Douglas A. Day

Abstract. Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f60, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f60~0.3% ± 0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f44 as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f60 and increasing f44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f60 signature. A statistically significant difference in f60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) = −0.01 to ~0.05, with a mean ΔOA/POA ~19%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8 ± 7 Tg OA yr−1 is estimated, of the order of 5 % of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

Secondary organic aerosol (SOA) is formed from the atmospheric oxidation of gas-phase organic compounds leading to the formation of particle mass. Gasoline- and diesel-powered motor vehicles, both on/off-road, are important sources of SOA precursors. They emit complex mixtures of gas-phase organic compounds that vary in volatility and molecular structure—factors that influence their contributions to urban SOA. However, the relative importance of each vehicle type with respect to SOA formation remains unclear due to conflicting evidence from recent laboratory, field, and modeling studies. Both are likely important, with evolving contributions that vary with location and over short time scales. This review summarizes evidence, research needs, and discrepancies between top-down and bottom-up approaches used to estimate SOA from motor vehicles, focusing on inconsistencies between molecular-level understanding and regional observations. The effect of emission controls (e.g., exhaust aftertreatment technologies, fuel formulation) on SOA precursor emissions needs comprehensive evaluation, especially with international perspective given heterogeneity in regulations and technology penetration. Novel studies are needed to identify and quantify “missing” emissions that appear to contribute substantially to SOA production, especially in gasoline vehicles with the most advanced aftertreatment. Initial evidence suggests catalyzed diesel particulate filters greatly reduce emissions of SOA precursors along with primary aerosol.

Abstract. Bioaerosols are relevant for public health and may play an important role in the climate system, but their atmospheric abundance, properties, and sources are not well understood. Here we show that the concentration of airborne biological particles in a North American forest ecosystem increases significantly during rain and that bioparticles are closely correlated with atmospheric ice nuclei (IN). The greatest increase of bioparticles and IN occurred in the size range of 2–6 μm, which is characteristic for bacterial aggregates and fungal spores. By DNA analysis we found high diversities of airborne bacteria and fungi, including groups containing human and plant pathogens (mildew, smut and rust fungi, molds, Enterobacteriaceae, Pseudomonadaceae). In addition to detecting known bacterial and fungal IN (Pseudomonas sp., Fusarium sporotrichioides), we discovered two species of IN-active fungi that were not previously known as biological ice nucleators (Isaria farinosa and Acremonium implicatum). Our findings suggest that atmospheric bioaerosols, IN, and rainfall are more tightly coupled than previously assumed.

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

Abstract. Organic aerosols (OA) represent one of the major constituents of submicron particulate matter (PM1) and comprise a huge variety of compounds emitted by different sources. Three intensive measurement field campaigns to investigate the aerosol chemical composition all over Europe were carried out within the framework of the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) and the intensive campaigns of European Monitoring and Evaluation Programme (EMEP) during 2008 (May–June and September–October) and 2009 (February–March). In this paper we focus on the identification of the main organic aerosol sources and we define a standardized methodology to perform source apportionment using positive matrix factorization (PMF) with the multilinear engine (ME-2) on Aerodyne aerosol mass spectrometer (AMS) data. Our source apportionment procedure is tested and applied on 25 data sets accounting for two urban, several rural and remote and two high altitude sites; therefore it is likely suitable for the treatment of AMS-related ambient data sets. For most of the sites, four organic components are retrieved, improving significantly previous source apportionment results where only a separation in primary and secondary OA sources was possible. Generally, our solutions include two primary OA sources, i.e. hydrocarbon-like OA (HOA) and biomass burning OA (BBOA) and two secondary OA components, i.e. semi-volatile oxygenated OA (SV-OOA) and low-volatility oxygenated OA (LV-OOA). For specific sites cooking-related (COA) and marine-related sources (MSA) are also separated. Finally, our work provides a large overview of organic aerosol sources in Europe and an interesting set of highly time resolved data for modeling purposes.

