Gaseous emissions from brake wear can form secondary particulate matter.

Road traffic is an important source of urban air pollutants. Due to increasingly strict controls of exhaust emissions from road traffic, their contribution to the total emissions has strongly decreased over time in high-income countries. In contrast, non-exhaust emissions from road vehicles are not yet legislated and now make up the major proportion of road traffic emissions in many countries. Brake wear, which occurs due to friction between brake linings and their rotating counterpart, is one of the main non-exhaust sources contributing to particle emissions. Since the focus of brake wear emission has largely been on particulate pollutants, little is currently known about gaseous emissions such as volatile organic compounds from braking and their fate in the atmosphere. This study investigates the oxidative ageing of gaseous brake wear emissions generated with a pin-on-disc tribometer, using an oxidation flow reactor. The results demonstrate, for the first time, that the photooxidation of gaseous brake wear emissions can lead to formation of secondary particulate matter, which could amplify the environmental impact of brake wear emissions.

Obscured Contribution of Oxygenated Intermediate-Volatility Organic Compounds to Secondary Organic Aerosol Formation from Gasoline Vehicle Emissions.

Secondary organic aerosol (SOA) formation from gasoline vehicles spanning a wide range of emission types was investigated using an oxidation flow reactor (OFR) by conducting chassis dynamometer tests. Aided by advanced mass spectrometric techniques, SOA precursors, including volatile organic compounds (VOCs) and intermediate/semivolatile organic compounds (I/SVOCs), were comprehensively characterized. The reconstructed SOA produced from the speciated VOCs and I/SVOCs can explain 69% of the SOA measured downstream of an OFR upon 0.5-3 days' OH exposure. While VOCs can only explain 10% of total SOA production, the contribution from I/SVOCs is 59%, with oxygenated I/SVOCs (O-I/SVOCs) taking up 20% of that contribution. O-I/SVOCs (e.g., benzylic or aliphatic aldehydes and ketones), as an obscured source, account for 16% of total nonmethane organic gas (NMOG) emission. More importantly, with the improvement in emission standards, the NMOG is effectively mitigated by 35% from China 4 to China 6, which is predominantly attributed to the decrease of VOCs. Real-time measurements of different NMOG components as well as SOA production further reveal that the current emission control measures, such as advances in engine and three-way catalytic converter (TWC) techniques, are effective in reducing the "light" SOA precursors (i.e., single-ring aromatics) but not for the I/SVOC emissions. Our results also highlight greater effects of O-I/SVOCs to SOA formation than previously observed and the urgent need for further investigation into their origins, i.e., incomplete combustion, lubricating oil, etc., which requires improvements in real-time molecular-level characterization of I/SVOC molecules and in turn will benefit the future design of control measures.

Study of secondary organic aerosol formation and aging using ambient air in an oxidation flow reactor during high pollution events over Delhi.

Secondary aerosols constitute a significant fraction of atmospheric aerosols, yet our understanding of their formation mechanism and fate is very limited. In this work, the secondary organic aerosol (SOA) formation and aging of ambient air of Delhi are studied using a potential aerosol mass (PAM) reactor, an oxidation flow reactor (OFR), coupled with aerosol chemical speciation monitor (ACSM), proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS), and scanning mobility particle sizer with counter (SMPS + C). The setup mimics atmospheric aging of up to several days with the generation of OH radicals. Variations in primary volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) as a function of photochemical age were investigated. Primary VOCs such as benzene, toluene, xylene, trimethyl benzene, etc. decrease and OVOCs like formic acid, formaldehyde, acetone, ethanol, etc. increase substantially upon oxidation in OFR. The highest organic aerosol (OA) enhancement was observed for the 4.2 equivalent photochemical days of aging i.e., 1.84 times the ambient concentration, and net OA loss was observed at very high OH exposure, typically after 8.4 days of photochemical aging due to heterogeneous oxidation followed by fragmentation/evaporation. In ambient air, OA enhancement is highest during nighttime due to the high concentrations of precursor VOCs in the atmosphere. SMPS + C results demonstrated substantial new particle formation upon aging and decrement in preexisting aerosol mass. This is the first experimental study conducting an in-situ evaluation of potential SOA mass generated from the ambient aerosols in India.

