[Show abstract][Hide abstract] ABSTRACT: The errors inherent in the fitting and integration of the pseudo-Gaussian ion peaks in Aerodyne high-resolution aerosol mass spectrometers (HR-AMSs) have not been previously addressed as a source of imprecision for these or similar instruments. This manuscript evaluates the significance of this imprecision and proposes a method for their estimation in routine data analysis. In the first part of this work, it is shown that peak-integration errors are expected to scale linearly with peak height for the constrained-peak-shape fits performed in the HR-AMS. An empirical analysis is undertaken to investigate the most complex source of peak-integration imprecision: the imprecision in fitted peak height, σ h. It is shown that the major contributors to σ h are the imprecision and bias inherent in the m/z calibration, both of which may arise due to statistical and physical non-idealities of the instrument. A quantitative estimation of these m/z-calibration imprecisions and biases show that they may vary from ion to ion, even for ions of similar m/z. In the second part of this work, the empirical analysis is used to constrain a Monte Carlo approach for the estimation of σ h and thus the peak-integration imprecision. The estimated σ h for selected well-separated peaks (for which m/z-calibration imprecision and bias could be quantitatively estimated) scaled linearly with peak height as expected (i.e. as n 1). In combination with the imprecision in peak-width quantification (which may be easily and directly estimated during quantification), peak-fitting imprecisions therefore dominate counting imprecisions (which scale as n 0.5) at high signals. The previous HR-AMS uncertainty model therefore underestimates the overall fitting imprecision even for well-resolved peaks. We illustrate the importance of this conclusion by performing positive matrix factorization on a synthetic HR-AMS data set both with and without its inclusion. In the third part of this work, the Monte Carlo approach is extended to the case of an arbitrary number of overlapping peaks. Here, a modification to the empirically constrained approach was needed, because the ion-specific m/z-calibration bias and imprecision can generally only be estimated for well-resolved peaks. The modification is to simply overestimate the m/z-calibration imprecision in all cases. This over-estimation results in only a slight overestimate of σ h , while significantly reducing the sensitivity of σ h to the unknown, ion-specific m/z-calibration biases. Thus, with only the mea-Published by Copernicus Publications on behalf of the European Geosciences Union. 4616 J. C. Corbin et al.: AMS peak-integration errors sured data and an approximate estimate of the order of magnitude of m/z-calibration biases as input, conservative and unbiased estimates of peak-integration imprecisions may be obtained for each peak in any ensemble of overlapping peaks.
[Show abstract][Hide abstract] ABSTRACT: Under certain conditions, secondary organic aerosol (SOA) particles can exist in the atmosphere in an amorphous solid or semi-solid state. To determine their relevance to processes such as ice nucleation or chemistry occurring within particles requires knowledge of the temperature and relative humidity (RH) range for SOA to exist in these states. In the CLOUD experiment at CERN, we deployed a new in-situ optical method to detect the viscosity of α-pinene SOA particles and measured their transition from the amorphous viscous to liquid state. The method is based on the depolarising properties of laboratory-produced non-spherical SOA particles and their transformation to non-depolarising spherical liquid particles during deliquescence. We found that particles formed and grown in the chamber developed an asymmetric shape through coagulation. A transition to spherical shape was observed as the RH was increased to between 35 % at −10 °C and 80 % at −38 °C, confirming previous calculations of the viscosity transition conditions. Consequently, α-pinene SOA particles exist in a viscous state over a wide range of ambient conditions, including the cirrus region of the free troposphere. This has implications for the physical, chemical and ice-nucleation properties of SOA and SOA-coated particles in the atmosphere.
[Show abstract][Hide abstract] ABSTRACT: Atmospheric amines may play a crucial role in formation of new aerosol particles via nucleation with sulfuric acid. Recent studies have revealed that concentrations below 1 pptV can significantly promote nucleation of sulfuric acid particles. While sulfuric acid detection is relatively straightforward, no amine measurements to date have been able to reach the critical sub-pptV concentration range and atmospheric amine concentrations are in general poorly characterized. In this work we present a proof-of-concept of an instrument capable of detecting dimethyl amine (DMA) with concentrations even down to 70 ppqV (parts per quadrillion, 0.07 pptV) for a 15 min integration time. Detection of ammonia and amines other than dimethyl amine is discussed. We also report results from the first ambient measurements performed in spring 2013 at a boreal forest site. While minute signals above the signal-to-noise ratio that could be attributed to trimethyl or propyl amine were observed, DMA concentration never exceeded the detection threshold of ambient measurements (150 ppqV), thereby questioning, though not excluding, the role of DMA in nucleation at this location.
