Potential Aerosol Mass Reactor Research Articles

Roles of Relative Humidity and Particle Size on Chemical Aging of Tropical Peatland Burning Particles: Potential Influence of Phase State and Implications for Hygroscopic Property

AbstractPeatland fires in Southeast Asia are an important source of primary organic aerosol (POA). Chemical aging of POA in the atmosphere produces oxygenated POA (OPOA). The OPOA production influences optical and hygroscopic properties, modulating the regional climate. However, the roles of environmental parameters such as relative humidity (RH) on chemical aging of peatland burning particles have rarely been investigated. Utilizing the potential aerosol mass (PAM) reactor, we conducted laboratory experiments for POA aging of particles generated from smoldering combustions of surface peat, fern, and Acacia leaves. The corresponding experiments for secondary organic aerosol formation were also separately conducted. Properties and chemical compositions of the resulting particle were quantified by both the hygroscopic tandem differential mobility analyzer and time‐of‐flight aerosol chemical speciation monitor (ToF‐ACSM). Conversion of peat combustion from POA to OPOA was pronounced when RH in the PAM reactor was higher. Considering that previous electromicroscopic observations demonstrated that peat combustion POA is likely (semi)solid, we postulate that oxidation of fresh peatland burning particles is faster at an elevated RH due to reduced viscosity following hygroscopic growth. Hygroscopicity parameter (κ) of aged POA particles linearly correlated with the mass fraction of OPOA that was quantified by the ToF‐ACSM. The above results highlight the importance of simultaneously measuring the chemical aging and particle phase state of peatland burning POA for quantifying their climatic impacts.

Photochemical aging of aerosol particles in different air masses arriving at Baengnyeong Island, Korea

Abstract. Atmospheric aerosol particles are a serious health risk, especially in regions like East Asia. We investigated the photochemical aging of ambient aerosols using a potential aerosol mass (PAM) reactor at Baengnyeong Island in the Yellow Sea during 4–12 August 2011. The size distributions and chemical compositions of aerosol particles were measured alternately every 6 min from the ambient air or through the highly oxidizing environment of a potential aerosol mass (PAM) reactor. Particle size and chemical composition were measured by using the combination of a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Inside the PAM reactor, O3 and OH levels were equivalent to 4.6 days of integrated OH exposure at typical atmospheric conditions. Two types of air masses were distinguished on the basis of the chemical composition and the degree of aging: air transported from China, which was more aged with a higher sulfate concentration and O : C ratio, and the air transported across the Korean Peninsula, which was less aged with more organics than sulfate and a lower O : C ratio. For both episodes, the particulate sulfate mass concentration increased in the 200–400 nm size range when sampled through the PAM reactor. A decrease in organics was responsible for the loss of mass concentration in 100–200 nm particles when sampled through the PAM reactor for the organics-dominated episode. This loss was especially evident for the m∕z 43 component, which represents less oxidized organics. The m∕z 44 component, which represents further oxidized organics, increased with a shift toward larger sizes for both episodes. It is not possible to quantify the maximum possible organic mass concentration for either episode because only one OH exposure of 4.6 days was used, but it is clear that SO2 was a primary precursor of secondary aerosol in northeast Asia, especially during long-range transport from China. In addition, inorganic nitrate evaporated in the PAM reactor as sulfate was added to the particles. These results suggest that the chemical composition of aerosols and their degree of photochemical aging, particularly for organics, are also crucial in determining aerosol mass concentrations.

Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels

Abstract. The chemical complexity of biomass burning organic aerosol (BBOA) greatly increases with photochemical aging in the atmosphere, necessitating controlled laboratory studies to inform field observations. In these experiments, BBOA from American white oak (Quercus alba) leaf and heartwood samples was generated in a custom-built emissions and combustion chamber and photochemically aged in a potential aerosol mass (PAM) flow reactor. A thermal desorption aerosol gas chromatograph (TAG) was used in parallel with a high-resolution time-of-flight aerosol mass spectrometer (AMS) to analyze BBOA chemical composition at different levels of photochemical aging. Individual compounds were identified and integrated to obtain relative decay rates for key molecules. A recently developed chromatogram binning positive matrix factorization (PMF) technique was used to obtain mass spectral profiles for factors in TAG BBOA chromatograms, improving analysis efficiency and providing a more complete determination of unresolved complex mixture (UCM) components. Additionally, the recently characterized TAG decomposition window was used to track molecular fragments created by the decomposition of thermally labile BBOA during sample desorption. We demonstrate that although most primary (freshly emitted) BBOA compounds deplete with photochemical aging, certain components eluting within the TAG thermal decomposition window are instead enhanced. Specifically, the increasing trend in the decomposition m∕z 44 signal (CO2+) indicates formation of secondary organic aerosol (SOA) in the PAM reactor. Sources of m∕z 60 (C2H4O2+), typically attributed to freshly emitted BBOA in AMS field measurements, were also investigated. From the TAG chemical speciation and decomposition window data, we observed a decrease in m∕z 60 with photochemical aging due to the decay of anhydrosugars (including levoglucosan) and other compounds, as well as an increase in m∕z 60 due to the formation of thermally labile organic acids within the PAM reactor, which decompose during TAG sample desorption. When aging both types of BBOA (leaf and heartwood), the AMS data exhibit a combination of these two contributing effects, causing limited change to the overall m∕z 60 signal. Our observations demonstrate the importance of chemically speciated data in fully understanding bulk aerosol measurements provided by the AMS in both laboratory and field studies.

