Molecular Insights into Chemical Reactions at Aqueous Aerosol Interfaces.

Atmospheric aerosols facilitate reactions between ambient gases and dissolved species. Here, we review our efforts to interrogate the uptake of these gases and the mechanisms of their reactions both theoretically and experimentally. We highlight the fascinating behavior of N2O5 in solutions ranging from pure water to complex mixtures, chosen because its aerosol-mediated reactions significantly impact global ozone, hydroxyl, and methane concentrations. As a hydrophobic, weakly soluble, and highly reactive species, N2O5 is a sensitive probe of the chemical and physical properties of aerosol interfaces. We employ contemporary theory to disentangle the fate of N2O5 as it approaches pure and salty water, starting with adsorption and ending with hydrolysis to HNO3, chlorination to ClNO2, or evaporation. Flow reactor and gas-liquid scattering experiments probe even greater complexity as added ions, organic molecules, and surfactants alter the interfacial composition and reaction rates. Together, we reveal a new perspective on multiphase chemistry in the atmosphere.

Probing the interfacial structure of aqueous surfactants through helium atom evaporation.

Dissolved helium atoms evaporate from liquids in super-Maxwellian speed distributions because their interactions are too weak to enforce full thermal equilibration at the surface as they are "squeezed" out of solution. The excess speeds of these He atoms reflect their final interactions with solvent and solute molecules at the surfaces of water and other liquids. We extend this observation by monitoring He atom evaporation from salty water solutions coated with surfactants. These surface-active molecules span neutral, anionic, and cationic amphiphiles: butanol, 3-methyl-1-butanol, pentanol, pentanoic acid, pentanoate, tetrabutylammonium, benzyltrimethylammonium, hexyltrimethylammonium, and dodecyltrimethylammonium, each characterized by surface tension measurements. The helium energy distributions, recorded in vacuum using a salty water microjet, reveal a sharp distinction between neutral and ionic surfactant films. Helium atoms evaporate through neutral surfactant monolayers in speed distributions that are similar to a pure hydrocarbon, reflecting the common alkyl chains of both. In contrast, He atoms appear to evaporate through ionic surfactant layers in distributions that are closer to pure salty water. We speculate that the ionic surfactants distribute themselves more loosely and deeply through the top layers of the aqueous solution than do neutral surfactants, with gaps between the surfactants that may be filled with salty water. This difference is supported by prior molecular dynamics simulations and ion scattering measurements of surfactant solutions.

Acidity across the interface from the ocean surface to sea spray aerosol.

Aerosols impact climate, human health, and the chemistry of the atmosphere, and aerosol pH plays a major role in the physicochemical properties of the aerosol. However, there remains uncertainty as to whether aerosols are acidic, neutral, or basic. In this research, we show that the pH of freshly emitted (nascent) sea spray aerosols is significantly lower than that of sea water (approximately four pH units, with pH being a log scale value) and that smaller aerosol particles below 1 µm in diameter have pH values that are even lower. These measurements of nascent sea spray aerosol pH, performed in a unique ocean-atmosphere facility, provide convincing data to show that acidification occurs "across the interface" within minutes, when aerosols formed from ocean surface waters become airborne. We also show there is a correlation between aerosol acidity and dissolved carbon dioxide but no correlation with marine biology within the seawater. We discuss the mechanisms and contributing factors to this acidity and its implications on atmospheric chemistry.

Rapid cloud removal of dimethyl sulfide oxidation products limits SO2 and cloud condensation nuclei production in the marine atmosphere.

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth's radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO2) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τHPMTF < 2 h) and terminates DMS oxidation to SO2 When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.

Weak Temperature Dependence of the Relative Rates of Chlorination and Hydrolysis of N2O5 in NaCl-Water Solutions.

