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

Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA

Secondary organic aerosol (SOA) is an important contributor to fine particulate matter (PM) mass in polluted regions, and its modeling remains poorly constrained. A box model is developed that uses recently published literature parameterizations and data sets to better constrain and evaluate the formation pathways and precursors of urban SOA during the CalNex 2010 campaign in Los Angeles. When using the measurements of intermediate-volatility organic compounds (IVOCs) reported in Zhao et al. (2014) and of semivolatile organic compounds (SVOCs) reported in Worton et al. (2014) the model is biased high at longer photochemical ages, whereas at shorter photochemical ages it is biased low, if the yields for VOC oxidation are not updated. The parameterizations using an updated version of the yields, which takes into account the effect of gas-phase wall losses in environmental chambers, show model–measurement agreement at longer photochemical ages, even though some low bias at short photochemical ages still remains. Furthermore, the fossil and non-fossil carbon split of urban SOA simulated by the model is consistent with measurements at the Pasadena ground site. Multi-generation oxidation mechanisms are often employed in SOA models to increase the SOA yields derived from environmental chamber experiments in order to obtain better model–measurement agreement. However, there are many uncertainties associated with these aging mechanisms. Thus, SOA formation in the model is compared to data from an oxidation flow reactor (OFR) in order to constrain SOA formation at longer photochemical ages than observed in urban air. The model predicts similar SOA mass at short to moderate photochemical ages when the aging mechanisms or the updated version of the yields for VOC oxidation are implemented. The latter case has SOA formation rates that are more consistent with observations from the OFR though. Aging mechanisms may still play an important role in SOA chemistry, but the additional mass formed by functionalization reactions during aging would need to be offset by gasphase fragmentation of SVOCs. All the model cases evaluated in this work show a large majority of the urban SOA (70–83 %) at Pasadena coming from the oxidation of primary SVOCs (P-SVOCs) and primary IVOCs (P-IVOCs). The importance of these two types of precursors is further supported by analyzing the percentage of SOA formed at long photochemical ages (1.5 days) as a function of the precursor rate constant. The P-SVOCs and P-IVOCs have rate constants that are similar to highly reactive VOCs that have been previously found to strongly correlate with SOA formation potential measured by the OFR. Finally, the volatility distribution of the total organic mass (gas and particle phase) in the model is compared against measurements. The total SVOC mass simulated is similar to the measurements, but there are important differences in the measured and modeled volatility distributions. A likely reason for the difference is the lack of particle-phase reactions in the model that can oligomerize and/or continue to oxidize organic compounds even after they partition to the particle phase

Chemical characterization of secondary organic aerosol at a rural site in the southeastern US: insights from simultaneous high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and FIGAERO chemical ionization mass spectrometer (CIMS) measurements

The formation and evolution of secondary organic aerosol (SOA) were investigated at Yorkville, GA, in late summer (mid-August to mid-October 2016). The organic aerosol (OA) composition was measured using two online mass spectrometry instruments, the high-resolution time-of-flight aerosol mass spectrometer (AMS) and the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct chemical ionization mass spectrometer (FIGAERO-CIMS). Through analysis of speciated organics data from FIGAERO-CIMS and factorization analysis of data obtained from both instruments, we observed notable SOA formation from isoprene and monoterpenes during both day and night. Specifically, in addition to isoprene epoxydiol (IEPOX) uptake, we identified isoprene SOA formation from non-IEPOX pathways and isoprene organic nitrate formation via photooxidation in the presence of NO_x and nitrate radical oxidation. Monoterpenes were found to be the most important SOA precursors at night. We observed significant contributions from highly oxidized acid-like compounds to the aged OA factor from FIGAERO-CIMS. Taken together, our results showed that FIGAERO-CIMS measurements are highly complementary to the extensively used AMS factorization analysis, and together they provide more comprehensive insights into OA sources and composition

Chemical characterization of secondary organic aerosol at a rural site in the southeastern US: insights from simultaneous high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and FIGAERO chemical ionization mass spectrometer (CIMS) measurements

