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Using chemical ionization mass spectrometry to detect particle-phase acids (acid-CIMS) and aerosol mass spectrometry (AMS) measurements from Colorado, USA, and two studies in Hyytiala, Finland, we quantify the fraction of organic aerosol (OA) mass that is composed of molecules with acid functional groups (facid). Molecules containing one or more carboxylic acid functionality contributed approximately 29% (45-51%) of the OA mass in Colorado (Finland). Organic acid mass concentration correlates well with AMS m/z 44 (primarily CO2+), a commonly used marker for highly oxidized aerosol. Using the average empirical relationship between AMS m/z 44 and organic acids in these three studies, together with m/z 44 data from 29 continental northern hemispheric (NH) AMS datasets, we estimate that molecules containing carboxylic acid functionality constitute on average 28% (range 10-50%) of NH continental OA mass with typically higher values at rural/remote sites and during summer and lower values at urban sites and during winter.

Secondary organic aerosol (SOA) derived from isoprene epoxydiols (IEPOX) has potential impacts on regional air quality and climate yet is poorly characterized under NOx-rich ambient environments. We report the first real-time characterization of IEPOX-derived SOA (IEPOX-SOA) in Eastern China in summer 2013 using comprehensive ambient measurements, along with model analysis. The ratio of IEPOX-SOA to isoprene high-NOx SOA precursors, e.g., methyl vinyl ketone and methacrolein, and the reactive uptake potential of IEPOX was lower than those generally observed in regions with prevailing biogenic emissions, low NOx levels, and high particle acidity, elucidating the suppression of IEPOX-SOA formation under NOx-rich environments. IEPOX-SOA showed high potential source regions to the south with large biogenic emissions, illustrating that the interactions between biogenic and anthropogenic emissions might have played an important role in affecting the formation of IEPOX-SOA in polluted environments in Eastern China.

[1] Nighttime chemical evolution of aerosol and trace gases in a coal-fired power plant plume was monitored with the Department of Energy Grumman Gulfstream-1 aircraft during the 2002 New England Air Quality Study field campaign. Quasi-Lagrangian sampling in the plume at increasing downwind distances and processing times was guided by a constant-volume balloon that was released near the power plant at sunset. While no evidence of fly ash particles was found, concentrations of particulate organics, sulfate, and nitrate were higher in the plume than in the background air. The enhanced sulfate concentrations were attributed to direct emissions of gaseous H2SO4, some of which had formed new particles as evidenced by enhanced concentrations of nucleation-mode particles in the plume. The aerosol species were internally mixed and the particles were acidic, suggesting that particulate nitrate was in the form of organic nitrate. The enhanced particulate organic and nitrate masses in the plume were inferred as secondary organic aerosol, which was possibly formed from NO3 radical-initiated oxidation of isoprene and other trace organic gases in the presence of acidic sulfate particles. Microspectroscopic analysis of particle samples suggested that some sulfate was in the form of organosulfates. Microspectroscopy also revealed the presence of sp2 hybridized C = C bonds, which decreased with increasing processing time in the plume, possibly because of heterogeneous chemistry on particulate organics. Constrained plume modeling analysis of the aircraft and tetroon observations showed that heterogeneous hydrolysis of N2O5 was negligibly slow. These results have significant implications for several issues related to the impacts of power plant emissions on air quality and climate.

[1] Photochemically processed urban emissions were characterized at a mountain top location, free from local sources, within the Mexico City Metropolitan Area. Analysis of the Mexico City emission plume demonstrates a strong correlation between secondary organic aerosol and odd oxygen (O3 + NO2). The measured oxygenated-organic aerosol correlates with odd oxygen measurements with an apparent slope of (104–180) μg m−3 ppmv−1 (STP) and r2 > 0.9. The dependence of the observed proportionality on the gas-phase hydrocarbon profile is discussed. The observationally-based correlation between oxygenated organic aerosol mass and odd oxygen may provide insight into poorly understood secondary organic aerosol production mechanisms by leveraging knowledge of gas-phase ozone production chemistry. These results suggest that global and regional models may be able to use the observed proportionality to estimate SOA as a co-product of modeled O3 production until more complete models of SOA formation become available.