Abstract Particulate brown carbon (BrC) in the atmosphere absorbs light at subvisible wavelengths and has poorly constrained but potentially large climate forcing impacts. BrC from biomass burning has virtually unknown lifecycle and atmospheric stability. Here, BrC emitted from intense wildfires was measured in plumes transported over 2 days from two main fires, during the 2013 NASA SEAC4RS mission. Concurrent measurements of organic aerosol (OA) and black carbon (BC) mass concentration, BC coating thickness, absorption Ångström exponent, and OA oxidation state reveal that the initial BrC emitted from the fires was largely unstable. Using back trajectories to estimate the transport time indicates that BrC aerosol light absorption decayed in the plumes with a half‐life of 9 to 15 h, measured over day and night. Although most BrC was lost within a day, possibly through chemical loss and/or evaporation, the remaining persistent fraction likely determines the background BrC levels most relevant for climate forcing.

Nighttime Sources Organic aerosols account for about half of the total mass of small (submicrometer) particles in the troposphere, and most of them are believed to form through the oxidation of volatile molecules, rather than being emitted directly from specific sources. These particles have important roles in many atmospheric processes, and therefore a better understanding of their complex composition and chemistry is desirable. Rollins et al. (p. 1210 ) report on measurements of particulate organic nitrates, an important class of organic aerosols that form at night. However, they also found that high concentrations of organic molecules can suppress the growth of organic nitrate particles. These observations should help improve efforts to reduce organic aerosol pollution.

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

Abstract. Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013–2025 decreases in anthropogenic emissions of 34 % for NOx (leading to a 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.

Abstract. We report the physical and chemical effects of photochemically aging dilute biomass-burning smoke. A "potential aerosol mass" (PAM) flow reactor was used with analysis by a high-resolution aerosol mass spectrometer and a proton-transfer-reaction ion-trap mass spectrometer during the FLAME-3 campaign. Hydroxyl (OH) radical concentrations in the reactor reached up to ~1000 times average tropospheric levels, producing effective OH exposures equivalent to up to 5 days of aging in the atmosphere, and allowing for us to extend the investigation of smoke aging beyond the oxidation levels achieved in traditional smog chambers. Volatile organic compound (VOC) observations show aromatics and terpenes decrease with aging, while formic acid and other unidentified oxidation products increase. Unidentified gas-phase oxidation products, previously observed in atmospheric and laboratory measurements, were observed here, including evidence of multiple generations of photochemistry. Substantial new organic aerosol (OA) mass ("net SOA"; secondary OA) was observed from aging biomass-burning smoke, resulting in total OA average of 1.42 ± 0.36 times the initial primary OA (POA) after oxidation. This study confirms that the net-SOA-to-POA ratio of biomass-burning smoke is far lower on average than that observed for urban emissions. Although most fuels were very reproducible, significant differences were observed among the biomasses, with some fuels resulting in a doubling of the OA mass, while for others a very small increase or even a decrease was observed. Net SOA formation in the photochemical reactor increased with OH exposure (OHexp), typically peaking around three days of equivalent atmospheric photochemical age (OHexp~3.9 × 1011 molecules cm−3 s), then leveling off at higher exposures. The amount of additional OA mass added from aging is positively correlated with initial POA concentration, but not with the total VOC concentration or the concentration of known SOA precursors. The mass of SOA formed often exceeded the mass of the known VOC precursors, indicating the likely importance of primary semivolatile/intermediate volatility species, and possibly of unidentified VOCs as SOA precursors in biomass burning smoke. Chemical transformations continued even after mass concentration stabilized. Changes in the biomass-burning tracer f60 ranged from substantially decreasing to remaining constant with increased aging. With increased OHexp, oxidation was always detected (as indicated by f44 and O/C). POA O/C ranged from 0.15 to 0.5, while aged OA O/C reached up to 0.87. The rate of oxidation and maximum O/C achieved differs for each biomass, and appears to increase with the initial O/C of the POA.

Abstract Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC 4 RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM 1 ) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM 1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM 1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM 1 emission estimate (1530 ± 570 Gg yr −1 ) is over 3 times that of the NEI PM 2.5 estimate and is also higher than the PM 2.5 emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions.

