Top-down versus bottom-up oxidation of a neonicotinoid pesticide by OH radicals.

Emerging contaminants (EC) distributed on surfaces in the environment can be oxidized by gas phase species (top-down) or by oxidants generated by the underlying substrate (bottom-up). One class of EC is the neonicotinoid (NN) pesticides that are widely distributed in air, water, and on plant and soil surfaces as well as on airborne dust and building materials. This study investigates the OH oxidation of the systemic NN pesticide acetamiprid (ACM) at room temperature. ACM on particles and as thin films on solid substrates were oxidized by OH radicals either from the gas phase or from an underlying TiO2 or NaNO2 substrate, and for comparison, in the aqueous phase. The site of OH attack is both the secondary >CH2 group as well as the primary -CH3 group attached to the tertiary amine nitrogen, with the latter dominating. In the case of top-down oxidation of ACM by gas phase OH radicals, addition to the -CN group also occurs. Major products are carbonyls and alcohols, but in the presence of sufficient water, their hydrolyzed products dominate. Kinetics measurements show ACM is more reactive toward gas phase OH radicals than other NN nitroguanidines, with an atmospheric lifetime of a few days. Bottom-up oxidation of ACM on TiO2 exposed to sunlight outdoors (temperatures were above 30 °C) was also shown to occur and is likely to be competitive with top-down oxidation. These findings highlight the different potential oxidation processes for EC and provide key data for assessing their environmental fates and toxicologies.

Implications for new particle formation in air of the use of monoethanolamine in carbon capture and storage.

Alkanolamines are currently being deployed in carbon capture and storage (CCS) technology worldwide, and atmospheric emissions have been found to coincide with locations exhibiting elevated concentrations of methanesulfonic acid (MSA). It is thus critical to understand the fate and potential atmospheric reactions of these chemicals. This study reports the characterization of sub-10 nm nanoparticles produced through the acid-base reaction between gas phase monoethanolamine (MEA) and MSA, a product of organosulfur compound oxidation in air, using a flow reactor under dry and humid (up to ∼60% RH) conditions. Number size distribution measurements show that MEA is even more efficient than methylamine in forming nanoparticles on reaction with MSA. This is attributed to the fact that the MEA structure contains both an -NH2 and an -OH group that facilitate hydrogen bonding within the clusters, in addition to the electrostatic interactions. Due to this already strong H-bond network, water has a relatively small influence on new particle formation (NPF) and growth in this system, in contrast to MSA reactions with alkylamines. Acid/base molar ratios of unity for 4-12 nm particles were measured using thermal desorption chemical ionization mass spectrometry. The data indicate that reaction of MEA with MSA may dominate NPF under some atmospheric conditions. Thus, the unique characteristics of alkanolamines in NPF must be taken into account for accurate predictions of impacts of CCS on visibility, health and climate.

Elucidating gas-surface interactions relevant to atmospheric particle growth using combined temperature programmed desorption and temperature-dependent uptake.

Understanding growth mechanisms for particles in air is fundamental to developing a predictive capability for their impacts on human health, visibility, and climate. In the case of highly viscous semi-solid or solid particles, the likelihood of impinging gases being taken up to grow the particle will be influenced by the initial uptake coefficient and by the residence time of the adsorbed gas on the surface. Here, a new approach that combines Knudsen cell capabilities for gas uptake measurements with temperature programmed desorption (TPD) for binding energy measurements of gases is described. The application of this unique capability to the uptake of organic gases on silica demonstrates its utility and the combination of thermodynamic and kinetic data that can be obtained. Lower limits to the initial net uptake coefficients at 170 K are (3.0 ± 0.6) × 10-3, (4.9 ± 0.6) × 10-3 and (4.3 ± 0.8) × 10-3 for benzene, 1-chloropentane, and methanol, respectively, and are reported here for the first time. The uptake data demonstrated that the ideal gas lattice model was appropriate, which informed the analysis of the TPD data. From the thermal desorption measurements, desorption energies of 34.6 ± 2.5, 45.8 ± 5.5, and 40.0 ± 5.6 kJ mol-1 (errors are 1σ) are obtained for benzene, 1-chloropentane, and methanol, respectively, and show good agreement with previously reported measurements. A multiphase kinetics model was applied to quantify uptake, desorption, and diffusion through the particle multilayers and hence extract desorption kinetics. Implications for uptake of organics on silica surfaces in the atmosphere and the utility of this system for determining relationships between residence times of organic gases and particle surfaces of varying composition are discussed in the context of developing quantitative predictions for growth of aerosol particles in air.

