High-resolution Time-of-flight Aerosol Mass Spectrometry Research Articles

The investigations on organic sources and inorganic formation processes and their implications on haze during late winter in Seoul, Korea

This study investigated the sources and formation processes of particulate matter (PM) with an aerodynamic diameter ≤1 μm (PM1) and black carbon (BC) in Seoul during late winter via high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and positive matrix factorization (PMF) analysis. In this study, secondary aerosols (75.1%) exhibited higher contributions than did primary aerosols (24.9%), suggesting the importance of secondary aerosol formation over primary aerosol emissions for NR-PM1+BC during late winter.Frequent haze episodes were observed and these were found to proceed in two distinct stages each with different pattern of sulfur oxidation ratio (SOR), nitrogen oxidation ratio (NOR) and meteorological conditions, such as the wind speed, direction and relative humidity (RH). Haze formation during stage 1 was caused mainly by local accumulation of primary aerosols and formation of local secondary aerosols under stagnant conditions. However, there were some impacts of down mixing of regional transport. Stage 2 took place during the night following stage 1 and was characterized by enhanced secondary aerosol formation. Enhancement of SOR might be due to accelerated aqueous phase reactions under higher RH and enhanced NOR is probably because of the heterogeneous uptake of N2O5 by ammonium sulfate aerosols ensued after sulfate formation. These findings suggest that the winter air quality in Seoul depends on complex processes, from not only emissions and transport from upwind areas but also from significant impacts of meteorological condition.

Seasonal characteristics of PM1 in Seoul, Korea, measured using HR-ToF-Aerosol Mass Spectrometer in 2018

In Korea, the characteristics of aerosols vary according to the four distinct seasons (spring, summer, fall, and winter); the seasonal variations are influenced by different air mass inflows of each season. Therefore, research is required to analyze the composition and characteristics of aerosols in different seasons. In this study, high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and positive matrix factorization (PMF) analyses were conducted in 2018 to examine the seasonal characteristics of aerosols with focus on organic aerosol in Seoul metropolitan area of South Korea. The results indicated that the seasonal non-refractory submicron particle (NR-PM1) concentration in Seoul metropolitan area ranged from 6.3 to 41.0 μg/m3, which was lower than those in other metropolitan areas of Northeast Asia and slightly higher than those in suburban and rural areas of South Asia and Europe. The organic aerosol concentration, which was the highest among PM1 components, ranged 3.5–14.24 μg/m3. In addition, a large increase in nitrate content was observed in high-concentration episodes. In all seasons, the O:C ratio and oxidation state were higher than those in previous studies, and it was estimated that the oxidation state was higher than those in other countries due to the influx of aged aerosols by long-range transport. In summer, the odd oxygen (Ox) concentration tends to be proportional to temperature and inversely proportional to humidity, indicating that the formation of fresh organic aerosol (OA) by active photochemical reaction is the main process of organic aerosol generation. In spring, fall, and winter, the Van Krevelen graph showed a slope of −0.68 ~ –0.99, indicating that carboxylic acid production was an important process for OA production. In addition, the causes of the high concentration episodes observed in spring and winter were estimated through the oxidation state of organic aerosols, PMF factor, and backward trajectory analyses.

Chemical characterization of submicron particulate matter (PM1) emitted by burning highland barley in the northeastern part of the Qinghai–Tibet Plateau

Tibetans in the Qinghai–Tibet Plateau (QTP) commonly burn highland barley during their traditional festivals. However, few studies have been focused on the physical and chemical properties of the particles emitted when such biomass is burned. A comprehensive field study was conducted on the top of Waliguan mountain (3816 m a.s.l.) at the northeastern border of the QTP to provide insights into aerosol characteristics in this remote site during July 2017 during which one of the most important Tibetan festivals (known as “Weisang”) occurred on 5–6 July. Extremely intense aerosol emissions occurred between 23:00 on 5 July and 08:00 on 6 July, and the dominant chemicals emitted in submicron particular matter (PM1) were organic aerosols (OAs) measured through a high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS). Fresh biomass burning OA (BBOA) and traffic-related hydrocarbon-like OA (HOA), decomposed by positive matrix factorization analysis on the OA high-resolution mass spectrum, contributed ~90% of the OA during the event. The BBOA mass spectrum was found to be very similar to that of traditional wood identified by HR-ToF-AMS, but with fewer nitrogen-containing species and a higher m/z 60 to 73 signal ratio. The BBOA emission factor during the event was 2.28 g kg−1, which was comparable to emission factors found for burning wheat, grass, dung, and hardwood in previous studies in Himalayas. The particle light extinction coefficient and the cloud condensation nuclei number concentration were clearly increased during the period of burning highland barley, suggesting that the aerosols emitted could significantly affect radiative forcing and cloud properties in the QTP.