The chemical complexity of atmospheric organic aerosol (OA) has caused substantial uncertainties in understanding its origins and environmental impacts. Here, we provide constraints on OA origins through compositional characterization with molecular-level details. Our results suggest that secondary OA (SOA) from monoterpene oxidation accounts for approximately half of summertime fine OA in Centreville, AL, a forested area in the southeastern United States influenced by anthropogenic pollution. We find that different chemical processes involving nitrogen oxides, during days and nights, play a central role in determining the mass of monoterpene SOA produced. These findings elucidate the strong anthropogenic-biogenic interaction affecting ambient aerosol in the southeastern United States and point out the importance of reducing anthropogenic emissions, especially under a changing climate, where biogenic emissions will likely keep increasing.

Abstract. Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown to reflect large variations in its detailed molecular composition. The low fC5H6O (< 3 ‰) reported in non-IEPOX-derived isoprene-SOA from chamber studies indicates that this tracer ion is specifically enhanced from IEPOX-SOA, and is not a tracer for all SOA from isoprene. We introduce a graphical diagnostic to study the presence and aging of IEPOX-SOA as a triangle plot of fCO2 vs. fC5H6O. Finally, we develop a simplified method to estimate ambient IEPOX-SOA mass concentrations, which is shown to perform well compared to the full PMF method. The uncertainty of the tracer method is up to a factor of ~ 2, if the fC5H6O of the local IEPOX-SOA is not available. When only unit mass-resolution data are available, as with the aerosol chemical speciation monitor (ACSM), all methods may perform less well because of increased interferences from other ions at m/z 82. This study clarifies the strengths and limitations of the different AMS methods for detection of IEPOX-SOA and will enable improved characterization of this OA component.

Abstract In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO 3 ) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO 3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM 1 ) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NO x emission control.

Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 μg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA.

Abstract The Deep Convective Clouds and Chemistry (DC3) field experiment produced an exceptional dataset on thunderstorms, including their dynamical, physical, and electrical structures and their impact on the chemical composition of the troposphere. The field experiment gathered detailed information on the chemical composition of the inflow and outflow regions of midlatitude thunderstorms in northeast Colorado, west Texas to central Oklahoma, and northern Alabama. A unique aspect of the DC3 strategy was to locate and sample the convective outflow a day after active convection in order to measure the chemical transformations within the upper-tropospheric convective plume. These data are being analyzed to investigate transport and dynamics of the storms, scavenging of soluble trace gases and aerosols, production of nitrogen oxides by lightning, relationships between lightning flash rates and storm parameters, chemistry in the upper troposphere that is affected by the convection, and related source characterization of the three sampling regions. DC3 also documented biomass-burning plumes and the interactions of these plumes with deep convection.

Abstract. Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼ 25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH 2 SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate.

This paper describes a new instrument that uses a combination of thermal dissociation and laser‐induced fluorescence detection of NO 2 for in situ detection of the sum total peroxy nitrates, the sum total of alkyl nitrates and hydroxyalkyl nitrates, and HNO 3 . The instrument is capable of routine, continuous in situ measurements of these three classes of compounds that are accurate (15%) with a low detection limit (90 parts per trillion (ppt) 10 s −1 , S/N ratio = 2 on a background of 1 ppb NO 2 and 30 ppt 10 s −1 on a background of 100 ppt NO 2 ). Theoretical analysis of potential interferences combined with laboratory experiments that test for interferences show that rapidly cooling the gas and dropping the pressure after the thermal dissociation reduces interferences to the order of 1–5%. Observations in ambient air at the University of California Blodgett Forest Research Station demonstrate the capabilities of this instrument under field conditions. These field observations are compared with independent total NO y observations.