[Show abstract][Hide abstract] ABSTRACT: Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H2SO4–H2O) system and the ternary system involving ammonia (H2SO4–H2O–NH3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H2SO4·NH3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H2SO4·NH3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry.
[Show abstract][Hide abstract] ABSTRACT: High concentrations of fine particles (PM2.5) are frequently observed during all seasons in Beijing, China, leading to severe air pollution and human health problems in this megacity. In this study, we conducted real-time measurements of non-refractory submicron aerosol (NR-PM1) species (sulfate, nitrate, ammonium, chloride, and organics) in Beijing using an Aerodyne Aerosol Chemical Speciation Monitor for 1 year, from July 2011 to June 2012. This is the first long-term, highly time-resolved (~ 15 min) measurement of fine particle composition in China. The seasonal average (± 1σ) mass concentration of NR-PM1 ranged from 52 (± 49) μg m−3 in the spring season to 62 (± 49) μg m−3 in the summer season, with organics being the major fraction (40–51%), followed by nitrate (17–25%) and sulfate (12–17%). Organics and chloride showed pronounced seasonal variations, with much higher concentrations in winter than in the other seasons, due to enhanced coal combustion emissions. Although the seasonal variations of secondary inorganic aerosol (SIA = sulfate + nitrate + ammonium) concentrations were not significant, higher contributions of SIA were observed in summer (57–61%) than in winter (43–46%), indicating that secondary aerosol production is a more important process than primary emissions in summer. Organics presented pronounced diurnal cycles that were similar among all seasons, whereas the diurnal variations of nitrate were mainly due to the competition between photochemical production and gas–particle partitioning. Our data also indicate that high concentrations of NR-PM1 (> 60 μg m−3) are usually associated with high ambient relative humidity (RH) (> 50%) and that severe particulate pollution is characterized by different aerosol composition in different seasons. All NR-PM1 species showed evident concentration gradients as a function of wind direction, generally with higher values associated with wind from the south, southeast or east. This was consistent with their higher potential as source areas, as determined by potential source contribution function analysis. A common high potential source area, located to the southwest of Beijing along the Taihang Mountains, was observed during all seasons except winter, when smaller source areas were found. These results demonstrate a high potential impact of regional transport from surrounding regions on the formation of severe haze pollution in Beijing.
[Show abstract][Hide abstract] ABSTRACT: New measurements of water diffusion in aerosol particles produced from secondary organic aerosol (SOA) material and from a number of organic/inorganic model mixtures (3-methylbutane-1,2,3-tricarboxylic acid (3-MBTCA), levoglucosan, levoglucosan/NH4HSO4, raffinose) indicate that water diffusion coefficients are determined by several properties of the aerosol substance and cannot be inferred from the glass transition temperature or bouncing properties. Our results suggest that water diffusion in SOA particles is faster than often assumed and imposes no significant kinetic limitation on water uptake and release at temperatures above 220 K. The fast diffusion of water suggests that heterogeneous ice nucleation on a glassy core is very unlikely in these systems. At temperatures below 220 K, model simulations of SOA droplets suggest that heterogeneous ice nucleation may occur in the immersion mode on glassy cores which remain embedded in a liquid shell when experiencing fast updraft velocities. The particles absorb significant quantities of water during these updrafts which plasticize their outer layers such that these layers equilibrate readily with the gas phase humidity before the homogeneous ice nucleation threshold is reached. Glass formation is thus unlikely to restrict homogeneous ice nucleation. Only under most extreme conditions near the very high tropical tropopause may the homogeneous ice nucleation rate coefficient be reduced as a consequence of slow condensed-phase water diffusion. Since the differences between the behavior limited or non limited by diffusion are small even at the very high tropical tropopause, condensed-phase water diffusivity is unlikely to have significant consequences on the direct climatic effects of SOA particles under tropospheric conditions.