Molecular insights on aging and aqueous-phase processing from ambient biomass burning emissions-influenced Po Valley fog and aerosol

Abstract. To study the influence of regional biomass burning emissions and secondary processes, ambient samples of fog and aerosol were collected in the Po Valley (Italy) during the 2013 Supersito field campaign. After the extent of fresh vs. aged biomass burning influence was estimated from proton nuclear magnetic resonance (1H NMR) and high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), two samples of fog water and two samples of PM1 aerosol were selected for ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Molecular compositions indicated that the water-soluble organic matter was largely non-polymeric without clearly repeating units. The selected samples had an atypically large frequency of molecular formulas containing nitrogen and sulfur (not evident in the NMR composition) attributed to multifunctional organonitrates and organosulfates. Higher numbers of organonitrates were observed in aerosol, and higher numbers of organosulfates were observed in fog water. Consistent with the observation of an enhanced aromatic proton signature in the 1H-NMR analysis, the average molecular formula double-bond equivalents and carbon numbers were higher in the fresh biomass-burning-influenced samples. The average O : C and H : C values from FT-ICR MS were higher in the samples with an aged influence (O : C = 0.50–0.58, and H : C = 1.31–1.37) compared to those with fresh influence (O : C = 0.43–0.48, and H : C = 1.13–1.30). The aged fog had a large set of unique highly oxygenated CHO fragments in the HR-ToF-AMS, which reflects an enrichment of carboxylic acids and other compounds carrying acyl groups, highlighted by the NMR analysis. Fog compositions were more oxidized and SOA (secondary organic aerosol)-like than aerosols as indicated by their NMR measured acyl-to-alkoxyl ratios and the observed molecular formula similarity between the aged aerosol and fresh fog, implying that fog nuclei must be somewhat aged. Overall, functionalization with nitrate and sulfate moieties, in addition to aqueous oxidation, triggers an increase in the molecular complexity in this environment, which is apparent in the FT-ICR MS results. This study demonstrates the significance of the aqueous phase in transforming the molecular chemistry of atmospheric organic matter and contributing to secondary organic aerosol.

Effect of relative humidity on non-refractory submicron aerosol evolution during summertime in Hangzhou, China

Relative humidity (RH) has a significant and complex effect on aerosols because of the aqueous phase process and gas-particle partition. The mass concentration and size distribution of organic aerosols, sulfate, nitrate, ammonium, and chloride were measured using high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS). These measurements were recorded from Aug. 5 to Sept. 23, 2016 in Binjiang District, Hangzhou, China, during which period more than 78% of the readings showed an RH over 60%, while the average temperature was 26 °C. Correlation analysis was applied to inorganic aerosol measurements while positive matrix factorization (PMF) was applied for source apportionment of organic aerosols (OA). The pattern of fixation of ammonium in aerosols changed as the RH increased, suggesting that RH enhances nitrate participation in particles, while sulfate is scavenged by droplets. All species of non-refractory submicron particles (NR-PM1) showed an increase in their peak size as the RH increased. Primary OA (POA) continuously accumulated as the RH increased. When RH 60%, there was a relatively slow decrease in OOA, dominated by the wet removal effect rather than oxidation. The degree of oxidation of OA decreased as RH increased; this can be explained by most of the OOA with higher hygroscopicity being removed as droplets.

Seasonal variations in high time-resolved chemical compositions, sources, and evolution of atmospheric submicron aerosols in the megacity Beijing