The Yosemite Aerosol Characterization Study of summer 2002 (YACS) occurred during an active fire season in the western United States and provided an opportunity to investigate many unresolved issues related to the radiative effects of biomass burning aerosols. Single particle analysis was performed on field‐collected aerosol samples using an array of electron microscopy techniques. Amorphous carbon spheres, or “tar balls,” were present in samples collected during episodes of high particle light scattering coefficients that occurred during the peak of a smoke/haze event. The highest concentrations of light‐absorbing carbon from a dual‐wavelength aethalometer (λ = 370 and 880 nm) occurred during periods when the particles were predominantly tar balls, indicating they do absorb light in the UV and near‐IR range of the solar spectrum. Closure experiments of mass concentrations and light scattering coefficients during periods dominated by tar balls did not require any distinct assumptions of organic carbon molecular weight correction factors, density, or refractive index compared to periods dominated by other types of organic carbon aerosols. Measurements of the hygroscopic behavior of tar balls using an environmental SEM indicate that tar balls do not exhibit deliquescence but do uptake some water at high (∼83%) relative humidity. The ability of tar balls to efficiently scatter and absorb light and to absorb water has important implications for their role in regional haze and climate forcing.

Abstract. At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign in the Colorado front range, July–August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of the role of NOx (NOx = NO + NO2) in oxidation of forest-emitted volatile organic compounds (VOCs) and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO2 + NO reactions. Aerosol-phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with [NO2] × [O3] but not with [O3]. These observations support the role of nighttime NO3-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests.

Abstract. Day-of-week patterns in human activities can be used to examine the ways in which differences in primary emissions result in changes in the rates of photochemical reactions, and the production of secondary pollutants. Data from twelve California Air Resources Board monitoring sites in Sacramento, CA, and the downwind Mountain Counties air basin are analyzed to reveal day of week patterns in ozone and its precursors in the summers of 1998–2002. Measurements of non-methane hydrocarbons are available for the summers of 2001–2003 at three of these sites and NOx at six of these sites for the full time period. This routine monitoring data is complemented by data sets of ozone and nitrogen oxide concentrations obtained in the summers of 2001 and 2003 at three sites in the region and comprehensive measurements of VOC reactivity at two sites in 2001. Daytime concentrations of nitrogen oxides (NOx≡NO+NO2) are approximately 35% lower on weekends at all the sites, whereas the VOC reactivity changes by less than 10%. All six sites in the Sacramento Valley have higher 8-h maximum average ozone on the weekend and are more likely to exceed the national standard of 85 ppb on the weekend. In contrast, all the sites in the Mountain Counties are less likely to exceed the federal ozone standard on the weekend. Analysis of the day-of-week trends in odd oxygen show that the weekend effect of ozone within Sacramento is strongly influenced by NO sources close to the monitoring sites. This suggests that ozone measurements from monitoring sites close to highways, including two rural locations, may not be representative of the regional abundance, and lead to underestimates of long term exposure for humans and ecosystems.

Abstract. We present results from the international field campaign DAURE (Determination of the sources of atmospheric Aerosols in Urban and Rural Environments in the Western Mediterranean), with the objective of apportioning the sources of fine carbonaceous aerosols. Submicron fine particulate matter (PM1) samples were collected during February–March 2009 and July 2009 at an urban background site in Barcelona (BCN) and at a forested regional background site in Montseny (MSY). We present radiocarbon (14C) analysis for elemental and organic carbon (EC and OC) and source apportionment for these data. We combine the results with those from component analysis of aerosol mass spectrometer (AMS) measurements, and compare to levoglucosan-based estimates of biomass burning OC, source apportionment of filter data with inorganic composition + EC + OC, submicron bulk potassium (K) concentrations, and gaseous acetonitrile concentrations. At BCN, 87 % and 91 % of the EC on average, in winter and summer, respectively, had a fossil origin, whereas at MSY these fractions were 66 % and 79 %. The contribution of fossil sources to organic carbon (OC) at BCN was 40 % and 48 %, in winter and summer, respectively, and 31 % and 25 % at MSY. The combination of results obtained using the 14C technique, AMS data, and the correlations between fossil OC and fossil EC imply that the fossil OC at Barcelona is ∼47 % primary whereas at MSY the fossil OC is mainly secondary (∼85 %). Day-to-day variation in total carbonaceous aerosol loading and the relative contributions of different sources predominantly depended on the meteorological transport conditions. The estimated biogenic secondary OC at MSY only increased by ∼40 % compared to the order-of-magnitude increase observed for biogenic volatile organic compounds (VOCs) between winter and summer, which highlights the uncertainties in the estimation of that component. Biomass burning contributions estimated using the 14C technique ranged from similar to slightly higher than when estimated using other techniques, and the different estimations were highly or moderately correlated. Differences can be explained by the contribution of secondary organic matter (not included in the primary biomass burning source estimates), and/or by an overestimation of the biomass burning OC contribution by the 14C technique if the estimated biomass burning EC/OC ratio used for the calculations is too high for this region. Acetonitrile concentrations correlate well with the biomass burning EC determined by 14C. K is a noisy tracer for biomass burning.