[Show abstract][Hide abstract] ABSTRACT: We report comprehensive, demonstrably contaminant-free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion-induced pathways conducted in the CERN CLOUD chamber. The recently developed Atmospheric Pressure interface-Time Of Flight-Mass Spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (105 to 109 molecules cm−3), relative humidity (11% to 58%), temperature (207K to 299K), and total ion concentration (0 to 6800 ions cm−3). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3 nm to 3.2 nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC-normalized CNT), which is described in a companion paper. The formation rates predicted by the QC-normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion-induced) sulfuric acid- water system. Formation rates increase with RH, sulfuric acid and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions neutral particle formation dominates at low temperatures, while ion-induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC-normalized CNT as a powerful tool to study neutral and ion-induced binary particle formation in atmospheric modeling.
Journal of Geophysical Research Atmospheres 09/2015; DOI:10.1002/2015JD023539 · 3.43 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The mitigation of air pollution in megacities remains a great challenge because of the complex sources and formation mechanisms of aerosol particles. The 2014 Asia- Pacific Economic Cooperation (APEC) summit in Beijing serves as a unique experiment to study the impacts of emission controls on aerosol composition, size distributions, and oxidative properties. Herein, a high-resolution time-of-flight aerosol mass spectrometer was deployed in urban Beijing for real-time measurements of size-resolved non-refractory submicron aerosol (NR-PM1) species from 14 October to 12 November 2014, along with a range of collocated measurements. The average (±σ) PM1 was 41.6 (±38.9) μg m−3 during APEC, which was decreased by 53 % compared with that before APEC. The aerosol composition showed substantial changes owing to emission controls during APEC. Secondary inorganic aerosols (SIA = sulfate + nitrate + ammonium) showed significant reductions of 62–69 %, whereas organics presented much smaller decreases (35 %). The results from the positive matrix factorization of organic aerosols (OA) indicated that highly oxidized secondary OA (SOA) showed decreases similar to those of SIA during APEC. However, primary OA (POA) from cooking, traffic, and biomass burning sources were comparable to those before APEC, indicating the presence of strong local source emissions. The oxidation properties showed corresponding changes in response to OA composition. The average oxygen-to-carbon level during APEC was 0.36 (±0.10), which is lower than the 0.43 (±0.13) measured before APEC, demonstrating a decrease in the OA oxidation degree. The changes in size distributions of primary and secondary species varied during APEC. SIA and SOA showed significant reductions in large accumulation modes with peak diameters shifting from ~ 650 to 400 nm during APEC, whereas those of POA remained relatively unchanged. The changes in aerosol composition, size distributions, and oxidation degrees during the aging processes were further illustrated in a case study of a severe haze episode. Our results elucidated a complex response of aerosol chemistry to emission controls, which has significant implications that emission controls over regional scales can substantially reduce secondary particulates. However, stricter emission controls for local source emissions are needed for further mitigating air pollution in the megacity of Beijing.
[Show abstract][Hide abstract] ABSTRACT: The composition of PM1 (particulate matter with diameter less than 1 μm) in the greater London area was characterized during the Clean Air for London (ClearfLo) project in winter 2012. Two High-Resolution Time-of-Flight Aerosol Mass Spectrometers (HR-ToF-AMS) were deployed at a rural site (Detling, Kent) and an urban site (North Kensington, London). The simultaneous and high-temporal resolution measurements at the two sites provide a unique opportunity to investigate the spatial distribution of PM1. We find that the organic aerosol (OA) concentration is comparable between the rural and urban sites, but the sources of OA are distinctly different. The concentration of solid fuel OA at the urban site is about twice as high as at the rural site, due to elevated domestic heating in the urban area. While the concentrations of oxygenated OA (OOA) are well-correlated between the two sites, the OOA concentration at the rural site is almost twice that of the urban site. At the rural site, more than 70 % of the carbon in OOA is estimated to be non-fossil, which suggests that OOA is likely related to aged biomass burning considering the small amount of biogenic SOA in winter. Thus, it is possible that the biomass burning OA contributes a larger fraction of ambient OA in wintertime than what previous field studies have suggested. A suite of instruments was deployed downstream of a thermal denuder (TD) to investigate the volatility of PM1 species at the rural Detling site. After heating at 250 °C in the TD, 40 % of the residual mass is OA, indicating the presence of non-volatile organics in the aerosol. Although the OA associated with refractory black carbon (rBC, measured by a soot-particle aerosol mass spectrometer) only accounts for < 10 % of the total OA (measured by a HR-ToF-AMS) at 250 °C, the two measurements are well-correlated, suggesting that the non-volatile organics have similar sources or have undergone similar chemical processing as rBC in the atmosphere. Finally, we discuss the relationship between the OA volatility and atomic O : C and find that particles with a wide range of O : C could have similar mass fraction remaining after heating. This analysis emphasizes the importance of understanding the distribution of volatility and O : C in bulk OA.