Combined Smog Chamber/Oxidation Flow Reactor Study on Aging of Secondary Organic Aerosol from Photooxidation of Aromatic Hydrocarbons.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 µg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.

Toxicity of fresh and aged anthropogenic smoke particles emitted from different burning conditions.

There is substantial evidence that photochemical reactions in the atmosphere cause physico-chemical transformation of combustion smoke, but how this processing modifies potential health effects in exposed populations is not well understood. Here we utilized a new approach to simulate photochemical aging of anthropogenic smoke emissions (a mixture of plastic, plywood, and cardboard smoke) from two different burning conditions (smoldering vs. flaming) and investigated their adverse outcomes associated with mutagenic activity and the relative potencies of different polycyclic aromatic hydrocarbons (PAHs). Aging resulted in increased oxygenated volatile organic compound (VOC) emissions but largely degraded particle-bound PAH components in the smoke. Chemical transformation during aging was more dramatic for flaming versus smoldering smoke. Due to the PAH degradation, mutagenicity of the aged smoke from flaming combustion was much lower (up to 4 times) than that of the fresh smoke on per-particle mass basis. However, on the basis of particle emitted per fuel mass burned, the aged and fresh smoke particles exhibited similar mutagenic activities, which were up to 3 times higher for smoldering versus flaming smoke emissions. Similarly, the PAH toxicity equivalent (PAH-TEQ) of the aged smoldering smoke was 3 times higher than that of the aged flaming smoke particles, suggesting that some PAHs (e.g., indeno[c,d]pyrene and benzo[b]fluoranthene) in the smoldering smoke were more photochemically stable during aging. These findings increase understanding of the evolution of smoke emitted at different burning conditions and the role of photochemical transformations on mutagenicity and PAH-induced toxicity.

Real time measurements of the secondary organic aerosol formation and aging from ambient air using an oxidation flow reactor in seoul during winter.

Herein, the formation and aging processes of organic aerosol (OA) in urban Seoul, Korea, during winter were investigated using a high-resolution aerosol mass spectrometer (HR-ToF-AMS) and an oxidation flow reactor (OFR). The results demonstrated that the highest secondary OA (SOA) production (ΔOA = 3.44 µg m-3 with a relative OA enhancement ratio (EROA) = 1.40) occurred at ∼2 eq. days of OH exposure. Particularly, higher SOA production was observed under the following atmospheric conditions: high relative humidity (RH) (>70%) and high PM1 mass concentration (>50 µg m-3), demonstrating that oxidation capacity, heterogeneous and aqueous phase reactions are important for further oxidation. Additionally, increased SOA formation occurs under both higher hydrocarbon-like OA and more oxidized OOA conditions. Further oxidation of both freshly emitted and aged and/or transported OA can be a remarkable further source of SOA in winter in Seoul and further downwind areas. In particular, the high mass concentration of MO-OOA in high total PM1 would be an important indication that SOA formation could be accelerated by a heterogeneous reaction, necessitating additional investigations on the haze formation process.

Emission factors for polycyclic aromatic hydrocarbons from laboratory biomass-burning and their chemical transformations during aging in an oxidation flow reactor.