During wintertime measurements in coastal southern California, organonitrate groups accounted for up to 10% of organic mass (OM) in submicron particles. In this study, we report the calibrated absorptivity, the uncertainties in the calibrations, the detection limits for 12 and 24 h ambient sampling, and the multipeak retrieval algorithm for the method developed. Organonitrate groups were observed when both submicron particle-phase nitrate and OM concentrations exceeded 1 μg m−3. These high concentrations were associated with a mixed urban fossil fuel combustion source type that had potential source regions near Riverside and the South Coast Air Basin. The high frequency of these organonitrate observations contrasts with a number of studies of aerosol particles in other regions with more humid conditions, in which organonitrate groups were not detected and submicron sulfate concentrations exceeded those of nitrate. Our results suggest both that organonitrates form and/or exist in significant concentrations during polluted urban conditions and that their lifetime may be limited by hydrolysis in the particle phase.

Abstract The Observations and Modeling of the Green Ocean Amazon 2014–2015 (GoAmazon2014/5) experiment took place around the urban region of Manaus in central Amazonia across 2 years. The urban pollution plume was used to study the susceptibility of gases, aerosols, clouds, and rainfall to human activities in a tropical environment. Many aspects of air quality, weather, terrestrial ecosystems, and climate work differently in the tropics than in the more thoroughly studied temperate regions of Earth. GoAmazon2014/5, a cooperative project of Brazil, Germany, and the United States, employed an unparalleled suite of measurements at nine ground sites and on board two aircraft to investigate the flow of background air into Manaus, the emissions into the air over the city, and the advection of the pollution downwind of the city. Herein, to visualize this train of processes and its effects, observations aboard a low-flying aircraft are presented. Comparative measurements within and adjacent to the plume followed the emissions of biogenic volatile organic carbon compounds (BVOCs) from the tropical forest, their transformations by the atmospheric oxidant cycle, alterations of this cycle by the influence of the pollutants, transformations of the chemical products into aerosol particles, the relationship of these particles to cloud condensation nuclei (CCN) activity, and the differences in cloud properties and rainfall for background compared to polluted conditions. The observations of the GoAmazon2014/5 experiment illustrate how the hydrologic cycle, radiation balance, and carbon recycling may be affected by present-day as well as future economic development and pollution over the Amazonian tropical forest.

Abstract. An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected) compared to daytime (average 0.9 µg m−3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 4.4 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. To our knowledge this is the first time that this has been shown when comparing VOC concentrations with SOA formation measured at the same time, rather than comparing measurements made at different times. Several recently developed instruments have quantified ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). An SOA yield of 18–58 % from those compounds can explain the observed SOA formation. S/IVOCs were the only pool of gas-phase carbon that was large enough to explain the observed SOA formation. This work suggests that these typically unmeasured gases play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. These measurements help clarify the magnitude of potential SOA formation from OH oxidation in forested environments and demonstrate methods for interpretation of ambient OFR measurements.

Abstract. Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH ∼ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ∼ −0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OSC ∼ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. These results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.