[Show abstract][Hide abstract] ABSTRACT: The megacity of Beijing has experienced frequent severe fine particle pollution during the last decade. Although the sources and formation mechanisms of aerosol particles have been extensively investigated on the basis of ground measurements, real-time characterization of aerosol particle composition and sources above the urban canopy in Beijing is rare. In this study, we conducted real-time measurements of non-refractory submicron aerosol (NR-PM1) composition at 260 m at the 325 m Beijing Meteorological Tower (BMT) from 10 October to 12 November 2014, by using an aerosol chemical speciation monitor (ACSM) along with synchronous measurements of size-resolved NR-PM1 composition at near ground level using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR–ToF–AMS). The NR-PM1 composition above the urban canopy was dominated by organics (46 %), followed by nitrate (27 %) and sulfate (13 %). The high contribution of nitrate and high NO3−/SO42− mass ratios illustrate an important role of nitrate in particulate matter (PM) pollution during the study period. The organic aerosol (OA) was mainly composed by secondary OA (SOA), accounting for 61 % on an average. Different from that measured at the ground site, primary OA (POA) correlated moderately with SOA, likely suggesting a high contribution from regional transport above the urban canopy. The Asia–Pacific Economic Cooperation (APEC) summit with strict emission controls provides a unique opportunity to study the impacts of emission controls on aerosol chemistry. All aerosol species were shown to have significant decreases of 40–80 % during APEC from those measured before APEC, suggesting that emission controls over regional scales substantially reduced PM levels. However, the bulk aerosol composition was relatively similar before and during APEC as a result of synergetic controls of aerosol precursors such as SO2, NOx, and volatile organic compounds (VOCs). In addition to emission controls, the routine circulations of mountain–valley breezes were also found to play an important role in alleviating PM levels and achieving the "APEC blue" effect. The evolution of vertical differences between 260 m and the ground level was also investigated. Our results show complex vertical differences during the formation and evolution of severe haze episodes that are closely related to aerosol sources and boundary layer dynamics.
[Show abstract][Hide abstract] ABSTRACT: Understanding organic composition of gases and particles is essential to identifying sources and atmospheric processing leading to organic aerosols (OA), but atmospheric chemical complexity and the analytical techniques available often limit such analysis. Here we present speciated measurements of semivolatile and intermediate volatility organic compounds (S/IVOCs) using a novel dual-use instrument (SVTAG-AMS) deployed at Manitou Forest, CO during the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen – Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) 2011 campaign. This instrument provides on-line speciation of ambient organic compounds with 2 h time resolution. The species in this volatility range are complex in composition, but their chemical identities reveal potential sources. Observed compounds of biogenic origin include sesquiterpenes with molecular formula C15H24 (e.g. β-caryophyllene and longifolene), which were most abundant at night. A variety of other biogenic compounds were observed, including sesquiterpernoids with molecular formula C15H22, abietatriene and other terpenoid compounds. Many of these compounds have been identified in essential oils and branch enclosure studies but were observed in ambient air for the first time in our study. Semivolatile polycyclic aromatic hydrocarbons (PAHs) and alkanes were observed with highest concentrations during the day and the dependence on temperature suggests the role of an evaporative source. Using statistical analysis by positive matrix factorization (PMF), we classify observed S/IVOCs by their likely sources and processes, and characterize them based on chemical composition. The total mass concentration of elutable S/IVOCs was estimated to be on the order of 0.7 μg m−3 and their volatility distributions are estimated for modeling aerosol formation chemistry.