We have measured the temperature dependence of the ClNO2 product yield in competition with hydrolysis following N2O5 uptake to aqueous NaCl solutions. For NaCl-D2O solutions spanning 0.0054-0.21 M, the ClNO2 product yield decreases on average by only 4 ± 3% from 5 to 25 °C. Less reproducible measurements at 0.54-2.4 M NaCl also fall within this range. The ratio of the rate constants for chlorination and hydrolysis of N2O5 in D2O is determined on average to be 1150 ± 90 at 25 °C up to 0.21 M NaCl, favoring chlorination. This ratio is observed to decrease significantly at the two highest concentrations. An Arrhenius analysis reveals that the activation energy for hydrolysis is just 3.0 ± 1.5 kJ/mol larger than for chlorination up to 0.21 M, indicating that Cl- and D2O attack on N2O5 has similar energetic barriers despite the differences in charge and complexity of these reactants. In combination with the measured preexponential ratio favoring chlorination of 300-200+400, we conclude that the strong preference of N2O5 to undergo chlorination over hydrolysis is driven by dynamic and entropic, rather than enthalpic, factors. Molecular dynamics simulations elucidate the distinct solvation between strongly hydrated Cl- and the hydrophobically solvated N2O5. Combining this molecular picture with the Arrhenius analysis implicates the role of water in mediating interactions between such distinctly solvated species and suggests a role for diffusion limitations on the chlorination reaction.

Global airborne sampling reveals a previously unobserved dimethyl sulfide oxidation mechanism in the marine atmosphere.

Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth's radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate.

Anthropogenic and Biogenic Contributions to the Organic Composition of Coastal Submicron Sea Spray Aerosol.

The organic composition of coastal sea spray aerosol is important for both atmospheric chemistry and public health but remains poorly characterized. Coastal waters contain an organic material derived from both anthropogenic processes, such as wastewater discharge, and biological processes, including biological blooms. Here, we probe the chemical composition of the organic fraction of sea spray aerosol over the course of the 2019 SeaSCAPE mesocosm experiment, in which a phytoplankton bloom was facilitated in natural coastal water from La Jolla, California. We apply untargeted two-dimensional gas chromatography to characterize submicron nascent sea spray aerosol samples, reporting ∼750 unique organic species traced over a 19 day phytoplankton bloom experiment. Categorization and quantitative compositional analysis reveal three major findings. First, anthropogenic species made up 30% of total submicron nascent sea spray aerosol organic mass under the pre-bloom condition. Second, biological activity drove large changes within the aerosolized carbon pool, decreasing the anthropogenic mass fraction by 89% and increasing the biogenic and biologically transformed fraction by a factor of 5.6. Third, biogenic marine organics are underrepresented in mass spectral databases in comparison to marine organic pollutants, with more than twice as much biogenic aerosol mass attributable to unlisted compounds.

Reactive Uptake of Hydroperoxymethyl Thioformate to Sodium Chloride and Sodium Iodide Aerosol Particles.

The oxidation products of dimethyl sulfide (DMS) contribute to the production and growth of cloud condensation nuclei (CCN) in the marine boundary layer. Recent work demonstrates that DMS is oxidized by OH radicals to the stable intermediate hydroperoxymethyl thioformate (HPMTF), which is both globally ubiquitous and efficiently lost to multiphase processes in the marine atmosphere. At present, there are no experimental measurements of the reactive uptake of HPMTF to aerosol particles, limiting model implementation of multiphase HPMTF chemistry. Using an entrained aerosol flow reactor combined with chemical ionization mass spectrometry (CIMS), we measured the reactive uptake coefficient (γ) of HPMTF to dry sodium chloride (NaCl), wet NaCl, and wet sodium iodide (NaI) particles to be (1.9 ± 1.3) × 10-4, (1.6 ± 0.6) × 10-3, and (9.2 ± 2.3) × 10-1, respectively. While we did not directly measure the condensed-phase products of HPMTF reactive uptake in this experiment, the ionization products observed in the CIMS instrument provide mechanistic insight on the reaction mechanism of HPMTF with halides.

Reactive VOC Production from Photochemical and Heterogeneous Reactions Occurring at the Air-Ocean Interface.