Peroxides on the Surface of Organic Aerosol Particles Using Matrix-Assisted Ionization in Vacuum (MAIV) Mass Spectrometry.

Organic peroxides are key intermediates in the atmosphere but are challenging to detect, especially in the particle phase, due to their instability, which has led to substantial gaps in the understanding of their environmental effects. We demonstrate that matrix-assisted ionization in vacuum (MAIV) mass spectrometry (MS), which does not require an ionization source, enables in situ characterization of peroxides and other products in the surface layers of organic particles. Hydroxyl radical oxidation of glutaric acid particles yields hydroperoxides and organic peroxides, which were detected with signals of the same order of magnitude as the major, more stable products. Product identification is supported by MS/MS analysis, peroxide standards, and offline high-resolution MS. The peroxide signals relative to the stable carbonyl and alcohol products are significantly larger using MAIV compared to those in the offline bulk analysis. This is also the case for analysis using fast, online easy ambient sonic-spray ionization mass spectrometry. These studies demonstrate the advantage of MAIV for the real-time characterization of labile peroxides in the surface layers of solid particles. The presence of peroxides on the surface may be important for surface oxidation processes as well as for the toxicity of inhaled particles.

Unexpected formation of oxygen-free products and nitrous acid from the ozonolysis of the neonicotinoid nitenpyram.

The neonicotinoid nitenpyram (NPM) is a multifunctional nitroenamine [(R1N)(R2N)C=CHNO2] pesticide. As a nitroalkene, it is structurally similar to other emerging contaminants such as the pharmaceuticals ranitidine and nizatidine. Because ozone is a common atmospheric oxidant, such compounds may be oxidized on contact with air to form new products that have different toxicity compared to the parent compounds. Here we show that oxidation of thin solid films of NPM by gas-phase ozone produces unexpected products, the majority of which do not contain oxygen, despite the highly oxidizing reactant. A further surprising finding is the formation of gas-phase nitrous acid (HONO), a species known to be a major photolytic source of the highly reactive hydroxyl radical in air. The results of application of a kinetic multilayer model show that reaction was not restricted to the surface layers but, at sufficiently high ozone concentrations, occurred throughout the film. The rate constant derived for the O3-NPM reaction is 1 × 10-18 cm3⋅s-1, and the diffusion coefficient of ozone in the thin film is 9 × 10-10 cm2⋅s-1 These findings highlight the unique chemistry of multifunctional nitroenamines and demonstrate that known chemical mechanisms for individual moieties in such compounds cannot be extrapolated from simple alkenes. This is critical for guiding assessments of the environmental fates and impacts of pesticides and pharmaceuticals, and for providing guidance in designing better future alternatives.

Gas Phase and Gas-Solid Interface Ozonolysis of Nitrogen Containing Alkenes: Nitroalkenes, Enamines, and Nitroenamines.