[1] Aerosol chemical composition, size distribution, and optical properties were measured during 17 aircraft flights in New England and Middle Atlantic States as part of the summer 2002 New England Air Quality Study field campaign. An Aerodyne aerosol mass spectrometer (AMS) was operated with a measurement cycle of 30 s, about an order of magnitude faster than used for ground-based measurements. Noise levels within a single measurement period were sub μg m−3. Volume data derived from the AMS were compared with volume measurements from a Passive Cavity Aerosol Spectrometer (PCASP) optical particle detector and a Twin Scanning Electrical Mobility Spectrometer (TSEMS); calculated light scattering was compared with measured values from an integrating nephelometer. The median ratio for AMS/TSEMS volume was 1.25 (1.33 with an estimated refractory component); the median ratio for AMS/nephelometer scattering was 1.18. A dependence of the AMS collection efficiency on aerosol acidity was quantified by a comparison between AMS and PCASP volumes in two high sulfate plumes. For the entire field campaign, the average aerosol concentration was 11 μg m−3. Compared with monitoring data from the IMPROVE network, the organic component made up a large fraction of total mass, varying from 70% in clean air to 40% in high concentration sulfate plumes. In combination with other optical and chemical measurements, the AMS gave information on secondary organic aerosol (SOA) production and the time evolution of aerosol light absorption. CO is taken as a conservative tracer of urban emissions and the ratios of organic aerosol and aerosol light absorption to CO examined as a function of photochemical age. Comparisons were made to ratios determined from surface measurements under conditions of minimal atmospheric processing. In air masses in which the NOx to NOy ratio has decreased to 10%, the ratio of organic aerosol to CO has quadrupled indicating that 75% of the organic aerosol is secondary. Also, the ratio of light absorption to CO has more than doubled, which is interpreted as an equivalent increase in the light absorption efficiency of black carbon due to aerosol ageing.

[1] An Aerodyne aerosol mass spectrometer (AMS) was deployed at the Pittsburgh Environmental Protection Agency Supersite from 7 to 22 September 2002 as part of the Pittsburgh Air Quality Study (PAQS). The main objectives of this deployment were to characterize the concentrations, size distributions, and temporal variations of nonrefractory (NR) chemical species in submicron particles (approximately PM1) and to further develop and evaluate the AMS. Reasonably good agreement was observed on particle concentrations, composition, and size distributions between the AMS data and measurements from collocated instruments (given the difference between the PM1 and PM2.5 size cuts), including TEOM, semicontinuous sulfate, 2-hour- and 24-hour-averaged organic carbon, SMPS, 4-hour-averaged ammonium, and micro-orifice uniform deposit impactor. Total NR-PM1 mass concentration in Pittsburgh accumulates over periods of several days punctuated with rapid cleaning due to rain or air mass changes. Sulfate and organics are the major NR-PM1 components while the concentrations of nitrate and chloride are generally low. Significant amounts of ammonium, which most of the time are consistent with sulfate present as ammonium sulfate, are also present in particles. However, there are periods when the aerosols are relatively acidic and more than 50% of sulfate is estimated to be in the form of ammonium bisulfate. No major enhancement of the organic concentration is observed during these acidic periods, which suggests that acid-catalyzed SOA formation was not an important process during this study. Size distributions of particulate sulfate, ammonium, organics, and nitrate vary on timescales of hours to days, showing unimodal, bimodal and even trimodal characteristics. The accumulation mode (peaking around 350–600 nm in vacuum aerodynamic diameter for the mass distributions) and the ultrafine mode (

[1] During the field campaign of the Study of Houston Atmospheric Radical Precursors/Surface-Induced Oxidation of Organics in the Troposphere (SHARP/SOOT) in Houston, Texas, a suite of aerosol instruments was deployed to directly measure a comprehensive set of aerosol properties, including the particle size distribution, effective density, hygroscopicity, and light extinction and scattering coefficients. Those aerosol properties are employed to quantify the mixing state and composition of ambient particles and to gain a better understanding of the formation and transformation of fine particulate matter in this region. During the measurement period, aerosols are often internally mixed, with one peak in the effective density distribution at 1.55 ± 0.07 g cm−3, consistent with a population composed largely of sulfates and organics. Episodically, a second mode below 1.0 g cm−3 is identified in the effective density distributions, reflecting the presence of freshly emitted black carbon (BC) particles. The measured effective density demonstrates a clear diurnal cycle associated with primary emissions from transportation and photochemical aging, with a minimum during the morning rush hour, increasing from 1.4 to 1.5 g cm−3 on average over 5 h, and remaining nearly constant throughout the afternoon. The average BC concentration derived from light-absorption measurements is 0.31 ± 0.22 µg m−3, and the average measured particle single scattering albedo is 0.94 ± 0.04. When elevated BC concentrations are observed, typically during the morning rush hours, single scattering albedo decreases, with a smallest measured value of about 0.7. Aerosol hygroscopicity measurements indicate that larger particles (e.g., 400 nm) are more hygroscopic than smaller particles (e.g., 100 nm). The measurements also reveal discernable meteorological impacts on the aerosol properties. After a frontal passage, the average particle effective density decreases, the average BC concentration increases, and the aerosol size distribution is dominated by new particle formation.