Oxidation flow reactors (OFRs) containing low-pressure mercury (Hg) lamps that emit UV light at both 185 and 254 nm (“OFR185”) to generate OH radicals and O3 are used in many areas of atmospheric science and in pollution control devices. The widely used potential aerosol mass (PAM) OFR was designed for studies on the formation and oxidation of secondary organic aerosols (SOA), allowing for a wide range of oxidant exposures and short experiment duration with reduced wall loss effects. Although fundamental photochemical and kinetic data applicable to these reactors are available, the radical chemistry and its sensitivities have not been modeled in detail before; thus, experimental verification of our understanding of this chemistry has been very limited. To better understand the chemistry in the OFR185, a model has been developed to simulate the formation, recycling, and destruction of radicals and to allow the quantification of OH exposure (OHexp) in the reactor and its sensitivities. The model outputs of OHexp were evaluated against laboratory calibration experiments by estimating OHexp from trace gas removal and were shown to agree within a factor of 2. A sensitivity study was performed to characterize the dependence of the OHexp, HO2/OH ratio, and O3 and H2O2 output concentrations on reactor parameters. OHexp is strongly affected by the UV photon flux, absolute humidity, reactor residence time, and the OH reactivity (OHR) of the sampled air, and more weakly by pressure and temperature. OHexp can be strongly suppressed by high OHR, especially under low UV light conditions. A OHexp estimation equation as a function of easily measurable quantities was shown to reproduce model results within 10% (average absolute value of the relative errors) over the whole operating range of the reactor. OHexp from the estimation equation was compared with measurements in several field campaigns and shows agreement within a factor of 3. The improved understanding of the OFR185 and quantification of OHexp resulting from this work further establish the usefulness of such reactors for research studies, especially where quantifying the oxidation exposure is important.

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C5H12O6S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM2.5) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM2.5 collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

We present results from a high-resolution chemical ionization time-of-flight mass spectrometer (HRToF-CIMS), operated with two different thermal desorption inlets, designed to characterize the gas and aerosol composition. Data from two field campaigns at forested sites are shown. Particle volatility distributions are estimated using three different methods: thermograms, elemental formulas, and measured partitioning. Thermogram-based results are consistent with those from an aerosol mass spectrometer (AMS) with a thermal denuder, implying that thermal desorption is reproducible across very different experimental setups. Estimated volatilities from the detected elemental formulas are much higher than from thermograms since many of the detected species are thermal decomposition products rather than actual SOA molecules. We show that up to 65% of citric acid decomposes substantially in the FIGAERO-CIMS, with ∼20% of its mass detected as gas-phase CO2, CO, and H2O. Once thermal decomposition effects on the detected formulas are taken into account, formula-derived volatilities can be reconciled with the thermogram method. The volatility distribution estimated from partitioning measurements is very narrow, likely due to signal-to-noise limits in the measurements. Our findings indicate that many commonly used thermal desorption methods might lead to inaccurate results when estimating volatilities from observed ion formulas found in SOA. The volatility distributions from the thermogram method are likely the closest to the real distributions.

<p><strong>Abstract.</strong> Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO<sub>3</sub>) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO<sub>3</sub> to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO<sub>3</sub> radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23–44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C<sub>10</sub>H<sub>17</sub>NO<sub>5</sub>, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C<sub>5</sub>H<sub>9</sub>NO<sub>5</sub> was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NO<sub><I>y</I></sub> budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO<sub>3</sub> uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO<sub>3</sub> + BVOCs.</p>

