Non-linear photochemical pathways in laser induced atmospheric aerosol formation

We measured the chemical composition and the size distribution of aerosols generated by femtosecond-Terawatt laser pulses in the atmosphere using an aerosol mass spectrometer (AMS). We show that nitric acid condenses in the form of ammonium nitrate, and that oxidized volatile organics also contribute to particle growth. These two components account for two thirds and one third, respectively, of the dry laser-condensed mass. They appear in two different modes centred at 380 nm and 150 nm. The number concentration of particles between 25 and 300 nm increases by a factor of 15. Pre-existing water droplets strongly increase the oxidative properties of the laser-activated atmosphere, substantially enhancing the condensation of organics under laser illumination.Comment: 19 pages, 5 figure

Secondary organic aerosol formation from smoldering and flaming combustion of biomass: a box model parametrization based on volatility basis set

International audienceResidential wood combustion remains one of the most important sources of primary organic aerosols (POA) and secondary organic aerosol (SOA) precursors during winter. The overwhelming majority of these precursors have not been traditionally considered in regional models, and only recently were lignin pyrolysis products and polycyclic aro-matics identified as the principal SOA precursors from flam-ing wood combustion. The SOA yields of these components in the complex matrix of biomass smoke remain unknown and may not be inferred from smog chamber data based on single-compound systems. Here, we studied the ageing of emissions from flaming and smoldering-dominated wood fires in three different residential stoves, across a wide range of ageing temperatures (− 10, 2 and 15 • C) and emission loads. Organic gases (OGs) acting as SOA precursors were monitored by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), while the evolution of the aerosol properties during ageing in the smog chamber was monitored by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). We developed a novel box model based on the volatility basis set (VBS) to determine the volatility distributions of the oxidation products from different precursor classes found in the emissions, grouped according to their emission pathways and SOA production rates. We show for the first time that SOA yields in complex emissions are consistent with those reported in literature from single-compound systems. We identify the main SOA precursors in both flaming and smoldering wood combustion emissions at different temperatures. While single-ring and polycyclic aromatics are significant precursors in flam-ing emissions, furans generated from cellulose pyrolysis appear to be important for SOA production in the case of smoldering fires. This is especially the case at high loads and low temperatures, given the higher volatility of furan oxidation products predicted by the model. We show that the oxidation products of oxygenated aromatics from lignin pyrolysis are expected to dominate SOA formation, independent of the combustion or ageing conditions, and therefore can be used as promising markers to trace ageing of biomass smoke in the field. The model framework developed herein may be gener-alizable for other complex emission sources, allowing determination of the contributions of different precursor classes to SOA, at a level of complexity suitable for implementation in regional air quality models

Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra

Receptor modelling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada’s CRUISER mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach was compared to the more common method of analysing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulphate and oxygenated organic aerosol containing factor (Sulphate-OA); an ammonium nitrate and oxygenated organic aerosol containing factor (Nitrate-OA); an ammonium chloride containing factor (Chloride); a hydrocarbon like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analysing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case, an Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR-ToF-AMS data, due to the ability to better understand the chemical nature of atypical factors from high resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably re-solved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra

Indoor terpene emissions from cooking with herbs and pepper and their secondary organic aerosol production potential

Cooking is widely recognized as an important source of indoor and outdoor particle and volatile organic compound emissions with potential deleterious effects on human health. Nevertheless, cooking emissions remain poorly characterized. Here the effect of herbs and pepper on cooking emissions was investigated for the first time to the best of our knowledge using state of the art mass spectrometric analysis of particle and gas-phase composition. Further, the secondary organic aerosol production potential of the gas-phase emissions was determined by smog chamber aging experiments. The emissions of frying meat with herbs and pepper include large amounts of mono-, sesqui- and diterpenes as well as various terpenoids and p-cymene. The average total terpene emission rate from the use of herbs and pepper during cooking is estimated to be 46 ± 5 gg-1 Herbs min-1. These compounds are highly reactive in the atmosphere and lead to significant amounts of secondary organic aerosol upon aging. In summary we demonstrate that cooking with condiments can constitute an important yet overlooked source of terpenes in indoor air