[1] Two Aerodyne aerosol mass spectrometers (AMSs) were deployed at Trinidad Head on the north Californian coast during the National Oceanographic and Atmospheric Administration Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) experiment, to study the physiochemical properties of submicron aerosol particles within the Pacific marine boundary layer. One AMS was modified to allow the study of sea salt-based particles, while the other used a temperature cycling system on its inlet. The reported loadings increased by a factor of 2 when the temperature approached the dew point, which is due to the inlet performance and has implications for other AMS experiments and applications. The processed data were compared with those of a particle into liquid sampler-ion chromatograph and showed that the ammonium, sulfate and organic fractions of the particles were consistently found within a single, normally acidic, accumulation mode at around 300 - 400 nm. However, when influenced by land-based sources, vehicle emissions and increased ammonium loadings were seen. The concentrations of nitrate in the accumulation mode were low, but it was also found within sea salt particles in the coarse mode and can be linked to the displacement of chloride. The organic fraction showed a high degree of chemical ageing and evidence of nitrogen-bearing organics was also observed. The particulate organic data were compared to the volatile organic carbon data derived from an in-situ gas chromatograph-mass spectrometer-flame ionization detector and relationships were found between the gas and particle phase chemicals in both the overall concentrations and the levels of oxidation.

[1] In the paper ‘‘Quantitative sampling using an Aerodyne aerosol mass spectrometer: 1. Techniques of data interpretation and error analysis’’ by J. D. Allan et al. (Journal of Geophysical Research, 108(D3), 4090, doi:10.1029/2002JD002358, 2003), the authors of the Jimenez et al. [2003] reference are incorrect. The correct reference is as follows: Jimenez, J. L., J. T. Jayne, Q. Shi, C. E. Kolb, D. R. Worsnop, I. Yourshaw, J. H. Seinfeld, R. C. Flagan, X. Zhang, K. A. Smith, J. W. Morris, and P. Davidovits, Ambient aerosol sampling using the Aerodyne aerosol mass spectrometer, J. Geophys. Res., 10.1029/ 2001JD001213, in press, 2003. JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 108, NO. D9, 4283, doi:10.1029/2003JD001607, 2003

[1] In part 1 of this series, techniques for generating quantitative information on fine airborne particulate-size and chemically resolved mass concentration from an Aerodyne aerosol mass spectrometer were introduced. Presented here are the results generated using these techniques from sampling U. K. urban air with such an instrument in Edinburgh during October 2000 and in Manchester during July 2001 and January 2002. Data on the total mass concentrations and size-resolved mass distributions of nitrate, sulfate, and organic compounds were obtained for all three campaigns and compared with data from other sources, including a micro-orifice uniform deposit impactor, total particle numbers, CO and NOx concentrations, local wind speed and temperature, and back trajectory analysis. All three locations showed evidence for emissions from local transport, with a mass modal aerodynamic diameter of around 100-200nm. This mode was dominated by hydrocarbons showing little evidence of oxidization. The three sites also exhibited a larger mode consisting of inorganic chemicals and oxidized organics, which appeared to be governed by sources external to the cities and showed evidence of internal mixing. The mass modal aerodynamic diameter varied between approximately 200-500 nm during the winter and 500-800 nm during the summer. The summer also showed an increased mass loading without an increase in total particle number. Evidence of material building up and ageing in the atmospheric surface layer during periods of low wind speeds was also observed.

Received 22 March 2002; revised 2 July 2002; accepted 5 August 2002; published 4 February 2003. [1] The aerosol mass spectrometer (AMS), manufactured by Aerodyne Research, Inc., has been shown to be capable of delivering quantitative information on the chemical composition and size of volatile and semivolatile fine airborne particulate matter with high time resolution. Analytical and software tools for interpreting the data from this instrument and generating meaningful, quantitative results have been developed and are presented here with a brief description of the instrument. These include the conversion of detected ion rates from the quadrupole mass spectrometer during the mass spectrum (MS) mode of operation to atmospheric mass concentrations of chemical species (in m gm � 3 ) by applying calibration data. It is also necessary to correct for variations in the electron multiplier performance, and a method involving the measurement of the instrument’s response to gas phase signals is also presented. The techniques for applying particle velocity calibration data and transforming signals from time of flight (TOF) mode to chemical mass distributions in terms of aerodynamic diameter (dM/dlog(Da) distributions) are also presented. It is also possible to quantify the uncertainties in both MS and TOF data by evaluating the ion counting statistics and variability of the background signal, respectively. This paper is accompanied by part 2 of this series, in which these methods are used to process and analyze AMS results on ambient aerosol from two U.K. cities at different times of the year. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0394 Atmospheric Composition and Structure: Instruments and techniques; 0399 Atmospheric Composition and Structure: General or miscellaneous; KEYWORDS: aerosols, chemical composition, mass spectrometry, analysis techniques