[Show abstract][Hide abstract] ABSTRACT: Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H2SO4-H2O) system, and the ternary system involving ammonia (H2SO4-H2O-NH3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a Chemical Ionization Mass Spectrometer (CIMS). From these measurements dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H2SO4 • NH3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H2SO4 • NH3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using Chemical Ionization-Atmospheric Pressure interface-Time Of Flight (CI-APi-TOF) mass spectrometry.
[Show abstract][Hide abstract] ABSTRACT: The composition of secondary organic aerosols (SOAs) formed by β-pinene ozonolysis was experimentally investigated in the Juelich aerosol chamber. Partitioning of oxidation products between gas and particles was measured through concurrent concentration measurements in both phases. Partitioning coefficients (Kp) of 2.23 × 10−5 ± 3.20 × 10−6 m3 μg−1 for nopinone, 4.86 × 10−4 ± 1.80 × 10−4 m3 μg−1 for apoverbenone, 6.84 × 10−4 ± 1.52 × 10−4 m3 μg−1 for oxonopinone and 2.00 × 10−3 ± 1.13 × 10−3 m3 μg−1 for hydroxynopinone were derived, showing higher values for more oxygenated species. The observed Kp values were compared with values predicted using two different semi-empirical approaches. Both methods led to an underestimation of the partitioning coefficients with systematic differences between the methods. Assuming that the deviation between the experiment and the model is due to non-ideality of the mixed solution in particles, activity coefficients of 4.82 × 10−2 for nopinone, 2.17 × 10−3 for apoverbenone, 3.09 × 10−1 for oxonopinone and 7.74 × 10−1 for hydroxynopinone would result using the vapour pressure estimation technique that leads to higher Kp. We discuss that such large non-ideality for nopinone could arise due to particle phase processes lowering the effective nopinone vapour pressure such as diol- or dimer formation. The observed high partitioning coefficients compared to modelled results imply an underestimation of SOA mass by applying equilibrium conditions.
[Show abstract][Hide abstract] ABSTRACT: Isoprene produced in forest ecosystems is the most abundantly emitted non-methane volatile organic compound in the Earth’s atmosphere. Recent laboratory and field studies suggest that photooxidation of isoprene forms appreciable amounts of secondary organic aerosol (SOA), which likely affects climate by scattering solar radiation and by acting as cloud condensation nuclei (CCN). As these climate effects depend on both aerosol size and number concentration, it is crucial to understand how SOA partitioning influences particle growth kinetics. Recent studies indicate that biogenic SOA becomes increasingly viscous as relative humidity decreases, with the theoretical implication that its reduced bulk diffusivity slows down further growth via condensation of semivolatile organic compounds. We present here evidences from chamber experiments and the CARES field campaign for such bulk diffusion-limited growth of isoprene SOA formed in the presence of pre-existing Aitken and accumulation mode aerosols and relative humidity ≤ 50%. Kinetic modeling of the aerosol size distribution evolution suggests that the condensing isoprene photooxidation products are semivolatile and the bulk diffusivity is on the order 10^-15 cm2 s-1. The model also successfully reproduces the evaporation kinetics of size-selected chamber particles using similar estimates of bulk diffusivity and volatility for isoprene SOA. As the bulk diffusion timescale decreases a hundred-fold with a ten-fold decrease in size, the hindered growth of viscous accumulation mode particles effectively promotes the growth of the Aitken mode particles that are competing to absorb the semivolatile vapors. Isoprene SOA formation over forests thus represents a Gaia-like self-regulating system that produces CCN more efficiently under progressively drier conditions.