Abstract. A severe regional haze problem in the megacity Beijing and surrounding areas, caused by fast formation and growth of fine particles, has attracted much attention in recent years. In order to investigate the secondary formation and aging process of urban aerosols, four intensive campaigns were conducted in four seasons between March 2012 and March 2013 at an urban site in Beijing (116.31° E, 37.99° N). An Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) was deployed to measure non-refractory chemical components of submicron particulate matter (NR-PM1). The average mass concentrations of PM1 (NR-PM1+black carbon) were 45.1 ± 45.8, 37.5 ± 31.0, 41.3 ± 42.7, and 81.7 ± 72.4 µg m−3 in spring, summer, autumn, and winter, respectively. Organic aerosol (OA) was the most abundant component in PM1, accounting for 31, 33, 44, and 36 % seasonally, and secondary inorganic aerosol (SNA, sum of sulfate, nitrate, and ammonium) accounted for 59, 57, 43, and 55 % of PM1 correspondingly. Based on the application of positive matrix factorization (PMF), the sources of OA were obtained, including the primary ones of hydrocarbon-like (HOA), cooking (COA), biomass burning OA (BBOA) and coal combustion OA (CCOA), and secondary component oxygenated OA (OOA). OOA, which can be split into more-oxidized (MO-OOA) and less-oxidized OOA (LO-OOA), accounted for 49, 69, 47, and 50 % in four seasons, respectively. Totally, the fraction of secondary components (OOA+SNA) contributed about 60–80 % to PM1, suggesting that secondary formation played an important role in the PM pollution in Beijing, and primary sources were also non-negligible. The evolution process of OA in different seasons was investigated with multiple metrics and tools. The average carbon oxidation states and other metrics show that the oxidation state of OA was the highest in summer, probably due to both strong photochemical and aqueous-phase oxidations. It was indicated by the good correlations (r = 0.53–0.75, p < 0.01) between LO-OOA and odd oxygen (Ox = O3 + NO2), and between MO-OOA and liquid water content in aerosols. BBOA was resolved in spring and autumn, influenced by agricultural biomass burning (e.g., field preparation burnings, straw burning after the harvest). CCOA was only identified in winter due to domestic heating. These results signified that the comprehensive management for biomass burning and coal combustion emissions is needed. High concentrations of chemical components in PM1 in Beijing, especially in winter or in adverse meteorological conditions, suggest that further strengthening the regional emission control of primary particulate and precursors of secondary species is expected.

New insights into atmospherically relevant reaction systems using direct analysis in real-time mass spectrometry (DART-MS)

Abstract. The application of direct analysis in real-time mass spectrometry (DART-MS), which is finding increasing use in atmospheric chemistry, to two different laboratory model systems for airborne particles is investigated: (1) submicron C3–C7 dicarboxylic acid (diacid) particles reacted with gas-phase trimethylamine (TMA) or butylamine (BA) and (2) secondary organic aerosol (SOA) particles from the ozonolysis of α-cedrene. The diacid particles exhibit a clear odd–even pattern in their chemical reactivity toward TMA and BA, with the odd-carbon diacid particles being substantially more reactive than even ones. The ratio of base to diacid in reacted particles, determined using known diacid–base mixtures, was compared to that measured by high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), which vaporizes the whole particle. Results show that DART-MS probes ∼ 30 nm of the surface layer, consistent with other studies on different systems. For α-cedrene SOA particles, it is shown that varying the temperature of the particle stream as it enters the DART-MS ionization region can distinguish between specific components with the same molecular mass but different vapor pressures. These results demonstrate the utility of DART-MS for (1) examining reactivity of heterogeneous model systems for atmospheric particles and (2) probing components of SOA particles based on volatility.

The effect of sub-zero temperature on the formation and composition of secondary organic aerosol from ozonolysis of alpha-pinene.

This study presents a newly constructed temperature controlled cold-room smog chamber at Aarhus University, Denmark. The chamber is herein utilized to study the effect of sub-zero temperature on the formation and chemical composition of secondary organic aerosol (SOA) from ozone initiated oxidation of α-pinene. The chemical composition of α-pinene SOA formed from dark ozonolysis of α-pinene at 293 K and 258 K was investigated using High-Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS) and Ultra-High Performance Liquid Chromatography/Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry (UHPLC/ESI-qToF-MS). For comparison, an OH-initiated oxidation experiment was performed at 293 K. In ozonolysis experiments it was found that oxygen-to-carbon (O : C) ratios were higher in the particles formed at 293 K compared to 258 K. A total of 16 different organic acids and 30 dimers esters were quantified in the collected particles composing up to 34% of the total α-pinene SOA mass with increased mass fraction of carboxylic acids in particles from α-pinene ozonolysis at 258 K compared to 293 K. In contrast, dimer esters showed suppressed formation at the sub-zero reaction temperature, thus contributing 3% to SOA mass at 258 K while contributing 9% at 293 K. SOA formed in the OH-initiated oxidation of α-pinene at 293 K resulted in low concentrations of dimer esters supporting Criegee intermediates as a possible pathway to dimer ester formation. Vapour pressure estimates of the identified carboxylic acids and dimer esters are presented and show how otherwise semi-volatile carboxylic acids at sufficiently low temperatures may classify as low or even extremely low volatile organic compounds (ELVOC), thus may add to an enhanced particle formation observed at the sub-zero temperature through gas-to-particle conversion. The change in chemical composition of the SOA particles with temperature is ascribed to a combination of effects: the decreased vapour pressures and hence increased condensation of carboxylic acids from the gas phase to the particle phase along with suppressed formation of the high molecular weight dimer esters and different gas and particle phase chemistry results in particles of different chemical composition as a consequence of low reaction temperatures.

