate and chloride mole fractions as well as a positive correlation between nitrate concentrations and "missing" chloride provides evidence for near-ubiquitous nitrate displacement of chloride. This displacement was strongly indicated in coastal sites and also evident inland, especially during cold months. Weak evidence for nitrogen dioxide as the source of nitrate was found for inland sites, but none was found for coastal sites, suggesting a nonlocal source for the particulate nitrate precursor.

Photochemical renoxification on commercial indoor photoactive paint.

Surface chemistry plays an important role in the indoor environment owing to the large indoor surface to volume ratio. This study explores the photoreactivity of surfaces painted with a photoactive paint in the presence of NOx. Two types of experiments are performed; illumination of painted surfaces with a nitrate deposit and illumination of painted surfaces in the presence of gaseous NO. For both types of experiments, illumination with a fluorescent bulb causes the greatest change in measured gaseous NOx concentrations. Results show that relative humidity and paint composition play an important role in the photoreactivity of indoor painted surfaces. Painted surfaces could contribute to gas-phase oxidant concentrations indoors.