The formation and evolution of secondary organic aerosol (SOA) were investigated at Yorkville, GA, in late summer (mid-August to mid-October 2016). The organic aerosol (OA) composition was measured using two online mass spectrometry instruments, the high-resolution time-of-flight aerosol mass spectrometer (AMS) and the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct chemical ionization mass spectrometer (FIGAERO-CIMS). Through analysis of speciated organics data from FIGAERO-CIMS and factorization analysis of data obtained from both instruments, we observed notable SOA formation from isoprene and monoterpenes during both day and night. Specifically, in addition to isoprene epoxydiol (IEPOX) uptake, we identified isoprene SOA formation from non-IEPOX pathways and isoprene organic nitrate formation via photooxidation in the presence of NO_x and nitrate radical oxidation. Monoterpenes were found to be the most important SOA precursors at night. We observed significant contributions from highly oxidized acid-like compounds to the aged OA factor from FIGAERO-CIMS. Taken together, our results showed that FIGAERO-CIMS measurements are highly complementary to the extensively used AMS factorization analysis, and together they provide more comprehensive insights into OA sources and composition

Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland

Time and size resolved data of trace elements were obtained from measurements with a rotating drum impactor (RDI) and subsequent X-ray fluorescence spectrometry. Trace elements can act as indicators for the identification of sources of particulate matter <10 μm (PM10) in ambient air. Receptor modeling was performed with positive matrix factorization (PMF) for trace element data from an urban background site in Zürich, Switzerland. Eight different sources were identified for the three examined size ranges (PM1-0.1, PM2.5-1 and PM 10-2.5): secondary sulfate, wood combustion, fire works, road traffic, mineral dust, de-icing salt, industrial and local anthropogenic activities. The major component was secondary sulfate for the smallest size range; the road traffic factor was found in all three size ranges. This trace element analysis is complemented with data from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS), assessing the PM1 fraction of organic aerosols. A separate PMF analysis revealed three factors related to three of the sources found with the RDI: oxygenated organic aerosol (OOA, related to inorganic secondary sulfate), hydrocarbon-like organic aerosol (HOA, related to road traffic) and biomass burning organic aerosol (BBOA), explaining 60 %, 22 % and 17 % of total measured organics, respectively. Since different compounds are used for the source classification, a higher percentage of the ambient PM10 mass concentration can be apportioned to sources by the combination of both methods. © 2011 Author(s)

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

Contributions of residential coal combustion to the air qualityin Beijing–Tianjin–Hebei (BTH), China: a case study

In the present study, the WRF-Chem model is used to assess contributions of residential coal combustion (RCC) emissions to the air quality in Beijing-Tianjin-Hebei (BTH) during a persistent air pollution episode from 9 to 25 January 2014. In general, the predicted temporal variations and spatial distributions of the mass concentrations of air pollutants are in good agreement with observations at monitoring sites in BTH. The WRF-Chem model also reasonably reproduces the temporal variations in aerosol species when compared with the aerosol mass spectrometer measurements in Beijing. The RCC emissions play an important role in the haze formation in BTH, contributing about 23.1% of PM2.5 (fine particulate matter) and 42.6% of SO2 during the simulation period on average. Organic aerosols dominate the PM2.5 from the RCC emissions in BTH, with a contribution of 42.8 %, followed by sulfate (17.1 %). The air quality in Beijing is remarkably improved when the RCC emissions in BTH and the surrounding areas are excluded in model simulations, with a 30% decrease in PM2.5 mass concentrations. However, if only the RCC emissions in Beijing are excluded, the local PM2.5 mass concentration is decreased by 18.0% on average. Our results suggest that the implementation of the residential coal replacement by clean energy sources in Beijing is beneficial to the local air quality. Should residential coal replacement be carried out in BTH and its surrounding areas, the air quality in Beijing would be improved remarkably. Further studies would need to consider uncertainties in the emission inventory and meteorological fields