Atmospheric polycyclic aromatic hydrocarbons (PAHs) can be emitted from different combustion sources including domestic biomass burning, internal combustion engines, and biomass burning (BB) in wild, prescribed, and agricultural fires. With climate warming and consequent global increases in frequency and severity of wildfires, BB is a dominant source of PAHs emitted into the atmosphere. In this study, six globally and regionally important and representative fuels (Alaskan peat, Moscow peat, Pskov peat, eucalyptus, Malaysian peat, and Malaysian agricultural peat) were burned under controlled conditions in the combustion chamber facility at the Desert Research Institute (DRI, Reno, NV, USA). Gas- and particle-phase BB emissions were aged in an oxidation flow reactor (OFR) to mimic five to sevendays of atmospheric aging. To sample gas- and particle-phase BB emissions, fresh and OFR-aged biomass-burning aerosols were collected on Teflon-impregnated glass fiber filters (TIGF) in tandem with XAD resin media for organic carbon speciation. The objectives of this study were to i) quantify the emission factors for 113 PAHs emitted from the combustion of the six selected fuels, ii) characterize the distribution of PAH compounds between gas and particle phases for these fuels, iii) identify the changes in PAHs during OFR-aging, and iv) evaluate toxicity potential with characterized compounds. We found that combustion emissions of gas-phase PAHs were more abundant (>80 % by mass) than particle-phase PAHs, for emissions from all combusted fuels. The mass fraction of substituted napthalenes in Moscow peat and Malaysian peat emissions were ∼70 % & 84 %, respectively, whereas in Eucalyptus the same fraction was <50 %, which indicates that these substituted compounds can be used as tracers for peat emissions. Mass concentrations of gas- and particle-phase PAHs were reduced by ∼70 % after OFR oxidation. However, the understanding of the fate of PAHs during OFR oxidation requires further investigations. Our results also indicate that the PAH toxicity of BB samples would be underestimated by 10-100 times if only the BaPeq for the 16 US EPA priority PAHs in the particle phase are included.

Role of Secondary Organic Matter on Soot Particle Toxicity in Reconstituted Human Bronchial Epithelia Exposed at the Air-Liquid Interface.

Secondary organic matter (SOM) formed from gaseous precursors constitutes a major mass fraction of fine particulate matter. However, there is only limited evidence on its toxicological impact. In this study, air-liquid interface cultures of human bronchial epithelia were exposed to different series of fresh and aged soot particles generated by a miniCAST burner combined with a micro smog chamber (MSC). Soot cores with geometric mean mobility diameters of 30 and 90 nm were coated with increasing amounts of SOM, generated from the photo-oxidation of mesitylene and ozonolysis of α-pinene. At 24 h after exposure, the release of lactate dehydrogenase (LDH), indicating cell membrane damage, was measured and proteome analysis, i.e. the release of 102 cytokines and chemokines to assess the inflammatory response, was performed. The data indicate that the presence of the SOM coating and its bioavailability play an important role in cytotoxicity. In particular, LDH release increased with increasing SOM mass/total particle mass ratio, but only when SOM had condensed on the outer surface of the soot cores. Proteome analysis provided further evidence for substantial interference of coated particles with essential properties of the respiratory epithelium as a barrier as well as affecting cell remodeling and inflammatory activity.

Limited Secondary Organic Aerosol Production from Acyclic Oxygenated Volatile Chemical Products.

Volatile chemical products (VCPs) have recently been identified as potentially important unconventional sources of secondary organic aerosol (SOA), in part due to the mitigation of conventional emissions such as vehicle exhaust. Here, we report measurements of SOA production in an oxidation flow reactor from a series of common VCPs containing oxygenated functional groups and at least one oxygen within the molecular backbone. These include two oxygenated aromatic species (phenoxyethanol and 1-phenoxy-2-propanol), two esters (butyl butyrate and butyl acetate), and four glycol ethers (carbitol, methyl carbitol, butyl carbitol, and hexyl carbitol). We measured gas- and particle-phase products with a suite of mass spectrometers and particle-sizing instruments. Only the aromatic VCPs produce SOA with substantial yields. For the acyclic VCPs, ether and ester functionality promotes fragmentation and hinders autoxidation, whereas aromatic rings drive SOA formation in spite of the presence of ether groups. Therefore, our results suggest that a potential strategy to reduce urban SOA from VCPs would be to reformulate consumer products to include less oxygenated aromatic compounds.