During the Atlanta Supersite Project, four particle mass spectrometers were operated together for the first time: NOAA's Particle Analysis by Laser Mass Spectrometer (PALMS), University of California at Riverside's Aerosol Time-of-Flight Mass Spectrometer (ATOFMS), University of Delaware's Rapid Single-Particle Mass Spectrometer II (RSMS-II), and Aerodyne's Aerosol Mass Spectrometer (AMS). Although these mass spectrometers are generally classified as similar instruments, they clearly have different characteristics due to their unique designs. One primary difference is related to the volatilization/ionization method: PALMS, ATOFMS, and RSMS-II utilize laser desorption/ionization, whereas particles in the AMS instrument are volatilized by impaction onto a heated surface with the resulting components ionized by electron impact. Thus mass spectral data from the AMS are representative of the ensemble of particles sampled, and those from the laser-based instruments are representative of individual particles. In addition, the AMS instrument cannot analyze refractory material such as soot, sodium chloride, and crustal elements, and some sulfate or water-rich particles may not always be analyzed with every laser-based instrument. A main difference among the laser-based mass spectrometers is that the RSMS-II instrument can obtain size-resolved single particle composition information for particles with aerodynamic diameters as small as 15 nm. The minimum sizes analyzed by ATOFMS and PALMS are 0.2 and about 0.35 μm, respectively, in aerodynamic diameter. Furthermore, PALMS, ATOFMS, and RSMS-II use different laser ionization conditions. Despite these differences the laser-based instruments found similar individual particle classifications, and their relative fractions among comparable sized particles from Atlanta were broadly consistent. Finally, the AMS measurements of the nitrate/sulfate mole ratio were highly correlated with composite measurements (r^2 = 0.93). In contrast, the PALMS nitrate/sulfate ion ratios were only moderately correlated (r^2 ∼ 0.7).

An Aerodyne aerosol mass spectrometer (AMS) was deployed during the Aerosol Characterization Experiment-Asia (ACE-Asia) field campaign on board the Center for Interdisciplinary Remotely Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft to measure the size-resolved chemical composition of submicron aerosols in the outflow from eastern Asia. Research flights were carried out from 31 March to 1 May 2001 in an area that covered 127°E–135°E and 32°N–38°N. Valid data from the AMS were obtained during 15 out of a total of 19 research flights. During the mission the AMS measured distinct layers (from the boundary layer to ∼3700 m) of submicron aerosols composed of sulfate, ammonium, and organics as the major nonrefractory components, separated by layers with much lower aerosol concentrations. Sulfate and organics mass concentrations of up to 10 μg m^(−3) and 13 μg m^(−3), respectively, were measured in some pollution layers. Back-trajectory analysis shows that the polluted layers originated in urban and industrial areas of China and Korea. The mass-weighed size distribution of the submicron sulfate was relatively constant from day to day and layer to layer, with an aerodynamic diameter mode of 400–500 nm and a width (full width half maximum) of about 450 nm in most of the layers. On the days with low influence of dust in the aerosol outflow, as indicated by other instruments aboard the Twin Otter, the total mass of nonrefractory aerosols estimated by the AMS correlated well with total volume of aerosols measured by a differential mobility analyzer.

Rate constants and products were measured for over 50 ion-molecule reactions involving SO3 or ions formed from SO3. All negative ions studied reacted with SO3 at or near the collisional rate by a variety of processes including charge transfer, O− transfer, ligand exchange, and clustering. Ambient negative ions tended to form SO− 4 or SO− 4 core ions. A chemical ionization detection scheme for monitoring SO3 in the atmosphere is presented based on CO−3 (H2O)n = 0–1 or NO−3 (H2O)n = 0–1 as the primary ions. The proposed scheme can be used in conjunction with previous schemes for monitoring SO2 and H2SO4 concentrations to measure all three gases simultaneously. The measurements also confirm that the ion chemistry used in separate studies to monitor the reaction of SO3 with H2O is correct and rapid and that the reaction of SO3 with positive ion water clusters does not contribute to H2SO4 production in the atmosphere.