Emerging contaminants are of concern due to their rapidly increasing numbers and potential ecological and human health effects. In this study, the synergistic effects of the presence of multifunctional nitro, amino and carbon-carbon double bond (C═C) groups on the gas phase ozonolysis in O2 or at the air/solid interface were investigated using five simple model compounds. The gas phase ozonolysis rate constants at 296 K were (3.5 ± 0.9) × 10-20 cm3 molecule-1 s-1 for 2-methyl-1-nitroprop-1-ene and (6.8 ± 0.8) × 10-19 cm3 molecule-1 s-1 for 4-methyl-4-nitro-1-pentene, with lifetimes of 134 and 7 days in the presence of 100 ppb ozone in the atmosphere, respectively. The rate constants for gas phase E-N,N-dimethyl-1-propenylamine and N,N-dimethylallylamine reactions with ozone were too fast (>10-18 cm3 molecule-1 s-1) to be measured, implying lifetimes of less than 5 days. A multiphase kinetics model (KM-GAP) was used to probe the gas-solid kinetics of 1-dimethylamino-2-nitroethylene, yielding a rate constant for the surface reaction of 1.8 × 10-9 cm2 molecule-1 s-1 and in the bulk 1× 10-16 cm3 molecule-1 s-1. These results show that a nitro group attached to the C═C lowers the gas phase rate constant by 2-3 orders of magnitude compared to the simple alkenes, while amino groups have the opposite effect. The presence of both groups provides counterbalancing effects. Products with deleterious health effects including dimethylformamide and formaldehyde were identified by FTIR. The identified products differentiate whether the initial site of ozone attack is C═C and/or the amino group. This study provides a basis for predicting the environmental fates of emerging contaminants and shows that both the toxicity of both the parent compounds and the products should be taken into account in assessing their environmental impacts.

Novel ionization reagent for the measurement of gas-phase ammonia and amines using a stand-alone atmospheric pressure gas chromatography (APGC) source.

RATIONALE: Contaminants present in ambient air or in sampling lines can interfere with the target analysis through overlapping peaks or causing a high background. This study presents a positive outcome from the unexpected presence of N-methyl-2-pyrrolidone, released from a PALL HEPA filter, in the analysis of atmospherically relevant gas-phase amines using chemical ionization mass spectrometry. METHODS: Gas-phase measurements were performed using a triple quadrupole mass spectrometer equipped with a modified atmospheric pressure gas chromatography (APGC) source which allows sampling of the headspace above pure amine standards. Gas-phase N-methyl-2-pyrrolidone (NMP) emitted from a PALL HEPA filter located in the inlet stream served as the ionizing agent. RESULTS: This study demonstrates that some alkylamines efficiently form a [NMP + amine+H]+ cluster with NMP upon chemical ionization at atmospheric pressure. The extent of cluster formation depends largely on the proton affinity of the amine compared with that of NMP. Aromatic amines (aniline, pyridine) and diamines (putrescine) were shown not to form cluster ions with NMP. CONCLUSIONS: The use of NMP as an ionizing agent with stand-alone APGC provided high sensitivity for ammonia and the smaller amines. The main advantages, in addition to sensitivity, are direct sampling into the APGC source and avoiding uptake on sampling lines which can be a significant problem with ammonia and amines.

Photochemistry of Solid Films of the Neonicotinoid Nitenpyram.

The environmental fates of nitenpyram (NPM), a widely used neonicotinoid insecticide, are not well-known. A thin solid film of NPM deposited on a germanium attenuated total reflectance (ATR) crystal was exposed to radiation from a low-pressure mercury lamp at 254 nm, or from broadband low pressure mercury photolysis lamps centered at 350 or 313 nm. The loss during photolysis was followed in time using FTIR. The photolysis quantum yields (ϕ), defined as the number of NPM molecules lost per photon absorbed, were determined to be (9.4 ± 1.5) × 10-4 at 350 nm, (1.0 ± 0.3) × 10-3 at 313 nm, and (1.2 ± 0.4) × 10-2 at 254 nm (±2σ). Imines, one with a carbonyl group, were detected as surface-bound products and gaseous N2O was generated in low (11%) yield. The UV-vis absorption spectra of NPM in water was different from that in acetonitrile, dichloromethane, and methanol, or in a thin solid film. The photolytic lifetime of solid NPM at a solar zenith angle at 35° is calculated to be 36 min, while that for NPM in water is 269 min, assuming that the quantum yield is the same as in the solid. Thus, there may be a significant sensitivity to the medium for photolytic degradation and the lifetime of NPM in the environment.

Uptake of water by an acid-base nanoparticle: theoretical and experimental studies of the methanesulfonic acid-methylamine system.