Oxidation Flow Reactor Results in a Chinese Megacity Emphasize the Important Contribution of S/IVOCs to Ambient SOA Formation.

Oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) formation potential of ambient air in Guangzhou, China was investigated using a field-deployed oxidation flow reactor (OFR). The OFR was used to mimic hours to weeks of atmospheric exposure to hydroxyl (OH) radicals within the 2-3 min residence time. A comprehensive investigation on the variation of VOCs and OVOCs as a function of OH exposure is shown. Substantial formation of organic acids and nitrogen-containing OVOC species were observed. Maximum SOA formation in the OFR was observed following 1-4 equiv days' OH exposure. SOA produced from known/measured VOC/IVOC precursors such as single-ring aromatics and long-chain alkanes can account for 52-75% of measured SOA under low NOx and 26-60% under high NOx conditions based on laboratory SOA yield parametrizations. To our knowledge, this is the first time that the contribution (8-20%) of long-chain (C8-C20) alkane oxidation to OFR SOA formation was quantified from direct measurement. By additionally estimating contribution from unmeasured semivolatile and intermediate volatility compounds (S/IVOCs) that are committed with C8-C20 alkanes, 64-100% of the SOA formation observed in the OFR can be explained, signifying the important contribution of S/IVOCs such as large cyclic alkanes to ambient SOA.

Using an oxidation flow reactor to understand the effects of gasoline aromatics and ethanol levels on secondary aerosol formation.

Fuel type and composition affect tailpipe emissions and secondary aerosol production from mobile sources. This study assessed the influence of gasoline fuels with varying levels of aromatics and ethanol on the primary emissions and secondary aerosol formation from a flexible fuel vehicle equipped with a port fuel injection engine. The vehicle was exercised over the LA92 and US06 driving cycles using a chassis dynamometer. Secondary aerosol formation potential was measured using a fast oxidation flow reactor. Results showed that the high aromatics fuels led to higher gaseous regulated emissions, as well as particulate matter (PM), black carbon, and total and solid particle number. The high ethanol content fuel (E78) resulted in reductions for the gaseous regulated pollutants and particulate emissions, with some exceptions where elevated emissions were seen for this fuel compared to both E10 fuels, depending on the driving cycle. Secondary aerosol formation potential was dominated by the cold-start phase and increased for the high aromatics fuel. Secondary aerosol formation was seen in lower levels for E78 due to the lower formation of precursor emissions using this fuel. In addition, operating driving conditions and aftertreatment efficiency played a major role on secondary organic and inorganic aerosol formation, indicating that fuel properties, driving conditions, and exhaust aftertreatment should be considered when evaluating the emissions of secondary aerosol precursors from mobile sources.

Secondary Organic Aerosol Formation of Fleet Vehicle Emissions in China: Potential Seasonality of Spatial Distributions.

Vehicle emissions are an important source of urban particular matter. To investigate the secondary organic aerosol (SOA) formation potential of real-world vehicle emissions, we exposed on-road air in Beijing to hydroxyl radicals generated in an oxidation flow reactor (OFR) under high-NOx conditions on-board a mobile laboratory and characterized SOA and their precursors with a suite of state-of-the-art instrumentation. The OFR produced 10-170 µg m-3 of SOA with a maximum SOA formation potential of 39-50 µg m-3 ppmv-1 CO that occurred following an integrated OH exposure of (1.3-2.0) × 1011 molecules cm-3 s. The results indicate relatively shorter photochemical ages for maximum SOA production than previous OFR results obtained under low-NOx conditions. Such timescales represent the balance of functionalization and fragmentation, possibly resulting in different spatial distributions of SOA in different seasons as the oxidant level changes. The detected precursors may explain as much as 13% of the observed SOA with the remaining plausibly contributed by the oxidation of undetected intermediate-volatility organic compounds. Extrapolation of the results suggests an annual SOA production rate of 0.78 Tg yr-1 from mobile gasoline sources in China, highlighting the importance of effective regulation of gaseous vehicular precursors to improve air quality in the future.