Abstract. Oxidation flow reactors (OFRs) using OH produced from low-pressure Hg lamps at 254 nm (OFR254) or both 185 and 254 nm (OFR185) are commonly used in atmospheric chemistry and other fields. OFR254 requires the addition of externally formed O3 since OH is formed from O3 photolysis, while OFR185 does not since O2 can be photolyzed to produce O3, and OH can also be formed from H2O photolysis. In this study, we use a plug-flow kinetic model to investigate OFR properties under a very wide range of conditions applicable to both field and laboratory studies. We show that the radical chemistry in OFRs can be characterized as a function of UV light intensity, H2O concentration, and total external OH reactivity (OHRext, e.g., from volatile organic compounds (VOCs), NOx, and SO2). OH exposure is decreased by added external OH reactivity. OFR185 is especially sensitive to this effect at low UV intensity due to low primary OH production. OFR254 can be more resilient against OH suppression at high injected O3 (e.g., 70 ppm), as a larger primary OH source from O3, as well as enhanced recycling of HO2 to OH, make external perturbations to the radical chemistry less significant. However if the external OH reactivity in OFR254 is much larger than OH reactivity from injected O3, OH suppression can reach 2 orders of magnitude. For a typical input of 7 ppm O3 (OHRO3 = 10 s−1), 10-fold OH suppression is observed at OHRext ~ 100 s−1, which is similar or lower than used in many laboratory studies. The range of modeled OH suppression for literature experiments is consistent with the measured values except for those with isoprene. The finding on OH suppression may have important implications for the interpretation of past laboratory studies, as applying OHexp measurements acquired under different conditions could lead to over a 1-order-of-magnitude error in the estimated OHexp. The uncertainties of key model outputs due to uncertainty in all rate constants and absorption cross-sections in the model are within ±25 % for OH exposure and within ±60 % for other parameters. These uncertainties are small relative to the dynamic range of outputs. Uncertainty analysis shows that most of the uncertainty is contributed by photolysis rates of O3, O2, and H2O and reactions of OH and HO2 with themselves or with some abundant species, i.e., O3 and H2O2. OHexp calculated from direct integration and estimated from SO2 decay in the model with laminar and measured residence time distributions (RTDs) are generally within a factor of 2 from the plug-flow OHexp. However, in the models with RTDs, OHexp estimated from SO2 is systematically lower than directly integrated OHexp in the case of significant SO2 consumption. We thus recommended using OHexp estimated from the decay of the species under study when possible, to obtain the most appropriate information on photochemical aging in the OFR. Using HOx-recycling vs. destructive external OH reactivity only leads to small changes in OHexp under most conditions. Changing the identity (rate constant) of external OH reactants can result in substantial changes in OHexp due to different reductions in OH suppression as the reactant is consumed. We also report two equations for estimating OH exposure in OFR254. We find that the equation estimating OHexp from measured O3 consumption performs better than an alternative equation that does not use it, and thus recommend measuring both input and output O3 concentrations in OFR254 experiments. This study contributes to establishing a firm and systematic understanding of the gas-phase HOx and Ox chemistry in these reactors, and enables better experiment planning and interpretation as well as improved design of future reactors.

Abstract. Organic aerosol (OA) is an important fraction of submicron aerosols. However, it is challenging to predict and attribute the specific organic compounds and sources that lead to observed OA loadings, largely due to contributions from secondary production. This is especially true for megacities surrounded by numerous regional sources that create an OA background. Here, we utilize in situ gas and aerosol observations collected on board the NASA DC-8 during the NASA–NIER KORUS-AQ (Korea–United States Air Quality) campaign to investigate the sources and hydrocarbon precursors that led to the secondary OA (SOA) production observed over Seoul. First, we investigate the contribution of transported OA to total loadings observed over Seoul by using observations over the Yellow Sea coupled to FLEXPART Lagrangian simulations. During KORUS-AQ, the average OA loading advected into Seoul was ∼1–3 µg sm−3. Second, taking this background into account, the dilution-corrected SOA concentration observed over Seoul was ∼140 µgsm-3ppmv-1 at 0.5 equivalent photochemical days. This value is at the high end of what has been observed in other megacities around the world (20–70 µgsm-3ppmv-1 at 0.5 equivalent days). For the average OA concentration observed over Seoul (13 µg sm−3), it is clear that production of SOA from locally emitted precursors is the major source in the region. The importance of local SOA production was supported by the following observations. (1) FLEXPART source contribution calculations indicate any hydrocarbons with a lifetime of less than 1 day, which are shown to dominate the observed SOA production, mainly originate from South Korea. (2) SOA correlated strongly with other secondary photochemical species, including short-lived species (formaldehyde, peroxy acetyl nitrate, sum of acyl peroxy nitrates, dihydroxytoluene, and nitrate aerosol). (3) Results from an airborne oxidation flow reactor (OFR), flown for the first time, show a factor of 4.5 increase in potential SOA concentrations over Seoul versus over the Yellow Sea, a region where background air masses that are advected into Seoul can be measured. (4) Box model simulations reproduce SOA observed over Seoul within 11 % on average and suggest that short-lived hydrocarbons (i.e., xylenes, trimethylbenzenes, and semi-volatile and intermediate-volatility compounds) were the main SOA precursors over Seoul. Toluene alone contributes 9 % of the modeled SOA over Seoul. Finally, along with these results, we use the metric ΔOA/ΔCO2 to examine the amount of OA produced per fuel consumed in a megacity, which shows less variability across the world than ΔOA∕ΔCO.