[Show abstract][Hide abstract] ABSTRACT: Particle size distributions in the range of 1.34-615 nm were recorded from 25 November 2013 to 25 January 2014 in urban Shanghai, using a combination of one nano condensation nucleus counter system, one nano scanning mobility particle sizer (SMPS), and one long-SMPS. Measurements of sulfur dioxide by an SO2 analyzer with pulsed UV fluorescence technique allowed calculation of sulfuric acid proxy. In addition, concentrations of ammonia were recorded with a differential optical absorption spectroscopy. During this 62-day campaign, 13 new particle formation (NPF) events were identified with strong bursts of sub-3 nm particles and subsequent fast growth of newly formed particles. The observed nucleation rate (J(1.34)), formation rate of 3 nm particles (J(3)), and condensation sink were 112.4-271.0 cm(-3) s(-1), 2.3-19.2 cm(-3) s(-1), and 0.030-0.10 s(-1), respectively. Subsequent cluster/nanoparticle growth (GR) showed a clear size dependence, with average values of GR(1.35 similar to 1.39), GR(1.39 similar to 1.46), GR(1.46 similar to 1.70), GR(1.70 similar to 2.39), GR(2.39 similar to 7), and GR(7 similar to 20) being 1.6 +/- 1.0, 1.4 +/- 2.2, 7.2 +/- 7.1, 9.0 +/- 11.4, 10.9 +/- 9.8, and 11.4 +/- 9.7 nm h(-1), respectively. Correlation between nucleation rate (J(1.34)) and sulfuric acid proxy indicates that nucleation rate J(1.34) was proportional to a 0.65 +/- 0.28 power of sulfuric acid proxy, indicating that the nucleation of particles can be explained by the activation theory. Correlation between nucleation rate (J(1.34)) and gas-phase ammonia suggests that ammonia was associated with NPF events. The calculated sulfuric acid proxy was sufficient to explain the subsequent growth of 1.34-3 nm particles, but its contribution became smaller as the particle size grew. Qualitatively, NPF events in urban Shanghai likely occur on days with low levels of aerosol surface area, meaning the sulfuric acid proxy is only a valid predictor when aerosol surface area is low.
[Show abstract][Hide abstract] ABSTRACT: Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state ([bar over OS][subscript C]) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H[subscript 2]O[superscript +] and CO[superscript +] ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H[subscript 2]O[superscript +], CO[superscript +], and CO[subscript 2][superscript +] fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO[superscript +] and especially H[subscript 2]O[superscript +] produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The [bar over OS][subscript C] values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 [bar over OS][subscript C] units). This indicates that [bar over OS][subscript C] is a more robust metric of oxidation than O : C, likely since [bar over OS][subscript C] is not affected by hydration or dehydration, either in the atmosphere or during analysis.
[Show abstract][Hide abstract] ABSTRACT: The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from <2 to 1400 pptv, [H2SO4] from 3.3 x 10(6) to 1.4 x 10(9) cm(-3) (0.1 to 56 pptv), and a temperature range from -25 to +20 degrees C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4 / only form at [NH3] / [H2SO4] < 0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Delta m/Delta n), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Delta m/Delta n saturated between 1 and 1.4 for [NH3] / [H2SO4] > 10. Positively charged clusters grew on average by Delta m/Delta n = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, in close resemblance to the acid-base bindings of ammonium bisulfate. Supported by model simulations, we substantiate previous evidence for acid-base reactions being the essential mechanism behind the formation of these clusters under atmospheric conditions and up to sizes of at least 2 nm. Our results also suggest that electrically neutral NH3-H2SO4 clusters, unobservable in this study, have generally the same composition as ionic clusters for [NH3] / [H2SO4] > 10. We expect that NH3-H2SO4 clusters form and grow also mostly by Delta m/Delta n > 1 in the atmosphere's boundary layer, as [NH3] / [H2SO4] is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH3-H2SO4 anion clusters during new-particle formation in the Finnish boreal forest. However, the exact role of NH3-H2SO4 clusters in boundary layer particle formation remains to be resolved.