Characterization of submicron aerosols influenced by biomass burning at a site in the Sichuan Basin, southwestern China

Abstract. Severe air pollution in Asia is often the consequence of a combination of large anthropogenic emissions and adverse synoptic conditions. However, limited studies on aerosols have been conducted under high emission intensity and under unique geographical and meteorological conditions. In this study, an Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and other state-of-the-art instruments were utilized at a suburban site, Ziyang, in the Sichuan Basin during December 2012 to January 2013. The chemical compositions of atmospheric submicron aerosols (PM1) were determined, the sources of organic aerosols (OA) were apportioned, and the aerosol secondary formation and aging process were explored as well. Due to high humidity and static air, PM1 maintained a relatively stable level during the whole campaign, with the mean concentration of 59.7 ± 24.1 µg m−3. OA was the most abundant component (36 %) in PM1, characterized by a relatively high oxidation state. Positive matrix factorization analysis was applied to the high-resolution organic mass spectral matrix, which deconvolved OA mass spectra into four factors: low-volatility (LV-OOA) and semivolatile oxygenated OA (SV-OOA), biomass burning (BBOA) and hydrocarbon-like OA (HOA). OOA (sum of LV-OOA and SV-OOA) dominated OA as high as 71 %. In total, secondary inorganic and organic formation contributed 76 % of PM1. Secondary inorganic species correlated well (Pearson r = 0.415–0.555, p < 0.01) with relative humidity (RH), suggesting the humid air can favor the formation of secondary inorganic aerosols. As the photochemical age of OA increased with higher oxidation state, secondary organic aerosol formation contributed more to OA. The slope of OOA against Ox( = O3+NO2) steepened with the increase of RH, implying that, besides the photochemical transformation, the aqueous-phase oxidation was also an important pathway of the OOA formation. Primary emissions, especially biomass burning, resulted in high concentration and proportion of black carbon (BC) in PM1. During the episode obviously influenced by primary emissions, the contributions of BBOA to OA (26 %) and PM1 (11 %) were much higher than those (10–17 %, 4–7 %) in the clean and other polluted episodes, highlighting the significant influence of biomass burning.

Combustion process apportionment of carbonaceous particulate emission from a diesel fuel burner

In this study, we present the impact of fuel additives (Fe, Al, and V) on the measured particulate organic matter (OM) fraction formed from the combustion of propane-heated diesel fuel (DF) in a DF Combustion Aerosol STandard (DF-CAST) burner prototype within the range of air-fuel-equivalence ratios (λDF) from 5.4 to 10.4. The OM fraction was measured by using high resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and unmixed into factor profiles by applying the SoFi program, a source apportionment tool using positive matrix factorization (PMF)/multilinear engine (ME-2) solvers. The separated factors were correlated with the particle light absorption properties at UV (370nm) and IR (950nm) wavelengths, NO3−, and NH4+ as well as exhaust gas (CO2, CO, NO, NH3, hydrocarbons (HC), and formaldehyde (HCHO)). Addition of Fe, Al, and V to the DF yielded apparent catalytic processes leading to the formation of nitrogen-containing particulate OM (CHN and CHON families). The separated factors were distinct in terms of their oxidation state, correlation with the measured particulate and gaseous emissions. Similarities in the separated factors based on temporal evolution were observed in DF and DF+additive experiments. This study gives a new insight in the modification of DF combustion particle properties in the presence of fuel additives.

