Matthew L. Dawson

Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

Airborne particles affect human health and significantly influence visibility and climate. A major fraction of these particles result from the reactions of gaseous precursors to generate low-volatility products such as sulfuric acid and high-molecular weight organics that nucleate to form new particles. Ammonia and, more recently, amines, both of which are ubiquitous in the environment, have also been recognized as important contributors. However, accurately predicting new particle formation in both laboratory systems and in air has been problematic. During the oxidation of organosulfur compounds, gas-phase methanesulfonic acid is formed simultaneously with sulfuric acid, and both are found in particles in coastal regions as well as inland. We show here that: (i) Amines form particles on reaction with methanesulfonic acid, (ii) water vapor is required, and (iii) particle formation can be quantitatively reproduced by a semiempirical kinetics model supported by insights from quantum chemical calculations of likely intermediate clusters. Such an approach may be more broadly applicable in models of outdoor, indoor, and industrial settings where particles are formed, and where accurate modeling is essential for predicting their impact on health, visibility, and climate.

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

Significance Sulfur dioxide (SO2) via its oxidation to sulfuric acid is a major source of airborne particles, which impact visibility, health, and climate. Sources of SO2 include the combustion of sulfur-containing fossil fuels and the oxidation of organosulfur compounds (OSCs) such as dimethyl sulfide. We show that as fossil fuel combustion is phased out in an urban coastal area, particle formation will decrease substantially but still continue at a reduced rate due to the contribution from OSC oxidation products. Furthermore, methanesulfonic acid generated simultaneously in OSC oxidation will become a significant contributor to particle formation, which should be taken into account in predictive models of air pollution and climate and may be especially important in agricultural areas with significant OSC sources. 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.

Analysis of secondary organic aerosols in air using extractive electrospray ionization mass spectrometry (EESI-MS)

Extractive electrospray ionization mass spectrometry (EESI-MS) has been shown, in other laboratories, to be a useful technique for the analysis of aerosols from a variety of sources. EESI-MS is applied here, for the first time, to the analysis of secondary organic aerosol (SOA) formed from the reaction of ozone and α-pinene. The results are compared to those obtained using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The SOA was generated in the laboratory and merged with electrospray droplets. The recovered ions were directed towards the inlet of a triple quadrupole mass spectrometer. Through the use of a denuder to remove gas phase compounds, the EESI-MS technique was found to be effective for measuring the major ozonolysis products either in particles alone or in a combination of vapor phase and particulate products. Due to its relatively simple setup and the avoidance of sample collection and work-up, EESI-MS shows promise as an excellent tool for the characterization of atmospherically relevant particles.

Surprising formation of p-cymene in the oxidation of α-pinene in air by the atmospheric oxidants OH, O3, and NO3.

Anthropogenic sources release into the troposphere a wide range of volatile organic compounds (VOCs) including aromatic hydrocarbons, whose major sources are believed to be combustion and the evaporation of fossil fuels. An important question is whether there are other sources of aromatics in air. We report here the formation of p-cymene [1-methyl-4-(1-methylethyl) benzene, C6H4(CH3)(C3H7)] from the oxidation of α-pinene by OH, O3, and NO3 at 1 atm in air and 298 K at low (<5%) and high (70%) relative humidities (RH). Loss of α-pinene and the generation of p-cymene were measured using GC-MS. The fractional yields of p-cymene relative to the loss of α-pinene, Δ [p-cymeme]/Δ [α-pinene], were measured to range from (1.6±0.2)×10(-5) for the O3 reaction to (3.0±0.3)×10(-4) for the NO3 reaction in the absence of added water vapor. The yields for the OH and O3 reactions increased by a factor of 4-8 at 70% RH (uncertainties are ±2s). The highest yields at 70% RH for the OH and O3 reactions, ∼15 times higher than for dry conditions, were observed if the walls of the Teflon reaction chamber had been previously exposed to H2SO4 formed from the OH oxidation of SO2. Possible mechanisms of the conversion of α-pinene to p-cymene and the potential importance in the atmosphere are discussed.