The ocean surface serves as a source and sink for a diverse set of reactive trace gases in the atmosphere, including volatile organic compounds (VOCs), reactive halogens, and oxidized and reduced nitrogen compounds. The exchange of reactive trace gases between the atmosphere and ocean has been shown to alter atmospheric oxidant concentrations and drive particle nucleation and growth. Uncertainties in cloud radiative forcing and aerosol-cloud interactions are among the largest uncertainties in current global climate models. Climate models are particularly sensitive to cloud cover over the remote ocean due to large changes in albedo between the ocean surface and cloud tops. Oceanic emissions contribute to cloud condensation nuclei concentrations, either through the direct emission of particles during wave breaking or through the formation of secondary aerosol particles following the emission of reactive gas-phase compounds. Despite generally small and diffuse oceanic emission rates for reactive trace gases, it has been shown that oxidant and particle number concentrations are acutely sensitive to air-sea trace gas exchange rates and the chemical composition of emitted species. To date, field measurements of air-sea reactive gas exchange have focused primarily on the emission of gases of biological origin, such as dimethyl sulfide (DMS). While DMS emissions are relatively well constrained, the gas-phase oxidation that connects DMS to sulfate aerosol is less well understood. Recent laboratory measurements suggest that heterogeneous and photochemical reactions occurring at the air-sea interface can also lead to the production and emission of a wide array of reactive VOC. When laboratory-based measurements are used to derive global scale emissions, the calculated sea-to-air fluxes of reactive VOC generated from heterogeneous and photochemical processes are comparable or larger in magnitude to the sea-to-air flux of DMS. It is not yet clear how the mechanisms proposed in these laboratory experiments translate to atmospheric conditions. The proposed abiotic emissions are also a potential source of VOC in regions of low biological activity, which carries important implications for regional and global modeling.This Account reviews recent laboratory and field experiments of biotic and abiotic ocean VOC emissions, with a specific focus on exploring open questions related to proposed abiotic reactive VOC emissions and the impact of including a large, abiotic VOC emission source on atmospheric oxidants and aerosol particles. To date, abiotic emissions are not typically included in global chemical transport models. The proposed abiotic emissions mechanisms discussed here have the potential to drive significant changes to current understanding of chemistry in the marine atmosphere if present at the magnitudes suggested by laboratory studies. In order to validate their proposed significance, a coordinated set of laboratory, field, and modeling studies under ocean-relevant conditions are necessary.

Atmospheric Benzothiazoles in a Coastal Marine Environment.

Organic emissions from coastal waters play an important but poorly understood role in atmospheric chemistry in coastal regions. A mesocosm experiment focusing on facilitated biological blooms in coastal seawater, SeaSCAPE (Sea Spray Chemistry and Particle Evolution), was performed to study emission of volatile gases, primary sea spray aerosol, and formation of secondary marine aerosol as a function of ocean biological and chemical processes. Here, we report observations of aerosol-phase benzothiazoles in a marine atmospheric context with complementary measurements of dissolved-phase benzothiazoles. Though previously reported dissolved in polluted coastal waters, we report the first direct evidence of the transfer of these molecules from seawater into the atmosphere. We also report the first gas-phase observations of benzothiazole in the environment absent a direct industrial, urban, or rubber-based source. From the identities and temporal dynamics of the dissolved and aerosol species, we conclude that the presence of benzothiazoles in the coastal water (and thereby their emissions into the atmosphere) is primarily attributable to anthropogenic sources. Oxidation experiments to explore the atmospheric fate of gas-phase benzothiazole show that it produces secondary aerosol and gas-phase SO2, making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

Diel Profile of Hydroperoxymethyl Thioformate: Evidence for Surface Deposition and Multiphase Chemistry.

Dimethyl sulfide (DMS; CH3SCH3), a biogenically produced trace gas emitted from the ocean, accounts for a large fraction of natural sulfur released to the marine atmosphere. The oxidation of DMS in the marine boundary layer (MBL), via the hydrogen abstraction pathway, yields the short-lived methylthiomethylperoxy radical (MSP; CH3SCH2OO). In the remote MBL, unimolecular isomerization of MSP outpaces bimolecular chemistry leading to the efficient formation of hydroperoxymethyl thioformate (HPMTF; HOOCH2SCHO). Here, we report the first ground observations and diurnal profiles of HPMTF mixing ratios, vertical fluxes, and deposition velocities to the ocean surface. Average daytime HPMTF mixing ratios, fluxes, and deposition velocities were recorded at 12.1 pptv, -0.11 pptv m s-1, and 0.75 cm s-1, respectively. The deposition velocity of HPMTF is comparable to other soluble gas phase compounds (e.g., HCOOH and HNO3), resulting in a deposition lifetime of 30 h under typical windspeeds (3 m s-1). A box model analysis incorporating the current mechanistic understanding of DMS oxidation chemistry and geostationary satellite cloud imagery data suggests that the lifetime of HPMTF in the MBL at this sampling location is likely controlled by heterogeneous loss to aerosol and uptake to clouds in the morning and evening.