[Show abstract][Hide abstract] ABSTRACT: Recent developments in high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made it possible to directly detect atmospheric organic compounds in real time with high sensitivity and with little or no fragmentation, including low-volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, using ions identified by high-resolution spectra from an HR-ToF-CIMS with acetate reagent ion chemistry, we develop an algorithm to estimate the vapor pressures of measured organic acids. The algorithm uses identified ion formulas and calculated double bond equivalencies, information unavailable in quadrupole CIMS technology, as constraints for the number of possible oxygen-containing functional groups. The algorithm is tested with acetate chemical ionization mass spectrometry (acetate-CIMS) spectra of O-3 and OH oxidation products of alpha-pinene and naphthalene formed in a flow reactor with integrated OH exposures ranged from 1.2 x 10(11) to 9.7 x 10(11) molec scm(-3), corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. The predicted condensed-phase secondary organic aerosol (SOA) average acid yields and O / C and H / C ratios agree within uncertainties with previous chamber and flow reactor measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.
[Show abstract][Hide abstract] ABSTRACT: The soot-particle aerosol mass spectrometer (SP-AMS) uses an intra-cavity infrared laser to vaporize refractory black carbon (rBC) containing particles, making the particle beam–laser beam overlap critical in determining the collection efficiency (CE) for rBC and associated non-refractory particulate matter (NR-PM). This work evaluates the ability of the SP-AMS to quantify rBC and NR-PM mass in internally mixed particles with different thicknesses of organic coating. Using apparent relative ionization efficiencies for uncoated and thickly coated rBC particles, we report measurements of SP-AMS sensitivity to NR-PM and rBC, for Regal Black, the recommended particulate calibration material. Beam width probe (BWP) measurements are used to illustrate an increase in sensitivity for highly coated particles due to narrowing of the particle beam, which enhances the CE of the SP-AMS by increasing the laser beam–particle beam overlap. Assuming complete overlap for thick coatings, we estimate CE for bare Regal Black particles of 0.6 ± 0.1, which suggests that previously measured SP-AMS sensitivities to Regal Black were underestimated by up to a factor of 2. The efficacy of the BWP measurements is highlighted by studies at a busy road in downtown Toronto and at a non-roadside location, which show particle beam widths similar to, but greater than that of bare Regal Black and coated Regal Black, respectively. Further BWP measurements at field locations will help to constrain the range of CE for fresh and aged rBC-containing particles. The ability of the SP-AMS to quantitatively assess the composition of internally mixed particles is validated through measurements of laboratory-generated organic coated particles, which demonstrate that the SP-AMS can quantify rBC and NR-PM over a wide range of particle compositions and rBC core sizes.
[Show abstract][Hide abstract] ABSTRACT: We performed a systematic intercomparison study of the chemistry and yields of SOA generated from OH oxidation of a common set of gas-phase precursors in a Potential Aerosol Mass (PAM) continuous flow reactor and several environmental chambers. In the flow reactor, SOA precursors were oxidized using OH concentrations ranging from 2.0×108 to 2.2×1010 molec cm−3 over exposure times of 100 s. In the environmental chambers, precursors were oxidized using OH concentrations ranging from 2×106 to 2×107 molec cm−3 over exposure times of several hours. The OH concentration in the chamber experiments is close to that found in the atmosphere, but the integrated OH exposure in the flow reactor can simulate atmospheric exposure times of multiple days compared to chamber exposure times of only a day or so. A linear correlation analysis of the mass spectra (m=0.91–0.92, r2=0.93–0.94) and carbon oxidation state (m=1.1, r2=0.58) of SOA produced in the flow reactor and environmental chambers for OH exposures of approximately 1011 molec cm−3 s suggests that the composition of SOA produced in the flow reactor and chambers is the same within experimental accuracy as measured with an aerosol mass spectrometer. This similarity in turn suggests that both in the flow reactor and in chambers, SOA chemical composition at low OH exposure is governed primarily by gas-phase OH oxidation of the precursors, rather than heterogeneous oxidation of the condensed particles. In general, SOA yields measured in the flow reactor are lower than measured in chambers for the range of equivalent OH exposures that can be measured in both the flow reactor and chambers. The influence of sulfate seed particles on isoprene SOA yield measurements was examined in the flow reactor. The studies show that seed particles increase the yield of SOA produced in flow reactors by a factor of 3 to 5 and may also account in part for higher SOA yields obtained in the chambers, where seed particles are routinely used.