Characteristics and temporal evolution of particulate emissions from a ship diesel engine

Due to current and upcoming regulations to address the adverse impacts of particulate matter (PM) from shipping emissions, the maritime sector is required to find energy-efficient ways to comply mainly by using low fuel sulfur content (FSC) in regulated seas. We studied the PM emission from a research ship diesel engine with fuel switching capability, optimized for HFO used at cruising, operated at representative engine loads resulting to varying excess O2 emission which was an indirect measurement of air–fuel mixture (λ), using heavy fuel oil (HFO, 1.6 S (%m)) and diesel fuel (DF, <0.001 S (%m)). We determined the characteristics and temporal evolution of the PM by using the High Resolution Time-of-Flight Aerosol Mass Spectrometry (HR-ToF-AMS) in combination with aethalometer, particle sizers, online gas phase, and filter measurements. The average emission factors were higher for HFO than for DF with relative percent differences of ∼200, ∼180, ∼150, and ∼145 for SO42−, inorganic elements, organic matter (OM), and PM2.5, respectively, while that for black carbon (BC) was similar for both fuels. The difference between HFO and DF in terms of carbonaceous emissions was higher at 100% and 25% than at 75% and 50% engine loads. The exhaust temperature (T) decreased with increasing λ leading to the enhanced emission of OM in HFO and reduced OM and BC emission in DF. Contributions of hydrocarbons and oxygenated hydrocarbons increased with λ for HFO and decreased with DF. Gas phase total hydrocarbon (THC) was well correlated with BC only for HFO and OM and BC for DF. Overall, using a lower FSC reduced average PM emissions, however, engine load, and λ were strongly linked to the characteristics and temporal evolution of major PM emissions. The information in this study may help the marine sector and policy-making process in evaluating and designing future solutions for shipping emission regulations and diagnostics.

Online determination of polycyclic aromatic hydrocarbon formation from a flame soot generator.

In this study, we produced a class of diffusion flame soot particles with varying chemical and physical properties by using the mini-Combustion Aerosol STandard (CAST) and applying varying oxidant gas flow rates under constant propane, quenching, and dilution gas supply. We varied the soot properties by using the following fuel-to-air equivalence ratios (Φ): 1.13, 1.09, 1.04, 1.00, 0.96, and 0.89. Within this Φ range, we observed drastic changes in the physical and chemical properties of the soot. Oxidant-rich flames (Φ < 1) were characterized by larger particle size, lower particle number concentration, higher black carbon (BC) concentration, lower brown carbon BrC.[BC](-1) than fuel-rich flames (Φ > 1). To investigate the polycyclic aromatic hydrocarbons (PAH) formation online, we developed a new method for quantification by using the one (13)C-containing doubly charged PAH ion in a high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS). The time-resolved concentration showed that the larger PAHs prevailed in the fuel-rich flames and diminished in the oxidant-rich flames. By comparison with the offline in situ derivatization-thermal-desorption gas-chromatography time-of-flight mass spectrometry (IDTD-GC-ToF-MS), we found that the concentration by using the HR-ToF-AMS was underestimated, especially for lower mass PAHs (C14-C18) in the fuel-rich flames possibly due to size limitation and degradation of semi-volatile species under high vacuum and desorption temperature in the latter. For oxidant-rich flames, the large PAHs (C20 and C22) were detected in the HR-ToF-AMS while it was not possible in IDTD-GC-ToF-MS due to matrix effect. The PAH formation was discussed based on the combination of our results and with respect to Φ settings.

Evaluating the degree of oxygenation of organic aerosol during foggy and hazy days in Hong Kong using high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS)

Abstract. The chemical characteristics of organic aerosol (OA) are still poorly constrained. Here we present observation results of the degree of oxygenation of OA based on high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) measurements made at a coastal site in Hong Kong from late April to the end of May in 2011. Two foggy periods and one hazy period were chosen for detailed analysis to compare the changes in the degree of oxygenation of OA due to different processes. Using HR-ToF-AMS measured inorganic species as input, the Extended Aerosol Inorganic Model (E-AIM) predicted a fine-particle liquid water content (LWCfp) up to 85 μg m−3 during the foggy days. Particle concentration as measured by HR-ToF-AMS was up to 60 μg m−3 during the hazy days and up to 30 μg m−3 during the foggy days. The degree of oxygenation of OA, as indicated by several parameters including the fraction of m/z 44 in organic mass spectra (f44), the elemental ratio of oxygen to carbon (O : C), and the carbon oxidation state (OSc), was evaluated against the odd oxygen (Ox) concentration, LWCfp, ionic strength (IS), and in situ pH (pHis). Observations suggest that the high concentration of OA (on average 11 μg m−3) and the high degree of oxygenation (f44 = 0.15, O : C = 0.51, and OSc = −0.31) during the hazy period were mainly due to gas-phase oxidation. During the foggy periods with low photochemical activities, the degree of oxygenation of OA was almost as high as that on the hazy days, and significantly higher than that during non-foggy/non-hazy days. However, the OA evolved quite differently in the two foggy periods. The first foggy period in late April saw a larger LWCfp and a lower Ox concentration and the OA were made up of ~ 20 % semi-volatile oxygenated organic aerosol (SVOOA) as resolved by positive matrix factorization (PMF). In the second foggy period in mid-May, higher Ox concentration and lower LWCfp were observed, and the OA were found to contain &gt; 50 % low-volatility oxygenated organic aerosols (LVOOA). An examination of the particle characteristics (pHis, IS, and LWCfp) suggests that partitioning may have been the dominating process through which oxygenated species were incorporated into the particle phase during the first foggy period, while oxidation in the aqueous phase dominated over gas-phase processes during the second foggy period.