HONO Emissions from Western U.S. Wildfires Provide Dominant Radical Source in Fresh Wildfire Smoke.

Wildfires are an important source of nitrous acid (HONO), a photolabile radical precursor, yet in situ measurements and quantification of primary HONO emissions from open wildfires have been scarce. We present airborne observations of HONO within wildfire plumes sampled during the Western Wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) campaign. ΔHONO/ΔCO close to the fire locations ranged from 0.7 to 17 pptv ppbv-1 using a maximum enhancement method, with the median similar to previous observations of temperate forest fire plumes. Measured HONO to NOx enhancement ratios were generally factors of 2, or higher, at early plume ages than previous studies. Enhancement ratios scale with modified combustion efficiency and certain nitrogenous trace gases, which may be useful to estimate HONO release when HONO observations are lacking or plumes have photochemical exposures exceeding an hour as emitted HONO is rapidly photolyzed. We find that HONO photolysis is the dominant contributor to hydrogen oxide radicals (HOx = OH + HO2) in early stage (<3 h) wildfire plume evolution. These results highlight the role of HONO as a major component of reactive nitrogen emissions from wildfires and the main driver of initial photochemical oxidation.

SN2 Reactions of N2O5 with Ions in Water: Microscopic Mechanisms, Intermediates, and Products.

Reactions of dinitrogen pentoxide (N2O5) greatly affect the concentrations of NO3, ozone, OH radicals, methane, and more. In this work, we employ ab initio molecular dynamics and other tools of computational chemistry to explore reactions of N2O5 with anions hydrated by 12 water molecules to shed light on this important class of reactions. The ions investigated are Cl-, SO42-, ClO4-, and RCOO- (R = H, CH3, C2H5). The following main results are obtained: (i) all the reactions take place by an SN2-type mechanism, with a transition state that involves a contact ion pair (NO2+NO3-) that interacts strongly with water molecules. (ii) Reactions of a solvent-separated nitronium ion (NO2+) are not observed in any of the cases. (iii) An explanation is provided for the suppression of ClNO2 formation from N2O5 reacting with salty water when sulfate or acetate ions are present, as found in recent experiments. (iv) Formation of novel intermediate species, such as (SO4NO2-) and RCOONO2, in these reactions is predicted. The results suggest atomistic-level mechanisms for the reactions studied and may be useful for the development of improved modeling of reaction kinetics in aerosol particles.

Production of Br2 from N2O5 and Br- in Salty and Surfactant-Coated Water Microjets.

Gas-liquid scattering experiments are used to investigate the oxidation-reduction reaction N2O5(g) + 2Br-(aq) → Br2(g) + NO3-(aq) + NO2-(aq), a model for the nighttime absorption of N2O5 into aerosol droplets containing halide ions. The detection of evaporating Br2 molecules provides our first observation of a gaseous reaction product generated by a water microjet in vacuum. N2O5 molecules are directed at a 35 µm diameter jet of 6 or 8 m LiBr in water at 263 or 240 K, followed by detection of both unreacted N2O5 and product Br2 molecules by velocity-resolved mass spectrometry. The N2O5 reaction probability at near-thermal collision energy is too small to be measured and likely lies below 0.2. However, the evaporating Br2 product can be detected and controlled by the presence of surfactants. The addition of 0.02 m 1-butanol, which creates ∼40% of a compact monolayer, reduces Br2 production by 35%. Following earlier studies, this reduction may be attributed to surface butanol molecules that block N2O5 entry or alter the near-surface distribution of Br-. Remarkably, addition of the cationic surfactant tetrabutylammonium bromide (TBABr) at 0.005 m (9% of a monolayer) reduces the Br2 signal by 85%, and a 0.050 m solution (58% of a monolayer) causes the Br2 signal to disappear entirely. A detailed analysis suggests that TBA+ efficiently suppresses Br2 evaporation because it tightly bonds to the Br3- intermediate formed in the highly concentrated Br- solution and thereby hinders the rapid release and evaporation of Br2.