The effect of water on the growth of dry nano-size acid-base particles is not yet known. In this paper, we investigate the uptake of water by nano-size particles composed of methanesulfonic acid (MSA) and methylamine (MA) using a combination of quantum chemical calculations and laboratory experiments. Calculations were performed on the (MSA-MA)4 cluster as the dry nanoparticle model, which forms a pseudo-cubic structure, to which twelve water molecules were added successively. Theoretical results show that the hydrated clusters (MSA-MA)4-(H2O)n, n = 1 to 12 are thermodynamically stable. In ab initio dynamic simulations, no loss of water or significant changes of structure are seen for at least 10 picoseconds. In all the clusters studied, most of the water molecules lie on the face of the (MSA-MA)4 initial dry unit, and water is found to be incorporated inside the initial unit for n ranging from five to twelve. Sizes of hydrated clusters exceed significantly that of the dry cluster only for n ≥ 6. These theoretical results suggest that dry MSA-MA clusters cannot dissociate in small quantities of water. Calculations of hydrated cluster distributions at steady state show that the cluster compositions studied, with up to 12 water molecules, encompass all the hydrated clusters under the experimental conditions (RH ∼ 19%, 300 K). Experiments performed in a glass flow reactor showed no changes in size or number concentration when particles formed from MSA-MA were subsequently exposed to water vapor, in contrast to increases in both size and number when water was present during particle formation. Thus, the results seem to imply for both experiment and theory that growth in size of a particle due to uptake of water requires the previous presence of some level of hydration. These results illustrate the importance for atmospheric models of understanding on a molecular basis the mechanisms of particle formation in air.

The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions.

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

Introductory lecture: atmospheric chemistry in the Anthropocene.

The term "Anthropocene" was coined by Professor Paul Crutzen in 2000 to describe an unprecedented era in which anthropogenic activities are impacting planet Earth on a global scale. Greatly increased emissions into the atmosphere, reflecting the advent of the Industrial Revolution, have caused significant changes in both the lower and upper atmosphere. Atmospheric reactions of the anthropogenic emissions and of those with biogenic compounds have significant impacts on human health, visibility, climate and weather. Two activities that have had particularly large impacts on the troposphere are fossil fuel combustion and agriculture, both associated with a burgeoning population. Emissions are also changing due to alterations in land use. This paper describes some of the tropospheric chemistry associated with the Anthropocene, with emphasis on areas having large uncertainties. These include heterogeneous chemistry such as those of oxides of nitrogen and the neonicotinoid pesticides, reactions at liquid interfaces, organic oxidations and particle formation, the role of sulfur compounds in the Anthropocene and biogenic-anthropogenic interactions. A clear and quantitative understanding of the connections between emissions, reactions, deposition and atmospheric composition is central to developing appropriate cost-effective strategies for minimizing the impacts of anthropogenic activities. The evolving nature of emissions in the Anthropocene places atmospheric chemistry at the fulcrum of determining human health and welfare in the future.

A cautionary note on the effects of laboratory air contaminants on ambient ionization mass spectrometry measurements.

RATIONALE: Ambient ionization mass spectrometry methods are convenient, sensitive and require little sample preparation. However, they are susceptible to species present in air surrounding the mass spectrometer. This study identifies some challenges associated with the potential impacts of indoor air contaminants on ionization and analysis involving open-air methods. METHODS: Unexpected effects of volatile organic compounds (VOCs) from floor maintenance activities on ambient ionization mass spectrometry were studied using three different ambient ionization techniques. Extractive electrospray ionization (EESI), direct analysis in real time (DART) and ionization by piezoelectric direct discharge (PDD) plasma were demonstrated in this study to be affected by indoor air contaminants. Identification of contaminant vapors was verified by comparison with standards using EESI-MS/MS product ion scans. RESULTS: Emissions of diethylene glycol monoethyl ether and ethylene glycol monobutyl ether are identified from floor stripping and waxing solutions using three ambient ionization mass spectrometry techniques. These unexpected indoor air contaminants are capable of more than 75% ion suppression of target analytes due to their high volatility, proton affinity and solubility compared with the target analytes. The contaminant vapors are also shown to form adducts with one of the target analytes. CONCLUSIONS: The common practice in MS analysis of subtracting a background air spectrum may not be appropriate if the presence of ionizable air contaminants alters the spectrum in unexpected ways. For example, VOCs released into air from floor stripping and waxing are capable of causing ion suppression of target analytes.