Comparison of FTIR and Particle Mass Spectrometry for the Measurement of Particulate Organic Nitrates

While multifunctional organic nitrates are formed during the atmospheric oxidation of volatile organic compounds, relatively little is known about their signatures in particle mass spectrometers. High resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) and FTIR spectroscopy on particles impacted on ZnSe windows were applied to NH(4)NO(3), NaNO(3), and isosorbide 5-mononitrate (IMN) particles, and to secondary organic aerosol (SOA) from NO(3) radical reactions at 22 degrees C and 1 atm in air with alpha- and beta-pinene, 3-carene, limonene, and isoprene. For comparison, single particle laser ablation mass spectra (SPLAT II) were also obtained for IMN and SOA from the alpha-pinene reaction. The mass spectra of all particles exhibit significant intensity at m/z 30, and for the SOA, weak peaks corresponding to various organic fragments containing nitrogen [C(x)H(y)N(z)O(a)](+) were identified using HR-ToF-AMS. The NO(+)/NO(2)(+) ratios from HR-ToF-AMS were 10-15 for IMN and the SOA from the alpha- and beta-pinene, 3-carene, and limonene reactions, approximately 5 for the isoprene reaction, 2.4 for NH(4)NO(3) and 80 for NaNO(3). The N/H ratios from HR-ToF-AMS for the SOA were smaller by a factor of 2 to 4 than the -ONO(2)/C-H ratios measured using FTIR. FTIR has the advantage that it provides identification and quantification of functional groups. The NO(+)/NO(2)(+) ratio from HR-ToF-AMS can indicate organic nitrates if they are present at more than 15-60% of the inorganic nitrate, depending on whether the latter is NH(4)NO(3) or NaNO(3). However, unique identification of specific organic nitrates is not possible with either method.

Chemical Composition of Gas- and Aerosol-Phase Products from the Photooxidation of Naphthalene

The current work focuses on the detailed evolution of the chemical composition of both the gas- and aerosol-phase constituents produced from the OH-initiated photooxidation of naphthalene under low- and high-NO(x) conditions. Under high-NO(x) conditions ring-opening products are the primary gas-phase products, suggesting that the mechanism involves dissociation of alkoxy radicals (RO) formed through an RO(2) + NO pathway, or a bicyclic peroxy mechanism. In contrast to the high-NO(x) chemistry, ring-retaining compounds appear to dominate the low-NO(x) gas-phase products owing to the RO(2) + HO(2) pathway. We are able to chemically characterize 53-68% of the secondary organic aerosol (SOA) mass. Atomic oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios measured in bulk samples by high-resolution electrospray ionization time-of-flight mass spectrometry (HR-ESI-TOFMS) are the same as the ratios observed with online high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), suggesting that the chemical compositions and oxidation levels found in the chemically-characterized fraction of the particle phase are representative of the bulk aerosol. Oligomers, organosulfates (R-OSO(3)), and other high-molecular-weight (MW) products are not observed in either the low- or high-NO(x) SOA; however, in the presence of neutral ammonium sulfate seed aerosol, an organic sulfonic acid (R-SO(3)), characterized as hydroxybenzene sulfonic acid, is observed in naphthalene SOA produced under both high- and low-NO(x) conditions. Acidic compounds and organic peroxides are found to account for a large fraction of the chemically characterized high- and low-NO(x) SOA. We propose that the major gas- and aerosol-phase products observed are generated through the formation and further reaction of 2-formylcinnamaldehyde or a bicyclic peroxy intermediate. The chemical similarity between the laboratory SOA and ambient aerosol collected from Birmingham, Alabama (AL) and Pasadena, California (CA) confirm the importance of PAH oxidation in the formation of aerosol within the urban atmosphere.