Brown Carbon in Primary and Aged Coal Combustion Emission

Smog chamber experiments were conducted to characterize the light absorption of brown carbon (BrC) from primary and photochemically aged coal combustion emissions. Light absorption was measured by the UV-visible spectrophotometric analysis of water and methanol extracts of filter samples. The single-scattering albedo at 450 nm was 0.73 ± 0.10 for primary emissions and 0.75 ± 0.13 for aged emissions. The light absorption coefficient at 365 nm of methanol extracts was higher than that of water extracts by a factor of 10 for primary emissions and a factor of 7 for aged emissions. This suggests that the majority of BrC is water-insoluble even after aging. The mass absorption efficiency of this BrC (MAE365) for primary OA (POA) was dependent on combustion conditions, with an average of 0.84 ± 0.54 m2 g-1, which was significantly higher than that for aged OA (0.24 ± 0.18 m2 g-1). Secondary OA (SOA) dominated aged OA and the decreased MAE365 after aging indicates that SOA is less light absorbing than POA and/or that BrC is bleached (oxidized) with aging. The estimated MAE365 of SOA (0.14 ± 0.08 m2 g-1) was much lower than that of POA. A comparison of MAE365 of residential coal combustion with other anthropogenic sources suggests that residential coal combustion emissions are among the strongest absorbing BrC organics

Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber

We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of different emissions sources without limitation from the instruments or facilities available at any single site. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric aging of emissions may be simulated over a range of temperatures (-7 to 25°C). A photolysis rate of NO2, JNO2, of (8.0±0.7)×10-3 s-1 was determined at 25°C. We demonstrate the utility of this new system by presenting results on the aging (OH=12×106 cm-3h) of emissions from a modern (Euro 5) gasoline car operated during a driving cycle (New European Driving Cycle, NEDC) on a chassis dynamometer in a vehicle test cell. Emissions from the entire NEDC were sampled and aged in the chamber. A thorough investigation of the composition of the gas phase emissions suggests that the observed SOA is from previously unconsidered precursors and processes. This large enhancement in PM mass from gasoline vehicle aerosol emissions due to SOA formation, if it occurs across a wider range of gasoline vehicles, would have significant implications for our understanding of the contribution of on-road gasoline vehicles to ambient aerosols.JRC.F.8-Sustainable Transpor

Effects of aerosol size and coating thickness on the molecular detection using extractive electrospray ionization

Extractive electrospray ionization (EESI) has been a well-known technique for high-throughput online molecular characterization of chemical reaction products and intermediates, detection of native biomolecules, in vivo metabolomics, and environmental monitoring with negligible thermal and ionization-induced fragmentation for over two decades. However, the EESI extraction mechanism remains uncertain. Prior studies disagree on whether particles between 20 and 400nm diameter are fully extracted or if the extraction is limited to the surface layer. Here, we examined the analyte extraction mechanism by assessing the influence of particle size and coating thickness on the detection of the molecules therein. We find that particles are extracted fully: organics-coated NH4NO3 particles with a fixed core volume (156 and 226nm in diameter without coating) showed constant EESI signals for NH4NO3 independent of the shell coating thickness, while the signals of the secondary organic molecules comprising the shell varied proportionally to the shell volume. We also found that the EESI sensitivity exhibited a strong size dependence, with an increase in sensitivity by 1-3 orders of magnitude as particle size decreased from 300 to 30nm. This dependence varied with the electrospray (ES) droplet size, the particle size and the residence time for coagulation in the EESI inlet, suggesting that the EESI sensitivity was influenced by the coagulation coefficient between particles and ES droplets. Overall, our results indicate that, in the EESI, particles are fully extracted by the ES droplets regardless of the chemical composition, when they are collected by the ES droplets. However, their coalescence is not complete and depends strongly on their size. This size dependence is especially relevant when EESI is used to probe size-varying particles as is the case in aerosol formation and growth studies with size ranges below 100nm. © 2021 The Author(s)

Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry : Cooking Emissions

Cooking processes produce gaseous and particle emissions that are potentially deleterious to human health. Using a highly controlled experimental setup involving a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), we investigate the emission factors and the detailed chemical composition of gas phase emissions from a broad variety of cooking styles and techniques. A total of 95 experiments were conducted to characterize nonmethane organic gas (NMOG) emissions from boiling, charbroiling, shallow frying, and deep frying of various vegetables and meats, as well as emissions from vegetable oils heated to different temperatures. Emissions from boiling vegetables are dominated by methanol. Significant amounts of dimethyl sulfide are emitted from cruciferous vegetables. Emissions from shallow frying, deep frying and charbroiling are dominated by aldehydes of differing relative composition depending on the oil used. We show that the emission factors of some aldehydes are particularly large which may result in considerable negative impacts on human health in indoor environments. The suitability of some of the aldehydes as tracers for the identification of cooking emissions in ambient air is discussed