Sea spray aerosol as a unique source of ice nucleating particles.

Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using "dry" geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

Sea spray aerosol chemical composition: elemental and molecular mimics for laboratory studies of heterogeneous and multiphase reactions.

Sea spray aerosol particles (SSA), formed through wave breaking at the ocean surface, contribute to natural aerosol particle concentrations in remote regions of Earth's atmosphere, and alter the direct and indirect effects of aerosol particles on Earth's radiation budget. In addition, sea spray aerosol serves as suspended surface area that can catalyze trace gas reactions. It has been shown repeatedly that sea spray aerosol is heavily enriched in organic material compared to the surface ocean. The selective enrichment of organic material complicates the selection of representative molecular mimics of SSA for laboratory or computational studies. In this review, we first provide a short introduction to SSA formation processes and discuss chemical transformations of SSA that occur in polluted coastal regions and remote pristine air. We then focus on existing literature of the chemical composition of nascent SSA generated in controlled laboratory experiments and field investigations. We combine the evidence on the chemical properties of nascent SSA with literature measurements of SSA water uptake to assess SSA molecular composition and liquid water content. Efforts to speciate SSA organic material into molecular classes and specific molecules have led to the identification of saccharides, alkanes, free fatty acids, anionic surfactants, dicarboxylic acids, amino acids, proteinaceous matter, and other large macromolecules. However to date, less than 25% of the organic mass of nascent SSA has been quantified at a molecular level. As discussed here, quantitative measurements of size resolved elemental ratios, combined with determinations of water uptake properties, provides unique insight on the concentration of ions within SSA as a function of particle size, pointing to a controlling role for relative humidity and the hygroscopicity of SSA organic material at small particle diameters.

N2O5 at water surfaces: binding forces, charge separation, energy accommodation and atmospheric implications.

Interactions of N2O5 with water media are of great importance in atmospheric chemistry and have been the topic of extensive research for over two decades. Nevertheless, many physical and chemical properties of N2O5 at the surface or in bulk water are unknown or not microscopically understood. This study presents extensive new results on the physical properties of N2O5 in water and at the surface of water, with a focus on their microscopic basis. The main results are obtained using ab initio molecular dynamics and calculations of a potential of mean force. These include: (1) collisions of N2O5 with water at 300 K lead to trapping at the surface for at least 20 ps and with 95% probability. (2) During that time, there is no N2O5 hydrolysis, evaporation, or entry into the bulk. (3) Charge separation between the NO2 and NO3 groups of N2O5, fluctuates significantly with time. (4) Energy accommodation of the colliding N2O5 at the surface takes place within picoseconds. (5) The binding energy of N2O5 to a nanosize amorphous ice particle at 0 K is on the order of 15 kcal mol-1 for the main surface site. N2O5 binding to the cluster is due to one weak hydrogen bond and to interactions between partial charges on the N2O5 and on water. (6) The free-energy profile was calculated for transporting N2O5 from the gas phase through the interface and into bulk water. The corresponding concentration profile exhibits a propensity for N2O5 at the aqueous surface. The free energy barrier for entry from the surface into the bulk was determined to be 1.8 kcal mol-1. These findings are used to interpret recent experiments. We conclude with implications of this study for atmospheric chemistry.

Control of Interfacial Cl2 and N2O5 Reactivity by a Zwitterionic Phospholipid in Comparison with Ionic and Uncharged Surfactants.