Secondary Organic Aerosol Production from Gasoline Vehicle Exhaust: Effects of Engine Technology, Cold Start, and Emission Certification Standard.

Secondary organic aerosol (SOA) formation from dilute exhaust from 16 gasoline vehicles was investigated using a potential aerosol mass (PAM) oxidation flow reactor during chassis dynamometer testing using the cold-start unified cycle (UC). Ten vehicles were equipped with gasoline direct injection engines (GDI vehicles) and six with port fuel injection engines (PFI vehicles) certified to a wide range of emissions standards. We measured similar SOA production from GDI and PFI vehicles certified to the same emissions standard; less SOA production from vehicles certified to stricter emissions standards; and, after accounting for differences in gas-particle partitioning, similar effective SOA yields across different engine technologies and certification standards. Therefore the ongoing, dramatic shift from PFI to GDI vehicles in the United States should not alter the contribution of gasoline vehicles to ambient SOA and the natural replacement of older vehicles with newer ones certified to stricter emissions standards should reduce atmospheric SOA levels. Compared to hot operations, cold-start exhaust had lower effective SOA yields, but still contributed more SOA overall because of substantially higher organic gas emissions. We demonstrate that the PAM reactor can be used as a screening tool for vehicle SOA production by carefully accounting for the effects of the large variations in emission rates.

Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (<sup>1</sup>H-NMR) analysis and HPLC HULIS determination

Abstract. The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance (1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1 × 1012 molec OH cm−3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

Inter-comparison of laboratory smog chamber and flow reactor systems on organic aerosol yield and composition

Abstract. A variety of tools are used to simulate atmospheric aging, including smog chambers and flow reactors. Traditional, large-scale smog chambers age emissions over the course of hours to days, whereas flow reactors rapidly age emissions using high oxidant concentrations to reach higher degrees of oxygenation than typically attained in smog chamber experiments. The atmospheric relevance of the products generated under such rapid oxidation warrants further study. However, no previously published studies have compared the yields and chemical composition of products generated in flow reactors and smog chambers from the same starting mixture. The yields and composition of the organic aerosol formed from the photo-oxidation of α-pinene and of wood-combustion emissions in a smog chamber (SC) and two flow reactors: a potential aerosol mass reactor (PAM) and a micro-smog chamber (MSC), were determined using aerosol mass spectrometry. Reactants were sampled from the SC and aged in the MSC and the PAM using a range of hydroxyl radical (OH) concentrations and then photo-chemically aged in the SC. The chemical composition, as well as the maximum yields and emission factors, of the products in both the α-pinene and wood-combustion systems determined with the PAM and the SC agreed reasonably well. High OH exposures have been shown previously to lower yields by breaking carbon–carbon bonds and forming higher volatility species, which reside largely in the gas phase; however, fragmentation in the PAM was not observed. The yields determined using the PAM for the α-pinene system were slightly lower than in the SC, possibly from increased wall losses of gas phase species due to the higher surface area to volume ratios in the PAM, even when offset with better isolation of the sampled flow from the walls. The α-pinene SOA results for the MSC were not directly comparable, as particles were smaller than the optimal AMS transmission range. The higher supersaturation in the flow reactors resulted in more nucleation than in the SC. For the wood-combustion system, emission factors measured from the MSC were typically lower than those measured from the SC. Lower emission factors in the MSC may have been due to considerable nucleation mode particles formed in the MSC which were not detected by the AMS or due to condensational loss of gases to the walls inside or after the MSC. More comprehensive coverage of the potential particle size range is needed in future SOA measurements to improve our understanding of the differences in yields when comparing the MSC to the SC. The PAM and the SC agreed within measurement uncertainties in terms of yields and composition for the systems and conditions studied here and this agreement supports the continued use of the PAM to study atmospheric aging.

Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas.