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Long-term measurements of the composition and mass concentration of particulate matter (PM) are essential for source apportionment, epidemiological studies, and air quality trends. Over the past ten years, the Aerosol Chemical Speciation Monitor (ACSM) has been widely used for long-term, in situ, high time resolution measurements. However, to date there are limited measurements with these instruments in Africa and South/Southeast Asia. The measurements that have been made in these regions suggest the presence of varied and complex sources. Current ACSMs have unit mass resolution (UMR), which impacts detection limits and separation and identification of ions, limiting source apportionment. Here, we present a new instrument, the Time-of-Flight ACSM with eXtended resolution (TOF-ACSM-X) with updated analysis software (Tofware) to allow for high-resolution peak fitting. The TOF-ACSM-X has a mass resolution of ~2000 m/Δm, which is approximately an order of magnitude higher than the other versions of the ACSM. This enhanced resolution improves ammonium detection limits by approximately 2-orders of magnitude, from ~0.200 μg m-3 to ~0.008 μg m-3 (TOF-ACSM versus TOF-ACSM-X, respectively), for 15-minute integration times. Intercomparisons of the TOF-ACSM-X with other measurements show improved performance in source apportionment and elemental analysis.

Oxidation flow reactors (OFRs) are an emerging tool for studying the formation and oxidative aging of organic aerosols and other applications. The majority of OFR studies to date have involved the generation of the hydroxyl radical (OH) to mimic daytime oxidative aging processes. In contrast, the use of the nitrate radical (NO3) in modern OFRs to mimic nighttime oxidative aging processes has been limited due to the complexity of conventional techniques that are used to generate NO3. Here, we present a new method that uses a laminar flow reactor (LFR) to continuously generate dinitrogen pentoxide (N2O5) in the gas phase at room temperature from the NO2 + O3 and NO2 + NO3 reactions. The N2O5 is then injected into a dark Potential Aerosol Mass (PAM) OFR and decomposes to generate NO3; hereafter, this method is referred to as “OFR-iN2O5” (where “i” stands for “injected”). To assess the applicability of the OFR-iN2O5 method towards different chemical systems, we present experimental and model characterization of the integrated NO3 exposure, NO3:O3, NO2:NO3, and NO2:O2 as a function of LFR and OFR conditions. These parameters were used to investigate the fate of representative organic peroxy radicals (RO2) and aromatic alkyl radicals generated from volatile organic compound (VOC) + NO3 reactions, and VOCs that are reactive towards both O3 and NO3. Finally, we demonstrate the OFR-iN2O5 method by generating and characterizing secondary organic aerosol from the β-pinene + NO3 reaction.

Ozone (O3), a potent greenhouse gas that is detrimental to human health, is typically found in elevated concentrations within biomass burning (BB) smoke plumes. The radical species OH, HO2, and RO2 (known collectively as ROx) have central roles in the formation of secondary pollutants including O3 but are poorly characterized for BB plumes. We present measurements of total peroxy radical concentrations ([XO2] ≡ [HO2] + [RO2]) and additional trace-gas and particulate matter measurements from McCall, Idaho during August 2018. There were five distinct periods in which BB smoke impacted this site. During BB events, O3 concentrations were enhanced as evidenced by ozone enhancement ratios (ΔO3/ ΔCO) that ranged up to 0.25 ppbv ppbv−1. [XO2] was similarly elevated during some BB events. Overall, quantified instantaneous ozone production rates (P(O3)) were only slightly impacted by the presence of smoke as NOx enhancements were minimal. Measured XO2 concentrations were compared to zero-dimensional box modeling results to evaluate the effectiveness of the Master Chemical Mechanism (MCM) and GEOS-Chem mechanisms during periods of BB influence and overall agreed within 31 %. One period of BB influence had distinct measured enhancements of 15 pptv XO2 that were not reflected in the model output, likely due to the presence of an unmeasured HOx source, quite likely nitrous acid (HONO). To our knowledge, this is the first BB study featuring peroxy radical measurements.

Single particle mass spectrometer (SPMS) instruments have been used for in-situ chemical characterization of atmospheric aerosols, both in the field and laboratory, for over two decades. SPMSs typi...

Aerodyne Aerosol mass spectrometers (AMS) or Aerosol chemical speciation monitors (ACSM), are widely-deployed to quantify organic aerosol (OA) mass concentration and size distribution in various field and laboratory studies across the world. A non-unity collection efficiency (CE, usually 0.45-1), resulting from particle bounce on standard vaporizer (SV), depends on chemical composition and phase of aerosol. The estimation of CE contributes a significant fraction of the total quantification uncertainty for these instruments. To address this uncertainty, a capture vaporizer (CV) was recently designed to reduce or eliminate particle bounce. Here, we evaluate the quantification of ambient submicron OA with the CV, including multiple biogenic- and anthropogenic-influenced field studies. Good agreement of OA between the SV and CV has been found (Slopes=0.84-1, R>0.9), consistent with both CE ~1 for ambient OA with the CV, and with the chemical composition-dependent CE (CDCE) previously developed of ambient SV d...

The San Joaquin Valley (SJV) of California has suffered persistent particulate matter (PM) pollution despite many years of control efforts. To further understand the chemical drivers of this problem and to support the development of State Implementation Plan for PM, a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) outfitted with a PM

Although secondary particulate matter is reported to be the main contributor of PM2.5 during haze in Chinese megacities, primary particle emissions also affect particle concentrations. In order to improve estimates of the contribution of primary sources to the particle number and mass concentrations, we performed source apportionment analyses using both chemical fingerprints and particle size distributions measured at the same site in urban Beijing from April to July 2018. Both methods resolved factors related to primary emissions, including vehicular emissions and cooking emissions, which together make up 76 % and 24 % of total particle number and organic aerosol (OA) mass, respectively. Similar source-types, including particles related to vehicular emissions (1.6 ± 1.1 μg m−3; 2.4 ± 1.8 × 103 cm−3 and 5.5 ± 2.8 × 103 cm−3 for two traffic-related components), cooking emissions (2.6 ± 1.9 μg m−3 and 5.5 ± 3.3 × 103 cm−3) and secondary aerosols (51 ± 41 μg m−3 and 4.2 ± 3.0 × 103 cm−3) were resolved by both methods. Converted mass concentrations from particle size distributions components were comparable with those from chemical fingerprints. Size distribution source apportionment separated vehicular emissions into a component with a mode diameter of 20 nm (Traffic-ultrafine) and a component with a mode diameter of 100 nm (Traffic-fine). Consistent with similar day and night-time diesel vehicle PM2.5 emissions estimated for the Beijing area, Traffic-fine, hydrocarbon-like OA (HOA, traffic-related factor resulting from source apportionment using chemical fingerprints), and black carbon (BC) showed similar diurnal patterns, with higher concentrations during the night and morning than during the afternoon when the boundary layer is higher. Traffic-ultrafine particles showed the highest concentrations during the rush-hour period, suggesting a prominent role of local gasoline vehicle emissions. In the absence of new-particle formation, our results show that vehicular (14 % and 30 % for ultrafine and fine particles, respectively) and cooking (32 %) emissions dominate the particle number concentration while secondary particulate matter (over 80 %) governs PM2.5 mass during the non-heating season in Beijing.

Particulate chloride is an important component of fine particulate matter in marine air masses. Recent field studies also report elevated concentrations of gas-phase reactive chlorine species and particulate chloride related to anthropogenic activities. This work focuses on particulate chloride detection and quantification issues observed for some quadrupole aerosol chemical speciation monitors (Q-ACSMs) which are designed for the long-term measurement of ambient aerosol composition. The ACSM reports particle concentrations based on the difference between measurements of ambient air (sample mode) and particle-free ambient air (filter mode). For our long-term campaign in Krakow, Poland, the Q-ACSM reports apparent negative total chloride concentration for most of the campaign when analyzed with the default fragmentation table. This is the result of the difference signal from m∕z 35 (35Cl+) being negative, which dominates over the positive difference signal from m∕z 36 (H35Cl+). Highly time-resolved experiments with NH4Cl, NaCl and KCl particles show that the signal response of m∕z 35 is non-ideal when the signal builds up and decreases slowly for all three salts, leading to a negative difference measurement. In contrast, the m∕z 36 signal exhibits a near step-change response for NH4Cl during the sampling and filter period, resulting in a positive difference signal. The response of m∕z 36 for NaCl and KCl is not as prompt as for NH4Cl but still fast enough to have a positive difference signal. Furthermore, it is shown that this behavior is mostly independent of vaporizer temperature. Based on these observations, this work presents an approach to correct the chloride concentration time series by adapting the standard fragmentation table coupled with a calibration of NH4Cl to obtain a relative ionization efficiency (RIE) based on the signal at m∕z 36 (H35Cl+). This correction can be applied to measurements in environments where chloride is dominated by NH4Cl. Caution should be exercised when other chloride salts dominate the ambient particulate chloride.

Aromatic volatile organic compounds (VOC) are key anthropogenic pollutants emitted to the atmosphere and are important for both ozone and secondary organic aerosol (SOA) formation in urban areas. Recent studies have indicated that aromatic hydrocarbons may follow previously unknown oxidation chemistry pathways, including autoxidation that can lead to the formation of highly oxidised products. In this study we evaluate the gas and particle phase ions formed during the hydroxyl radical oxidation of substituted C9-aromatic isomers (1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, propyl benzene and isopropyl benzene) and a substituted polyaromatic hydrocarbon (1-methyl naphthalene) under low and medium NOx conditions. The majority of product signal in both gas and particle phases comes from ions which are common to all precursors, though signal distributions are distinct for different VOCs. Gas and particle phase composition are distinct from one another, and comparison with the near explicit gas phase Master Chemical Mechanism (MCMv3.3.1) highlights a range of missing highly oxidised products in the pathways. In the particle phase, the bulk of product signal from all precursors comes from ring scission ions, many of which have undergone further oxidation to form HOMs. Under perturbation of OH oxidation with increased NOx, the contribution of HOM ion signals to the particle phase signal remains elevated for more substituted aromatic precursors. Up to 25 % of product signal comes from ring-retaining ions including highly oxygenated organic molecules (HOMs); this is most important for the more substituted aromatics. Unique products are a minor component in these systems, and many of the dominant ions have ion formulae concurrent with other systems, highlighting the challenges in utilising marker ions for SOA.

To reduce the quantification uncertainty of commercial aerosol mass spectrometers (AMS) and aerosol chemical speciation monitors (ACSM), a new capture vaporizer (CV) was recently built to replace the standard vaporizer (SV). A collection efficiency (CE) ∼ 1 in the CV AMS/ACSM has been demonstrated for ambient aerosols, but the CV also leads to increased thermal decomposition of the analytes because of longer residence time and vaporizer surface contact. This study reports on the performance of the CV for analyzing organic aerosol (OA) elemental composition and source apportionment, using both HR-ToF-AMS and ACSM for the first time. The methodology for obtaining elemental ratios from AMS spectra is updated to account for differences in OA fragmentation between the CV and SV. An artifact CO+ signal is observed for some chemically reduced laboratory compounds. If that signal is included in elemental analysis, the O:C is substantial overestimated, while accurate results are observed if the anomalous CO+ is ig...

The San Joaquin Valley (SJV) of California has suffered persistent particulate matter (PM) pollution despite many years of control efforts. To further understand the chemical drivers of this problem and to support the development of State Implementation Plan for PM, a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) outfitted with a PM2.5 lens and a capture vaporizer has been deployed at the Fresno-Garland air monitoring site of the California Air Resource Board (CARB) since Oct. 2018. The instrument measured non-refractory species in PM2.5 continuously at 10-min resolution. In this study, the data acquired from Oct. 2018 to May 2019 were analyzed to investigate the chemical characteristics, sources and atmospheric processes of PM2.5 in the SJV. Comparisons of the ToF-ACSM measurement with various co-located aerosol instruments show good agreements. The inter-comparisons indicated that PM2.5 in Fresno was dominated by submicron particles during the winter whereas refractory species accounted for a major fraction of PM2.5 mass during the autumn associated with elevated PM10 loadings. A rolling window positive matrix factorization analysis was applied to the organic aerosol (OA) mass spectra using the Multilinear Engine (ME-2) algorithm. Three distinct OA sources were identified, including vehicle emissions, local and regional biomass burning, and formation of oxygenated species. There were significant seasonal variations in PM2.5 composition and sources. During the winter, residential wood burning and oxidation of nitrogen oxides were major contributors to the occurrence of haze episodes with PM2.5 dominated by biomass burning OA and nitrate. In autumn, agricultural activities and wildfires were found to be the main cause of PM pollution. PM2.5 concentrations decreased significantly after spring and were dominated by oxygenated OA during March to May. Our results highlight the importance of using seasonally dependent control strategies to mitigate PM pollution in the SJV.

A PM2.5-capable aerosol chemical speciation monitor (ACSM) was deployed in urban Nanjing, China for the first time to measure in-situ non-refractory fine particle (NR-PM2.5) composition from October 20 to November 19, 2015 along with parallel measurements of submicron aerosol (PM1) species by a standard ACSM. Our results show that the NR-PM2.5 species (organics, sulfate, nitrate, and ammonium) measured by the PM2.5-ACSM are highly correlated (r2 > 0.9) with those measured by a Sunset Lab OC/EC Analyzer and a Monitor for AeRosols and GAses (MARGA). The comparisons between the two ACSMs illustrated similar temporal variations in all NR species between PM1 and PM2.5, yet substantial mass fractions of aerosol species were observed in the size range of 1–2.5 μm. On average, NR-PM1–2.5 contributed 53 % of the total NR-PM2.5 with sulfate and secondary organic aerosols (SOA) being the two largest contributors (26 % and 27 %, respectively). Rapid formation and thereafter growth of secondary inorganic aerosols (SIA) were observed under fog processing in NH3-rich environments. Positive matrix factorization of organic aerosol showed similar temporal variations in both primary and secondary OA between PM1 and PM2.5 although the mass spectra were slightly different due to more thermal decomposition on the capture vaporizer of PM2.5-ACSM. We observed an enhancement of SOA under high relative humidity conditions, which is associated with simultaneous increases in particle surface area, gas-phase species (NO2, SO2, and NH3) concentrations and aerosol water content driven by anthropogenic SIA. These results likely indicate an enhanced reactive uptake of SOA precursors upon aqueous particles. Therefore, reducing anthropogenic NOx, SO2, and NH3 emissions might not only reduce SIA but also SOA burden during haze episodes in China.

The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was redeployed at the Jefferson Street (JST) site in downtown Atlanta, Georgia (GA) for 1 year (March 20, 2014–February 08, 2015) to chemically characterize non-refractory submicron particulate matter (NR-PM1) in near real-time and to assess whether organic aerosol (OA) types and amounts change from year-to-year. Submicron organic aerosol (OA) mass spectra were analyzed by season using multilinear engine (ME-2) to apportion OA subtypes to potential sources and chemical processes. A suite of real-time collocated measurements from the Southeastern Aerosol Research and Characterization (SEARCH) network was compared with ME-2 factor solutions to aid in the interpretation of OA subtypes during each season. OA tracers measured from high-volume filter samples using gas chromatography interfaced with electron ionization-mass spectrometry (GC/EI-MS) also aided in identifying OA sources. The initial application of ME-2 to the yearlong ACSM dataset revealed that OA source apportionment by season was required to better resolve sporadic OA types. Spring and fall OA mass spectral datasets were separated into finer periods to capture potential OA sources resulting from non-homogeneous emissions during transitioning periods. NR-PM1 was highest in summer (16.7 ± 8.4 μg m−3) and lowest in winter (8.0 ± 5.7 μg m−3), consistent with prior studies. OA dominated NR-PM1 mass (56–74% on average) in all seasons. Hydrocarbon-like OA (HOA) from primary emissions was observed in all seasons, averaging 5–22% of total OA mass. Strong correlations of HOA with carbon monoxide (CO) (R = 0.71–0.88) and oxides of nitrogen (NOx) (R = 0.55–0.79) indicated that vehicular traffic was the likely source. Biomass burning OA (BBOA) was observed in all seasons, with lower contributions (2%) in summer and higher in colder seasons (averaging 8–20% of total OA mass). BBOA correlated strongly with levoglucosan (R = 0.78–0.95) during colder seasons, which supports that BBOA is likely derived from fresh biomass/residential burning. However, weaker correlation with levoglucosan (R = 0.38) in summer suggested a more aged aerosol. During warmer seasons, OA from the reactive uptake of isoprene epoxydiols (IEPOX) onto acidic sulfate aerosol was resolved by ME-2 (denoted as IEPOX-OA), averaging 25–29% of the total OA mass. Temporal variation of IEPOX-OA was nearly coincident with that of 91Fac OA (a factor dominated by a distinct ion at m/z 91). The largest contribution of IEPOX-OA to total OA (29%) was found in summer, whereas the largest contribution of 91Fac to total OA (24%) occurred in early fall. Moderate negative correlation between IEPOX-OA and aerosol acidity was observed during late spring (−0.67) and summer (−0.42), consistent with laboratory studies showing that IEPOX-OA is enhanced in the presence of acidic aerosols. Finally, the largest OA mass in all seasons (46–70% of total OA) was derived from oxygenated OA denoted as low-volatility oxygenated OA (LV-OOA) and semi-volatile oxygenated OA (SV-OOA).

We determined particulate matter (PM) emissions in the exhaust plumes from two gas turbine aircraft engines: a CF34-3A1 turbofan engine and a TPE331-6-252B turboprop engine in a dedicated study on in-service general aviation aircraft. The engine power states were from 16% to 100% engine thrust. Both nucleation and soot mode particles were observed from the emission exhausts of the CF34-3A1 engine but only soot particle mode was detected from the TPE331-6-252B engine. For the CF34-3A1 engine, the contribution of soot mode to total PM emissions was dominant at high power, while at decreased engine power states nucleation mode organic PM became important. PM emissions indices of the TPE331-6-252B engine were found to be generally larger than those of the CF34-3A1 engine. For both engines, medium power conditions (40–60% of thrust) yielded the lowest PM emissions. For the TPE331-6-252B engine, volatile PM components including organic and sulfate were more than 50% in mass at low power, while non-volatile black carbon became dominant at high power conditions such as takeoff.

This work describes results obtained from the 2016 Aerosol Chemical Speciation Monitor (ACSM) intercomparison exercise performed at the Aerosol Chemical Monitor Calibration Center (ACMCC, France). Fifteen quadrupole ACSMs (Q_ACSM) from the European Research Infrastructure for the observation of Aerosols, Clouds and Trace gases (ACTRIS) network were calibrated using a new procedure that acquires calibration data under the same operating conditions as those used during sampling and hence gets information representative of instrument performance. The new calibration procedure notably resulted in a decrease in the spread of the measured sulfate mass concentrations, improving the reproducibility of inorganic species measurements between ACSMs as well as the consistency with co-located independent instruments. Tested calibration procedures also allowed for the investigation of artifacts in individual instruments, such as the overestimation of m/z 44 from organic aerosol. This effect was quantified by the m/z (mass-to-charge) 44 to nitrate ratio measured during ammonium nitrate calibrations, with values ranging from 0.03 to 0.26, showing that it can be significant for some instruments. The fragmentation table correction previously proposed to account for this artifact was applied to the measurements acquired during this study. For some instruments (those with high artifacts), this fragmentation table adjustment led to an “overcorrection” of the f44 (m/z 44/Org) signal. This correction based on measurements made with pure NH4NO3, assumes that the magnitude of the artifact is independent of chemical composition. Using data acquired at different NH4NO3 mixing ratios (from solutions of NH4NO3 and (NH4)2SO4) we observe that the magnitude of the artifact varies as a function of composition. Here we applied an updated correction, dependent on the ambient NO3 mass fraction, which resulted in an improved agreement in organic signal among instruments. This work illustrates the benefits of integrating new calibration procedures and artifact corrections, but also highlights the benefits of these intercomparison exercises to continue to improve our knowledge of how these instruments operate, and assist us in interpreting atmospheric chemistry. © 2019, © 2019 Author(s). Published with license by Taylor & Francis Group, LLC., Funding text #1 aLaboratoire de Météorologie Physique (LaMP), Aubiere, France; bInstitut National de l’Environnement Industriel et des Risques (INERIS), Verneuil-en-Halatte, France; cLaboratoire des Sciences du Climat et de l’Environnement (LSCE), CNRS-CEA-UVSQ, Gif-sur-Yvette, France; dAerodyne Research, Inc, Billerica, Massachusetts, USA; eEnvironment Energy and Water Research Center, The Cyprus Institute, Nicosia, Cyprus; fEstonian Environmental Research Center (EERC), Tallinn, Estonia; gFinnish meteorological institute (FMI), Helsinki, Finland; hIERSD, National Observatory of Athens, Athens, Greece; iDepartment of the Environment, Centre for Energy, Environment and Technology Research (CIEMAT), Madrid, Spain; jDeutscher Wetterdienst, Meteorologisches Observatorium Hohenpeißenberg, Hohenpeißenberg, Germany; kInstitute for Atmospheric and Earth System Research (INAR)/Physics, Faculty of Science, University of Helsinki, Helsinki, Finland; lLeibniz Institute for Tropospheric Research, Leipzig, Germany; mEnvironmental Research Group, MRC-HPA Centre for Environment and Health, King’s College London, London, United Kingdom; nInstitute of Environmental Assessment and Water Research (IDAEA-CSIC), Barcelona, Spain; oLaboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen PSI, Switzerland; pNational Institute of R&D for Optoelectronics (INOE), Ilfov, Romania; qProambiente S.c.r.l CNR Research Area, Bologna, Italy Funding text #2 This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 654109. The US Department of Energy Small Business Innovative Research program (award number DE-SC0017041) provided support for development of ACSM calibration procedures. CNRS, CEA, and INERIS are acknowledged for financial support of the ACMCC. The intercomparison campaign and the following data treatment have been conducted in collaboration with the French reference laboratory for air quality monitoring (LCSQA), funded by the French Ministry of Environment. COST action CA16109 Chemical On-Line cOmpoSition and Source Apportionment of fine aerosoLs COLOSSAL grant is gratefully acknowledged for the support of data workshops. M.C. Minguillón acknowledges the Ramón y Cajal fellowship awarded by the Spanish Ministry of Economy, Industry and Competitiveness. The CIEMAT participation has been partially funded by MINECO/AEI/FEDER, UE (CGL2017-85344-R and CGL2017-90884-REDT) and TIGAS-CM (Y2018/EMT- 5177) Project. PSI is grateful for financial support by the Federal Office for the Environment in Switzerland.

We measured the gas-particle partitioning of vehicle emitted primary organic aerosol (POA) in a traffic tunnel with three independent methods: artifact corrected bare-quartz filters, thermodenuder (TD) measurements, and thermal-desorption gas-chromatography mass-spectrometry (TD-GC-MS). Results from all methods consistently show that vehicle emitted POA measured in the traffic tunnel is semivolatile under a wide range of fleet compositions and ambient conditions. We compared the gas-particle partitioning of POA measured in both tunnel and dynamometer studies and found that volatility distributions measured in the traffic tunnel are similar to volatility distributions measured in the dynamometer studies, and predict similar gas-particle partitioning in the TD. These results suggest that the POA volatility distribution measured in the dynamometer studies can be applied to describe gas-particle partitioning of ambient POA emissions. The POA volatility distribution measured in the tunnel does not have significant diurnal or seasonal variations, which indicate that a single volatility distribution is adequate to describe the gas-particle partitioning of vehicle emitted POA in the urban environment.

The aerodynamic lens system of the Aerodyne Aerosol Mass Spectrometer (AMS) was analyzed using the Aerodynamic Lens Calculator. Using this tool, key loss mechanisms were identified, and a new lens design that can extend the transmission of particulate matter up to 2.5 μm in diameter (PM2.5) was proposed. The new lens was fabricated and experimentally characterized. Test results indicate that this modification to the AMS lens can significantly improve the transmission of large sized particles, successfully achieving a high transmission efficiency up to PM2.5 range.© 2016 American Association for Aerosol Research

The elemental composition of organic material in environmental samples – including atmospheric organic aerosol, dissolved organic matter, and other complex mixtures – provides insights into their sources and environmental processing. However, standard analytical techniques for measuring elemental ratios typically require large sample sizes (milligrams of material or more). Here we characterize a method for measuring elemental ratios in environmental samples, requiring only micrograms of material, using a small-volume nebulizer (SVN). The technique uses ultrasonic nebulization of samples to generate aerosol particles (100–300 nm diameter), which are then analyzed using an aerosol mass spectrometer (AMS). We demonstrate that the technique generates aerosol from complex organic mixtures with minimal changes to the elemental composition of the organic material and that quantification is possible using internal standards (e.g., NH415NO3). Sample volumes of 2–4 µL with total solution concentrations of at least 0.2 g L−1 form sufficient particle mass for elemental ratio measurement by the AMS, despite only a small fraction (∼ 0.1 %) of the sample forming fine particles after nebulization (with the remainder ending up as larger droplets). The method was applied to aerosol filter extracts from the field and laboratory, as well as to the polysaccharide fraction of dissolved organic matter (DOM) from the North Pacific Ocean. In the case of aerosol particles, the mass spectra and elemental ratios from the SVN–AMS agree with those from online AMS sampling. Similarly, for DOM, the elemental ratios determined from the SVN–AMS agree with those determined using combustion analysis. The SVN–AMS provides a platform for the rapid quantitative analysis of the elemental composition of complex organic mixtures and non-refractory inorganic salts from microgram samples with applications that include analysis of aerosol extracts and terrestrial, aquatic, and atmospheric dissolved organic matter.

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall - early-winter period (November-December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36 % for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment.

Mass concentrations calculated from Aerodyne's aerosol mass spectrometers depend on particle collection efficiency (CE) and relative ionization efficiency (RIE, relative to the primary calibrant ammonium nitrate). We present new laboratory RIE measurements for a wide range of organic aerosol species (RIEOA). An improved laboratory RIE calibration protocol with size and mass selection of calibrant particles and a light scattering-based detection of CE is used. Simpler calibrations of alcohol RIEs using binary mixtures with NH4NO3 are demonstrated. Models that account for only thermal velocity and electron ionization of vaporized molecules do not reproduce RIEOA measurements, confirming that other processes are significant. The relationship between RIEOA and average carbon oxidation state (), a metric used to describe atmospheric OA, is investigated. An average RIEOA of 1.6 ± 0.5 (2σ) is found for −1.0 < < 0.5, a range consistent with most ambient OA except hydrocarbon-like organic aerosol (HOA) and cooking organic aerosol (COA). RIEOA from 2 to 7 are found for below and above this range. The RIEOA typically used for ambient OA (1.4 ± 0.3) is within the laboratory RIEOA measurement uncertainty of oxidized organic species, but is a factor of 2 to 5 lower than that of reduced species. Such biases in OA mass concentrations have not been observed in published field analyses. Chemically reduced ambient OA may have composition, phase states, or compensating CE effects that are not mimicked well in the laboratory. This work highlights the need for further ambient OA studies to better constrain the composition dependence of ambient RIEOA, and the need to always calibrate with the OA under study for laboratory experiments. Copyright © 2018 American Association for Aerosol Research

The Aerosol Mass Spectrometer (AMS) and Aerosol Chemical Speciation Monitor (ACSM) are widely used for quantifying submicron aerosol mass concentration and composition, in particular for organic aerosols (OA). Using the standard vaporizer (SV) installed in almost all commercial instruments, a collection efficiency (CE) correction, varying with aerosol phase and chemical composition, is needed to account for particle bounce losses. Recently, a new “capture vaporizer” (CV) has been shown to achieve CE∼1 for ambient aerosols, but its chemical detection properties show some differences from the SV due to the increased residence time of particles and vaporized molecules inside the CV. This study reports on the properties and changes of mass spectra of OA in CV-AMS using both AMS and ACSM for the first time. Compared with SV spectra, larger molecular-weight fragments tend to shift toward smaller ions in the CV due to additional thermal decomposition arising from increased residence time and hot surface collisions. Artifact CO+ ions (and to a lesser extent, H2O+), when sampling long chain alkane/alkene-like OA (e.g., squalene) in the CV during the laboratory studies, are observed, probably caused by chemical reactions between sampled OA and molybdenum oxides on the vaporizer surfaces (with the carbon derived from the incident OA). No evidence for such CO+ enhancement is observed for ambient OA. Tracer ion marker fractions (fm/z =, i.e., the ratio of the organic signal at a given m/z to the total OA signal), which are used to characterize the impact of different sources are still present and usable in the CV. A public, web-based spectral database for mass spectra from CV-AMS has been established. Copyright © 2018 American Association for Aerosol Research

Online non-refractory submicron aerosol mass spectrometer (AMS) measurements in urban areas have successfully allowed the apportionment of specific sources and/or physical and chemical properties of the organic fraction. However, in order to be fully representative of PM pollution, a comprehensive source apportionment analysis is needed by taking into account all major components of submicron aerosols, creating strengthened bonds between the organic components and pollution sources. We present here a novel two-step methodology to perform such an analysis, by taking advantage of high time resolution of monitoring instruments: the aerosol chemical speciation monitor (ACSM) and the multi-wavelength absorption measurements (Aethalometer AE31) in Paris, France. As a first step, organic aerosols (OA) were deconvolved to hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and oxygenated OA (OOA) with positive matrix factorization (PMF), and black carbon was deconvolved into its wood burning and fossil fuel combustion fractions. A second PMF analysis was then carried out with organic factors, BC fractions and inorganic species (nitrate, sulfate, ammonium, chloride), leading to a four-factor solution allowing highly time-resolved characterization of the major sources of PM1. Outputs of this PMF2 include two dominant combustion sources (wood burning and traffic) as well as semi-volatile and low-volatile secondary aerosols. While HOA is found to be emitted by both wood burning and traffic, the latter sources occurred to significantly contribute also to OOA.

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

Southern Africa is a significant source region of atmospheric pollution, yet long-term data on pollutant concentrations and properties from this region are rather limited. A recently established atmospheric measurement station in South Africa, Welgegund, is strategically situated to capture regional background concentrations, as well as emissions from the major source regions in the interior of South Africa. We measured non-refractive submicron aerosols (NR-PM1) and black carbon over a one year period in Welgegund, and investigated the seasonal and diurnal patterns of aerosol concentration levels, chemical composition, acidity and oxidation level. Based on air mass back trajectories, four distinct source regions were determined for NR-PM1. Supporting data utilised in our analysis included particle number size distributions, aerosol absorption, trace gas concentrations, meteorological variables and the flux of carbon dioxide. The dominant submicron aerosol constituent during the dry season was organic aerosol, reflecting high contribution from savannah fires and other combustion sources. Organic aerosol concentrations were lower during the wet season, presumably due to wet deposition as well as reduced emissions from combustion sources. Sulfate concentrations were usually high and exceeded organic aerosol concentrations when air-masses were transported over regions containing major point sources. Sulfate and nitrate concentrations peaked when air masses passed over the industrial Highveld (iHV) area. In contrast, concentrations were much lower when air masses passed over the cleaner background (BG) areas. Air masses associated with the anti-cyclonic recirculation (ACBIC) source region contained largely aged OA. Positive Matrix Factorization (PMF) analysis of aerosol mass spectra was used to characterise the organic aerosol (OA) properties. The factors identified were oxidized organic aerosols (OOA) and biomass burning organic aerosols (BBOA) in the dry season and low-volatile (LV-OOA) and semi-volatile (SV-OOA) organic aerosols in the wet season. The results highlight the importance of primary BBOA in the dry season, which represented 33% of the total OA. Aerosol acidity and its potential impact on the evolution of OOA are also discussed.

Real-time continuous chemical measurements of fine aerosol were made using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) during summer and fall 2011 in downtown Atlanta, Georgia. Organic mass spectra measured by the ACSM were analyzed by positive matrix factorization (PMF), yielding three conventional factors: hydrocarbon-like organic aerosol (HOA), semivolatile oxygenated organic aerosol (SV-OOA), and low-volatility oxygenated organic aerosol (LV-OOA). An additional OOA factor that contributed to 33 ± 10% of the organic mass was resolved in summer. This factor had a mass spectrum that strongly correlated (r(2) = 0.74) to that obtained from laboratory-generated secondary organic aerosol (SOA) derived from synthetic isoprene epoxydiols (IEPOX). Time series of this additional factor is also well correlated (r(2) = 0.59) with IEPOX-derived SOA tracers from filters collected in Atlanta but less correlated (r(2)0.3) with a methacrylic acid epoxide (MAE)-derived SOA tracer, α-pinene SOA tracers, and a biomass burning tracer (i.e., levoglucosan), and primary emissions. Our analyses suggest IEPOX as the source of this additional factor, which has some correlation with aerosol acidity (r(2) = 0.3), measured as H(+) (nmol m(-3)), and sulfate mass loading (r(2) = 0.48), consistent with prior work showing that these two parameters promote heterogeneous chemistry of IEPOX to form SOA.

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.

The aerosol mass spectrometer (AMS) and aerosol chemical speciation monitor (ACSM) are widely used for quantifying aerosol composition. The quantification uncertainty of these instruments is dominated by the collection efficiency (CE) due to particle bounce. A new “capture vaporizer” (CV) has been recently developed to achieve unit CE. In this study, we examine the performance of the CV while sampling ambient aerosols. AMS/ACSMs using the original standard vaporizer (SV) and CV were operated in parallel during three field studies. Concentrations measured with the CV (assuming CE = 1) and SV (using the composition-dependent CE of Middlebrook et al.), as well as SMPS and PILS-IC are compared. Agreement is good in all cases, verifying that CE ∼ 1 in the CV when sampling ambient particles. Specific findings include: (a) The fragmentation pattern of ambient nitrate and sulfate species observed with the CV was shifted to smaller m/z, suggesting additional thermal decomposition. (b) The differences in fragmentation patterns of organic vs. inorganic nitrate and sulfur species are still distinguishable in the CV, however, with much lower signal-to-noise compared to the SV. (c) Size distribution broadening is significant, but its impact is limited in field studies since ambient distributions are typically quite broad. Consistent size distributions were measured with the SV and CV. (d) In biogenic areas, UMR nitrate is overestimated based on the default fragmentation table (∼factor of 2–3 in SOAS) for both vaporizers, due to underestimation of the organic interferences. We also report a new type of small interference: artifact chloride signal can be observed in the AMS when high nitrate mass concentration is sampled with both the SV (∼0.5% chloride/nitrate) or CV (∼0.2% chloride/nitrate). Our results support the improved quantification with the CV AMS and characterize its chemical detection properties. Copyright © 2017 American Association for Aerosol Research

The atmospheric nitrous oxide concentration has increased by 20% since 1750. Analyses of Antarctic firn and archived air samples reveal seasonal cycles in the isotopic signature of nitrous oxide, which can help to disentangle the contribution of surface sources.

We present a new instrument, the Aerosol Chemical Speciation Monitor (ACSM), which routinely characterizes and monitors the mass and chemical composition of non-refractory submicron particulate matter in real time. Under ambient conditions, mass concentrations of particulate organics, sulfate, nitrate, ammonium, and chloride are obtained with a detection limit

The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) is well suited for measuring non-refractory particulate matter up to approximately 1.0 µm in aerodynamic diameter (NR-sub-PM1). However, for larger particles the detection efficiency is limited by losses in the sampling inlet system and through the standard aerodynamic focusing lens. In addition, larger particles have reduced collection efficiency due to particle bounce at the vaporizer. These factors have limited the NR-sub-PM1 ACSM from meeting PM2.5 (particulate matter with aerodynamic diameter smaller than 2.5 µm) monitoring standards. To overcome these limitations, we have redesigned the sampling inlet, the aerodynamic lens, and particle vaporizer. Both the new lens and vaporizer are tested in the lab using a quadruple aerosol mass spectrometer (QAMS) system equipped with light scattering module. Our results show that the capture vaporizer introduces additional thermal decomposition of both inorganic and organic compounds, requiring modifications to the standard AMS fragmentation table, which is used to partition ion fragments to chemical classes. Experiments with mixed NH4NO3 and (NH4)2SO4 particles demonstrated linearity in the NH4+ ion balance, suggesting that there is no apparent matrix effect in the thermal vaporization-electron impact ionization detection scheme for mixed inorganic particles. Considering a typical ambient PM2.5 size distribution, we found that 89% of the non-refractory mass is detected with the new system, while only 65% with the old system. The NR-PM2.5 system described here can be adapted to existing Aerodyne Aerosol Mass Spectrometer (AMS) and ACSM systems. Copyright © 2017 American Association for Aerosol Research

Aerosol particles formed in the atmosphere are important to the Earth's climate system due to their ability to affect cloud properties. At present, little is known about the atmospheric chemistry responsible for the growth of newly formed aerosol particles to climate-relevant sizes. Here combining detailed aerosol measurements with a theoretical framework we found that depending on the gaseous precursors and size of the newly formed particles, the growth was dominated by either sulfuric acid accompanied by ammonium or organic compounds originating in either biogenic emissions or savannah fires. The contribution of sulfuric acid was larger during the early phases of the growth, but in clean conditions organic compounds dominated the growth from 1.5 nm up to climatically relevant sizes. Furthermore, our analysis indicates that in polluted environments the contribution of sulfuric acid to the growth may have been underestimated by up to a factor of 10.

As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for three weeks during the late fall–early winter period (November–December 2013). The first week was dedicated to tuning and calibration of each instrument whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r2 > 0.9) were observed systematically for each individual ACSM across all chemical families except for chloride for which three ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025) and were found to be of 9, 15, 19, 28 and 36 % for NR-PM1, nitrate, organic matter, sulfate and ammonium respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of ACSMs, detailed intercomparison results are presented as well as a discussion of some recommendations about best calibration practices, standardized data processing and data treatment.

The high atmospheric concentrations of toxic gases, particulate matter, and acids in the areas immediately surrounding volcanoes can have negative impacts on human and ecological health. To better understand the atmospheric fate of volcanogenic emissions in the near field (in the first few hours after emission), we have carried out real-time measurements of key chemical components of the volcanic plume from Kı̅lauea on the Island of Hawai'i. Measurements were made at two locations, one ∼ 3 km north-northeast of the vent and the other 31 km to the southwest, with sampling at each site spanning a range of meteorological conditions and volcanic influence. Instrumentation included a sulfur dioxide monitor and an Aerosol Chemical Speciation Monitor, allowing for a measurement of the partitioning between the two major sulfur species (gas-phase SO2 and particulate sulfate) every 5 min. During trade wind conditions, which sent the plume toward the southwest site, sulfur partitioning exhibited a clear diurnal pattern, indicating photochemical oxidation of SO2 to sulfate; this enabled the quantitative determination of plume age (5 h) and instantaneous SO2 oxidation rate (2.4 × 10(-6) s(-1) at solar noon). Under stagnant conditions near the crater, the extent of SO2 oxidation was substantially higher, suggesting faster oxidation. The particles within the plume were extremely acidic, with pH values (controlled largely by ambient relative humidity) as low as -0.8 and strong acidity (controlled largely by absolute sulfate levels) up to 2200 nmol/m(3). The high variability of sulfur partitioning and particle composition underscores the chemically dynamic nature of volcanic plumes, which may have important implications for human and ecological health.

Chemically resolved (organic, nitrate, sulfate, ammonium) data of non-refractory submicron (NR-PM1) aerosol from the first long-term deployment (27 July 2012 to 02 October 2013) of a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) at the Swiss high-altitude site Jungfraujoch (JFJ; 3580 m a.s.l.) are presented. Besides total mass loadings, diurnal variations and relative species contributions during the different meteorological seasons, geographical origin and sources of organic aerosol (OA) are discussed. Backward transport simulations show that the highest (especially sulfate) concentrations of NR-PM1 were measured in air masses advected to the station from regions south of the JFJ, while lowest concentrations were seen from western regions. OA source apportionment for each season was performed using the Source Finder (SoFi) interface for the multilinear engine (ME-2). OA was dominated in all seasons by oxygenated OA (OOA, 71–88 %), with lesser contributions from local tourism-related activities (7–12 %) and hydrocarbon-like OA related to regional vertical transport (3–9 %). In summer the OOA can be separated into a background low-volatility OA (LV-OOA I, possibly associated with long-range transport) and a slightly less oxidised low-volatility OA (LV-OOA II) associated with regional vertical transport. Wood burning-related OA associated with regional transport was detected during the whole winter 2012/2013 and during rare events in summer 2013, in the latter case attributed to small-scale transport for the surrounding valleys. Additionally, the data were divided into periods with free tropospheric (FT) conditions and periods with planetary boundary layer (PBL) influence, enabling the assessment of the composition for each. Most nitrate and part of the OA are injected from the regional PBL, while sulfate is mainly produced in the FT. The south/north gradient of sulfate is also pronounced in FT air masses (sulfate mass fraction from the south: 45 %; from the north: 29 %). Furthermore, a detailed investigation of specific marker fragments of the OA spectra (f43, f44, f55, f57, f60) showed different degrees of ageing depending on season.

Photoionization efficiency spectra of (14)N2, (15)N(14)N, and (15)N2 from 15.5 to 18.9 eV were measured using synchrotron radiation at the Advanced Light Source at Lawrence Berkeley National Laboratory with a resolution of 6 meV, and significant changes in peak energies and intensities upon isotopic substitution were observed. Previously, we reported the isotope shifts and their applications to Titan's atmosphere. Here, we report more extensive experimental details and tabulate the isotope shifts of many transitions in the N2 spectrum, including those for (15)N(14)N, which have not been previously reported. The isotope shifts are used to address several long-standing ambiguities in spectral peak assignments just above the ionization threshold of N2. The feature at 15.677 eV (the so-called second "cathedral" peak) is of particular interest in this respect. The measured isotope shifts for this peak relative to (14)N2 are 0.015 ± 0.001 eV for (15)N2 and 0.008 ± 0.001 eV for (15)N(14)N, which match most closely with the isotope shifts predicted for transitions to the (A (2)Πu v' = 2)4sσ(g) (1)Π(u) state using Herzberg equations for the isotopic differences in harmonic oscillator energy levels plus the first anharmonic correction of 0.0143 eV for (15)N2 and 0.0071 eV for (15)N(14)N. More generally, the isotope shifts measured for both (15)N2 and (15)N(14)N relative to (14)N2 provide new benchmarks for theoretical calculations of interferences between direct and indirect autoionization states which can interact to produce intricate resonant structures in molecular photoionization spectra in regions near ionization thresholds.

The Aerodyne Aerosol Chemical Speciation Monitor (ACSM) was recently developed to provide long-term real-time continuous measurements of ambient non-refractory (i.e., organic, sulfate, ammonium, nitrate, and chloride) submicron particulate matter (NR-PM1). Currently, there are a limited number of field studies that evaluate the long-term performance of the ACSM against established monitoring networks. In this study, we present seasonal intercomparisons of the ACSM with collocated fine aerosol (PM2.5) measurements at the Southeastern Aerosol Research and Characterization (SEARCH) Jefferson Street (JST) site near downtown Atlanta, GA, during 2011–2012. The collocated measurements included a second ACSM, continuous and integrated sulfate, nitrate, and ammonium measurements, as well as a semi-continuous Sunset organic carbon/elemental carbon (OC/EC) analyzer, continuous tapered element oscillating microbalance (TEOM), 24 h integrated Federal Reference Method (FRM) filters, and continuous scanning electrical mobility system-mixing condensation particle counter (SEMS-MCPC). Intercomparison of the two collocated ACSMs resulted in strong correlations (r2 > 0.8) for all chemical species, except chloride (r2 = 0.21); mass concentration for all chemical species agreed within ±27%, indicating that ACSM instruments are capable of stable and reproducible operation. Chemical constituents measured by the ACSM are also compared with those obtained from the continuous measurements from JST. Since the continuous measurement concentrations are adjusted to match the integrated filter measurements, these comparisons reflect the combined uncertainties of the ACSM, continuous, and filter measurements. In general, speciated ACSM mass concentrations correlate well (r2 > 0.7) with the continuous measurements from JST, although the correlation for nitrate is weaker (r2 = 0.55) in summer. Differences between ACSM mass concentrations and the filter-adjusted JST continuous data are 5–27%, 4–25%, and 34–51% for sulfate, ammonium, and nitrate, respectively. These comparisons are all close to the stated ±30% accuracy of the ACSM except for nitrate. These discrepancies could be due to positive biases in the ACSM nitrate concentrations from interferences at the NO+ (m/z 30) fragment ion and/or negative artifacts in the nitrate filter measurement (from volatilization of NH4NO3) are also possible. The organic matter OM/OC ratios derived from linear regression of ACSM OM vs. Sunset OC/EC analyzer are 4.18 ± 0.04 and 3.59 ± 0.02 for summer and fall, respectively. Linear correlations of the ACSM NR-PM1 plus EC with TEOM PM2.5 mass are strong (r2 > 0.7) with percentage difference of 19% and 80% during summer and fall, respectively. On the other hand, the ACSM NR-PM1 correlation with FRM PM1 is high (r2 > 0.8) with percentage difference of ±47% over three seasons. Correlation of ACSM NR-PM1 plus EC mass with SEMS-MCPC PM1 volume concentration results in an estimation of aerosol density of 1.61 g cm−3 for fall 2012 period. ACSM organic concentrations measured during this study were obtained using relative ionization efficiency (RIE) values observed in Aerodyne Aerosol Mass Spectrometer (AMS). Explicit calibration of the ACSM relative ionizations for ammonium, nitrate, and sulfate, during this study was shown to improve the comparisons between ACSM and collocated measurements for these species. The accuracy of the organic and total mass concentrations would likely also be improved if organic relative ionization efficiency values for the ACSM were available during this study. Laboratory calibrations of ACSM relative ionization efficiencies using organic particles of known composition are recommended for future studies.

[1] Measurements and models of the spatiotemporal variability of surface N2O mixing ratios and isotopic compositions are increasingly used to constrain the global N2O budget. However, large variability observed on the small spatial scales of soil chambers and shipboard sampling, which appears to be very sensitive to local environmental conditions, has made extrapolation to the global scale difficult. In this study, we present measurements of the isotopic composition of N2O (δ15Nbulk, δ15Nα, δ15Nβ, and δ18O) from whole-air samples collected at altitudes of 0.5 to 19km by the NASA DC-8 and WB-57 aircraft during the Costa Rica-Aura Validation Experiment (CR-AVE) and the Tropical Composition, Cloud and Climate Coupling Experiment (TC4) campaigns in January–February 2006 and July–August 2007, respectively. The vertical profiles of isotopic composition showed predictable, repeating patterns consistent with the influence of a surface source at lower altitudes and the influence of stratospheric photochemistry in the lower stratosphere. Their correlations with marine tracers at lower altitudes are consistent with a predominantly oceanic source, although a soil source cannot be ruled out. Measurements in a combustion plume revealed a strong depletion in 15N at the central nitrogen atom (i.e., low δ15Nα values), providing new information on N2O isotopic compositions from combustion. This new data set demonstrates that a coherent picture of the isotopic composition of tropospheric N2O is possible at currently attainable precisions and that its variations from 0.5 km to the lower stratosphere are a useful tool in investigating the sources and distributions of this important greenhouse gas.

Photoionization efficiency spectra of 14N2, 15N14N, and 15N2 from 15.5 to 18.9 eV were measured using synchrotron radiation at the Advanced Light Source at Lawrence Berkeley National Laboratory with a resolution of 6 meV, and significant changes in peak energies and intensities upon isotopic substitution were observed. Previously, we reported the isotope shifts and their applications to Titan's atmosphere. Here, we report more extensive experimental details and tabulate the isotope shifts of many transitions in the N2 spectrum, including those for 15N14N, which have not been previously reported. The isotope shifts are used to address several long-standing ambiguities in spectral peak assignments just above the ionization threshold of N2. The feature at 15.677 eV (the so-called second “cathedral” peak) is of particular interest in this respect. The measured isotope shifts for this peak relative to 14N2 are 0.015 ± 0.001 eV for 15N2 and 0.008 ± 0.001 eV for 15N14N, which match most closely with the isotope shifts predicted for transitions to the (A 2Πu v′ = 2)4sσg 1Πu state using Herzberg equations for the isotopic differences in harmonic oscillator energy levels plus the first anharmonic correction of 0.0143 eV for 15N2 and 0.0071 eV for 15N14N. More generally, the isotope shifts measured for both 15N2 and 15N14N relative to 14N2 provide new benchmarks for theoretical calculations of interferences between direct and indirect autoionization states which can interact to produce intricate resonant structures in molecular photoionization spectra in regions near ionization thresholds.