Gas-liquid scattering experiments reveal that charge-separated but neutral (zwitterionic) surfactants catalyze the oxidation of dissolved Br- to Br2 by gaseous Cl2 at the surface of a 0.3 M NaBr/glycerol solution. Solutions of NaBr dissolved in glycerol with no surfactant were compared with solutions coated with zwitterionic, cationic, and anionic surfactants at dilute surface concentrations of 1.1 to 1.5 × 1014 cm-2 (less than 65% of maximum chain packing). The zwitterionic phospholipid enhances Cl2 conversion of Br- to Br2 by a factor of 1.61 ± 0.15, in comparison with a 14-fold enhancement by a cationic surfactant (tetrahexylammonium) and a five-fold suppression by an anionic surfactant (dodecyl sulfate). Further studies indicate that even an uncharged surfactant, monododecanoylglycerol, enhances Cl2 → Br2 production. Similar behavior is observed for the oxidation of Br- to Br2 by N2O5; it is just slightly suppressed by the phospholipid and strongly enhanced by the cationic surfactant. Collectively, these results suggest that attractions and repulsions between the negative Br- ions and the positive and negative charges of the surfactant headgroups draw Br- ions to the surface or repel them away. At low coverages, ion-induced dipole and dispersion interactions between the CH2 groups and Br- or Cl2 may also enhance reactivity. These results demonstrate that the hydrocarbon chains of loosely packed surfactants do not necessarily block gas-liquid reactions but that positively charged, and even uncharged, groups can instead facilitate reactions by bringing gas-phase and solution-phase reagents together in the interfacial region.

Reactions of N2O5 with Salty and Surfactant-Coated Glycerol: Interfacial Conversion of Br- to Br2 Mediated by Alkylammonium Cations.

Gas-liquid scattering and product-yield experiments are used to investigate reactions of N2O5 with glycerol containing Br- and surfactant ions. N2O5 oxidizes Br- to Br2 for every solution tested: 2.7 M NaBr, 0.03 M tetrahexylammonium bromide (THABr), 0.03 M THABr + 0.5 M NaBr, 0.03 M THABr + 0.5 M NaCl, 0.03 M THABr + 0.01 M sodium dodecyl sulfate (SDS), and 0.01 M cetyltrimethylammonium bromide (CTABr). N2O5 also reacts with glycerol itself to produce mono- and dinitroglycerin. Surface tension measurements indicate that 0.03 M THABr and 2.7 M NaBr have similar interfacial Br- concentrations, though their bulk Br- concentrations differ by 90-fold. We find that twice as much Br2 is produced in the presence of THA+, implying that the conversion of Br- to Br2 is initiated at the interface, perhaps mediated by the charged, hydrophobic pocket within the surface THA+ cation. The addition of 0.5 M NaBr, 0.5 M NaCl, or 0.01 M SDS to 0.03 M THABr lowers the Br2 production rate by 23%, 63%, and 67% of the THABr value, respectively. When CTA+ is substituted for THA+, Br2 production drops to 12% of the THABr value. The generation of Br2 under such different conditions implies that trace amounts of surface-active alkylammonium ions can catalyze interfacial N2O5 reactions, even when salts and other surfactants are present.

A controlling role for the air-sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer.

The lifetime of reactive nitrogen and the production rate of reactive halogens in the marine boundary layer are strongly impacted by reactions occurring at aqueous interfaces. Despite the potential importance of the air-sea interface in serving as a reactive surface, few direct field observations are available to assess its impact on reactive nitrogen deposition and halogen activation. Here, we present direct measurements of the vertical fluxes of the reactant-product pair N2O5 and ClNO2 to assess the role of the ocean surface in the exchange of reactive nitrogen and halogens. We measure nocturnal N2O5 exchange velocities (Vex = -1.66 ± 0.60 cm s(-1)) that are limited by atmospheric transport of N2O5 to the air-sea interface. Surprisingly, vertical fluxes of ClNO2, the product of N2O5 reactive uptake to concentrated chloride containing surfaces, display net deposition, suggesting that elevated ClNO2 mixing ratios found in the marine boundary layer are sustained primarily by N2O5 reactions with aerosol particles. Comparison of measured deposition rates and in situ observations of N2O5 reactive uptake to aerosol particles indicates that N2O5 deposition to the ocean surface accounts for between 26% and 42% of the total loss rate. The combination of large Vex, N2O5 and net deposition of ClNO2 acts to limit NOx recycling rates and the production of Cl atoms by shortening the nocturnal lifetime of N2O5. These results indicate that air-sea exchange processes account for as much as 15% of nocturnal NOx removal in polluted coastal regions and can serve to reduce ClNO2 concentrations at sunrise by over 20%.