New Particle Formation from Methanesulfonic Acid and Amines/Ammonia as a Function of Temperature.

Previous studies have shown that methanesulfonic acid (MSA) reacts with amines and ammonia to form particles, which is expected to be particularly important in coastal and agricultural areas. We present the first systematic study of temperature dependence of particle formation from the reactions of MSA with trimethylamine (TMA), dimethylamine (DMA), methylamine (MA), and ammonia over the range of 21-28 °C and 0.4-5.9 s in a flow reactor under dry conditions and in the presence of 3 × 1017 cm-3 water vapor. Overall activation energies (Eoverall) for particle formation calculated from the dependence of rates of particle formation on temperature for all of these bases are negative. The negative Eoverall is interpreted in terms of reverse reactions that decompose intermediate clusters in competition with the forward reactions that grow the clusters into particles. The average values of Eoverall for the formation of detectable particles are: TMA, -(168 ± 19) kcal mol-1; DMA, -(134 ± 30) kcal mol-1; MA, -(68 ± 23) kcal mol-1; NH3, -(110 ± 16) kcal mol-1 (±1σ). The strong inverse dependence of particle formation with temperature suggests that particle formation may not decline proportionally with concentrations of MSA and amines if temperature also decreases, for example at higher altitudes or in winter.

The Role of Oxalic Acid in New Particle Formation from Methanesulfonic Acid, Methylamine, and Water.

Atmospheric particles are notorious for their effects on human health and visibility and are known to influence climate. Though sulfuric acid and ammonia/amines are recognized as main contributors to new particle formation (NPF), models and observations have indicated that other species may be involved. It has been shown that nucleation from methanesulfonic acid (MSA) and amines, which is enhanced with added water, can also contribute to NPF. While organics are ubiquitous in air and likely to be involved in NPF by stabilizing small clusters for further growth, their effects on the MSA-amine system are not known. This work investigates the effect of oxalic acid (OxA) on NPF from the reaction of MSA and methylamine (MA) at 1 atm and 294 K in the presence and absence of water vapor using an aerosol flow reactor. OxA and MA do not efficiently form particles even in the presence of water, but NPF is enhanced when adding MSA to OxA-MA with and without water. The addition of OxA to MSA-MA mixtures yields a modest NPF enhancement, whereas the addition of OxA to MSA-MA-H2O has no effect. Possible reasons for these effects are discussed.

Photochemistry of Thin Solid Films of the Neonicotinoid Imidacloprid on Surfaces.

Imidacloprid (IMD) is the most widely used neonicotinoid insecticide found on environmental surfaces and in water. Analysis of surface-bound IMD photolysis products was performed using attenuated total reflectance Fourier transfer infrared (ATR-FTIR) analysis, electrospray ionization (ESI-MS), direct analysis in real time mass spectrometry (DART-MS), and transmission FTIR for gas-phase products. Photolysis quantum yields (ϕ) for loss of IMD were determined to be (1.6 ± 0.6) × 10-3 (1s) at 305 nm and (8.5 ± 2.1) × 10-3 (1s) at 254 nm. The major product is the imidacloprid urea derivative (IMD-UR, 84% yield), with smaller amounts of the desnitro-imidacloprid (DN-IMD, 16% yield) product, and gaseous nitrous oxide (N2O). Theoretical calculations show that the first step of the main mechanism is the photodissociation of NO2, which then recombines with the ground electronic state of IMD radical to form IMD-UR and N2O in a thermally driven process. The photolytic lifetime of IMD at a solar zenith angle of 35° is calculated to be 16 h, indicating the significant reaction of IMD over the course of a day. Desnitro-imidacloprid has been identified by others as having increased binding to target receptors compared to IMD, suggesting that photolysis on environmental surfaces increases toxicity.

Nanoparticles grown from methanesulfonic acid and methylamine: microscopic structures and formation mechanism.