Infrared Studies of the Reaction of Methanesulfonic Acid with Trimethylamine on Surfaces

Organosulfur compounds generated from a variety of biological as well as anthropogenic sources are oxidized in air to form sulfuric acid and methanesulfonic acid (MSA). Both of these acids formed initially in the gas phase react with ammonia and amines in air to form and grow new particles, which is important for visibility, human health and climate. A competing sink is deposition on surfaces in the boundary layer. However, relatively little is known about reactions after they deposit on surfaces. We report here diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) studies of the reaction of MSA with trimethylamine (TMA) on a silicon powder at atmospheric pressure in synthetic air and at room temperature, either in the absence or in the presence of water vapor. In both cases, DRIFTS spectra of the product surface species are essentially the same as the transmission spectrum obtained for trimethylaminium methanesulfonate, indicating the formation of the salt on the surface with a lower limit to the reaction probability of γ > 10(-6). To the best of our knowledge, this is the first infrared study to demonstrate this chemistry from the heterogeneous reaction of MSA with an amine on a surface. This heterogeneous chemistry appears to be sufficiently fast that it could impact measurements of gas-phase amines through reactions with surface-adsorbed acids on sampling lines and inlets. It could also represent an additional sink for amines in the boundary layer, especially at night when the gas-phase reactions of amines with OH radical and ozone are minimized.

Simulated sensitivity of secondary organic aerosol in the South Coast Air Basin of California to nitrogen oxides and other chemical parameters

ABSTRACT Sensitivity of secondary organic aerosol (SOA) concentrations in the South Coast Air Basin (SoCAB) of California to nitrogen oxide (NOx) emission is simulated using gas-phase chemistry and gas-particle partitioning modules. These modules are implemented into a three-dimensional air quality model applied for high-pollution summer meteorology and 2008 emissions. To test sensitivity, NOx emissions in all locations and at all times are scaled by factors ranging from 0.1 to 10.0 in separate model runs. The basin-wide average SOA concentration exhibits a ‘turnover’ NOx emission multiplicative factor, above and below which the average SOA concentration decreases. For the entire SoCAB, this critical NOx emission factor is ∼0.3; while the magnitude of SOA concentrations changes with time, this peak value (∼0.2–0.3) appears to be relatively independent of the hour of the simulated day. When considering individual locations within the SoCAB, this peak factor shows a slightly broader range. Projected emissions for 2023 indicate a decrease in basin-average SOA concentration; the response at individual locations, however, can be either positive or negative, indicating the need for location-specific considerations. Ensembles of module simulations based on parameter values selected using efficient sampling techniques (Latin Hypercube method) are used to identify parameters to which SOA predictions are significantly sensitive. Total SOA predictions are most sensitive (in no particular order) to concentrations of O3, unsaturated species formed from the gas-phase oxidation of monoaromatic compounds, and substituted products from long-chain alkane oxidation. Secondary inorganic aerosol species, likely through influencing aerosol liquid water, control at least partially the formation of SOA upwind. In addition, the rate at which unsaturated bicyclic oxidation products of monoaromatic compounds are oxidized by hydroxyl radical impacts significantly SOA prediction. These findings emphasize the need for consideration of long-chain alkanes and monoaromatic species when designing emission control strategies.

New particle formation and growth from methanesulfonic acid, trimethylamine and water (vol 17, pg 13699, 2015)

PCCP View Article Online CORRECTION Cite this: Phys. Chem. Chem. Phys., DOI: 10.1039/c7cp90021j View Journal | View Issue Correction: New particle formation and growth from methanesulfonic acid, trimethylamine and water Haihan Chen, Michael J. Ezell, Kristine D. Arquero, Mychel E. Varner, Matthew L. Dawson, R. Benny Gerber and Barbara J. Finlayson-Pitts* 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. rsc.li/pccp In the above paper, particle formation from the reaction of methanesulfonic acid (MSA) with trimethylamine (TMA) was reported. In these studies, a cylinder containing a custom mixture of TMA in air from a commercial gas supplier was used. Recent work in this laboratory 1 shows significantly less particle formation from the MSA–TMA reaction when the gas phase TMA is generated using a permeation tube where NH 3 was not detected, and where the detection limits for NH 3 were at least an order of magnitude smaller than those in the earlier work. We believe that the higher rates of particle formation reported earlier are due to the presence of some unknown contaminants (likely NH 3 at concentrations lower than the detection limit of a less sensitive instrument used for analysis at that time) in the commercial custom mixture. We have confirmed in separate experiments that particles formed by reaction of MSA with TMA from permeation tubes increased significantly upon addition of NH 3 . This does not change the conclusions of the paper that the MSA–TMA reaction forms particles, that water increases particle formation in this system and that this reaction is likely to occur in air. It does, however, provide a cautionary note on the quality and reliability of gas mixtures of amines from commercial gas suppliers. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers. References 1 H. Chen and B. J. Finlayson-Pitts, Environ. Sci. Technol., 2017, 51, 243–252. Department of Chemistry, University of California, Irvine, Irvine, CA 92697, USA. E-mail: bjfinlay@uci.edu; Fax: +1 949 824 2420; Tel: +1 949 824 7670 This journal is