Effects of driving conditions on secondary aerosol formation from a GDI vehicle using an oxidation flow reactor.

A comprehensive study on the effects of photochemical aging on exhaust emissions from a vehicle equipped with a gasoline direct injection engine when operated over seven different driving cycles was assessed using an oxidation flow reactor. Both primary emissions and secondary aerosol production were measured over the Federal Test Procedure (FTP), LA92, New European Driving Cycle (NEDC), US06, and the Highway Fuel Economy Test (HWFET), as well as over two real-world cycles developed by the California Department of Transportation (Caltrans) mimicking typical highway driving conditions. We showed that the emissions of primary particles were largely depended on cold-start conditions and acceleration events. Secondary organic aerosol (SOA) formation also exhibited strong dependence on the cold-start cycles and correlated well with SOA precursor emissions (i.e., non-methane hydrocarbons, NMHC) during both cold-start and hot-start cycles (correlation coefficients 0.95-0.99), with overall emissions of ∼68-94 mg SOA per g NMHC. SOA formation significantly dropped during the hot-running phases of the cycles, with simultaneous increases in nitrate and ammonium formation as a result of the higher nitrogen oxide (NOx) and ammonia emissions. Our findings suggest that more SOA will be produced during congested, slow speed, and braking events in highways.

Atmospheric photochemistry and secondary aerosol formation of urban air in Lyon, France.

Photochemical aging of volatile organic compounds (VOCs) in the atmosphere is an important source of secondary organic aerosol (SOA). To evaluate the formation potential of SOA at an urban site in Lyon (France), an outdoor experiment using a Potential Aerosol Mass (PAM) oxidation flow reactor (OFR) was conducted throughout entire days during January-February 2017. Diurnal variation of SOA formations and their correlation with OH radical exposure (OHexp), ambient pollutants (VOCs and particulate matters, PM), Relative Humidity (RH), and temperature were explored in this study. Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of (0.2-1.2)×1012 molecule/(cm3•sec), corresponding to several days to weeks of equivalent atmospheric photochemical aging. The results informed that urban air at Lyon has high potency to contribute to SOA, and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis. Maximum SOA formation (36 µg/m3) was obtained at OHexp of about 7.4 × 1011molecule/(cm3•sec), equivalent to approximately 5 days of atmospheric oxidation. The correlation between SOA formation and ambient environment conditions (RH & temperature, VOCs and PM) was observed. It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.

[Diurnal Variation of SOA Formation Potential from Ambient Air at an Urban Site in Beijing].

Secondary organic aerosol (SOA) is an important component of atmospheric fine particles (PM2.5). The study of the diurnal variation of SOA formation potential is important for understanding the evolution of SOA and its contribution to fine particle pollution. The oxidation flow reactor (OFR) was used to study the SOA formation potential of ambient air in summer at an urban site in Beijing. The high concentration of OH radicals in the reactor can oxidize the volatile organic compounds (VOCs) and lead to SOA formation. The hour average SOA formation potential varied between 3.9-9.4 µg·m-3 in a day and had a higher value at night than in the daytime. The lowest value of SOA formation potential was about 3.9 µg·m-3 observed at 16:00 in the afternoon. This variation of SOA formation potential is consistent with the typical VOCs, such as toluene, and inversely related to the concentration of ozone. In addition to the impact of change in the height of the boundary layer, experimental data showed that the reduction of VOCs in photo-oxidation in the daytime was an important reason for the decrease of SOA formation potential in daytime. Compared to similar studies in developed countries, the SOA formation potential was higher in Beijing due to the higher concentrations of VOCs and might make an important contribution to the fine particle pollution in Beijing.