Mechanisms of particle formation and growth in the atmosphere are of great interest due to their impacts on climate, health and visibility. However, the microscopic structures and related properties of the smallest nanoparticles are not known. In this paper we pursue computationally a microscopic description for the formation and growth of methanesulfonic acid (MSA) and methylamine (MA) particles under dry conditions. Energetic and dynamics simulations were used to assess the stabilities of proposed model structures for these particles. Density functional theory (DFT) and semi-empirical (PM3) calculations suggest that (MSA-MA)4 is a major intermediate in the growth process, with the dissociation energies, enthalpies and free energies indicating considerable stability for this cluster. Dynamics simulations show that this species is stable for at least 100 ps at temperatures up to 500 K, well above atmospheric temperatures. In order to reach experimentally detectable sizes (>1.4 nm), continuing growth is suggested to occur via clustering of (MSA-MA)4. The dimer (MSA-MA)4(MSA-MA)4 may be one of the smaller experimentally measured particles. Step by step addition of MSA to (MSA-MA)4, is also a likely potential growth mechanism when MSA is excess. In addition, an MSA-MA crystal is predicted to exist. These studies demonstrate that computations of particle structure and dynamics in the nano-size range can be useful for molecular level understanding of processes that grow clusters into detectable particles.

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

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.

Particle formation and growth from oxalic acid, methanesulfonic acid, trimethylamine and water: a combined experimental and theoretical study.

Atmospheric particles influence visibility, health and climate but the mechanisms of their formation from initial clusters and their growth to detectable particles remain largely unknown. Previous studies show that reactions of methanesulfonic acid (MSA) with ammonia and amines form particles, a process which is enhanced by water. We report here results from a combined experimental-theoretical investigation of the effect of oxalic acid (OxA) on particle formation and growth from the reaction of MSA with trimethylamine (TMA) in the absence and presence of water. The gas phase reactants were mixed in an aerosol flow reactor (1 atm, 294 K). Particle number concentrations and size distributions were measured as a function of reaction time from 0.8-12 s. The interaction of OxA with TMA with and without water does not lead to significant particle formation. When OxA is present during the reaction of MSA with TMA, there is little change (≤2 times more) in the particle number concentration but particles are larger compared to the base case of MSA with TMA alone. However, the presence of water with MSA and TMA overwhelms the effect of OxA so that OxA has no significant impact on particle number concentration or size. Results of these experiments suggest the MSA hydrate is important for particle formation and growth of the four component OxA-MSA-TMA-H2O system. These results are compared to earlier studies of the effect of OxA on the MSA-methylamine reaction and interpreted based on theoretically calculated properties of small clusters of the components.

Kinetics, mechanisms and ionic liquids in the uptake of n-butylamine onto low molecular weight dicarboxylic acids.

Atmospheric particles adversely affect visibility, health, and climate, yet the kinetics and mechanisms of particle formation and growth are poorly understood. Multiphase reactions between amines and dicarboxylic acids (diacids) have been suggested to contribute. In this study, the reactions of n-butylamine (BA) with solid C3-C8 diacids were studied at 296 ± 1 K using a Knudsen cell interfaced to a quadrupole mass spectrometer. Uptake coefficients for amines on the diacids with known geometric surface areas were measured at initial amine concentrations from (3-50) × 1011 cm-3. Uptake coefficients ranged from 0.7 ± 0.1 (2σ) for malonic acid (C3) to <10-6 for suberic acid (C8), show an odd-even carbon number effect, and decrease with increasing chain length within each series. Butylaminium salts formed from evaporation of aqueous solutions of BA with C3, C5 and C7 diacids (as well as C8) were viscous liquids, suggesting that ionic liquids (ILs) form on the surface during the reactions of gas phase amine with the odd carbon diacids. Predictions from the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) were quantitatively consistent with uptake occurring via dissolution of the underlying diacid into the IL layer and reaction with amine taken up from the gas phase. The butylaminium salts formed from the C4 and C6 diacids were solids, and their uptake coefficients were smaller. These experiments and kinetic modeling demonstrate the unexpected formation of ILs in a gas-solid reaction, and suggest that ILs should be considered under some circumstances in atmospheric processes.

Correction: New particle formation and growth from methanesulfonic acid, trimethylamine and water.

Correction for 'New particle formation and growth from methanesulfonic acid, trimethylamine and water' by Haihan Chen et al., Phys. Chem. Chem. Phys., 2015, 17, 13699-13709.