Abstract. Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to water vapor mixing ratio (H2O) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportionally to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to volatile organic compound (VOC) consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. We define “riskier OFR conditions” as those with either low H2O (< 0.1 %) or high OHRext ( ≥ 100 s−1 in OFR185 and > 200 s−1 in OFR254). We strongly suggest avoiding such conditions as the importance of non-OH reactants can be substantial for the most sensitive species, although OH may still dominate under some riskier conditions, depending on the species present. Photolysis at non-tropospheric wavelengths (185 and 254 nm) may play a significant (> 20 %) role in the degradation of some aromatics, as well as some oxidation intermediates, under riskier reactor conditions, if the quantum yields are high. Under riskier conditions, some biogenics can have substantial destructions by O3, similarly to the troposphere. Working under low O2 (volume mixing ratio of 0.002) with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in laboratory studies and by humidification. Photolysis of secondary organic aerosol (SOA) samples is estimated to be significant (> 20 %) under the upper limit assumption of unity quantum yield at medium (1 × 1013 and 1.5 × 1015 photons cm−2 s−1 at 185 and 254 nm, respectively) or higher UV flux settings. The need for quantum yield measurements of both VOC and SOA photolysis is highlighted in this study. The results of this study allow improved OFR operation and experimental design and also inform the design of future reactors.

Abstract Organosulfates are important secondary organic aerosol (SOA) components and good tracers for aerosol heterogeneous reactions. However, the knowledge of their spatial distribution, formation conditions, and environmental impact is limited. In this study, we report two organosulfates, an isoprene‐derived isoprene epoxydiols (IEPOX) (2,3‐epoxy‐2‐methyl‐1,4‐butanediol) sulfate and a glycolic acid (GA) sulfate, measured using the NOAA Particle Analysis Laser Mass Spectrometer (PALMS) on board the NASA DC8 aircraft over the continental U.S. during the Deep Convective Clouds and Chemistry Experiment (DC3) and the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). During these campaigns, IEPOX sulfate was estimated to account for 1.4% of submicron aerosol mass (or 2.2% of organic aerosol mass) on average near the ground in the southeast U.S., with lower concentrations in the western U.S. (0.2–0.4%) and at high altitudes (<0.2%). Compared to IEPOX sulfate, GA sulfate was more uniformly distributed, accounting for about 0.5% aerosol mass on average, and may be more abundant globally. A number of other organosulfates were detected; none were as abundant as these two. Ambient measurements confirmed that IEPOX sulfate is formed from isoprene oxidation and is a tracer for isoprene SOA formation. The organic precursors of GA sulfate may include glycolic acid and likely have both biogenic and anthropogenic sources. Higher aerosol acidity as measured by PALMS and relative humidity tend to promote IEPOX sulfate formation, and aerosol acidity largely drives in situ GA sulfate formation at high altitudes. This study suggests that the formation of aerosol organosulfates depends not only on the appropriate organic precursors but also on emissions of anthropogenic sulfur dioxide (SO 2 ), which contributes to aerosol acidity.

Abstract Emissions from 15 agricultural fires in the southeastern U.S. were measured from the NASA DC‐8 research aircraft during the summer 2013 Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC 4 RS) campaign. This study reports a detailed set of emission factors (EFs) for 25 trace gases and 6 fine particle species. The chemical evolution of the primary emissions in seven plumes was examined in detail for ~1.2 h. A Lagrangian plume cross‐section model was used to simulate the evolution of ozone (O 3 ), reactive nitrogen species, and organic aerosol (OA). Observed EFs are generally consistent with previous measurements of crop residue burning, but the fires studied here emitted high amounts of SO 2 and fine particles, especially primary OA and chloride. Filter‐based measurements of aerosol light absorption implied that brown carbon (BrC) was ubiquitous in the plumes. In aged plumes, rapid production of O 3 , peroxyacetyl nitrate (PAN), and nitrate was observed with ΔO 3 /ΔCO, ΔPAN/ΔNO y , and Δnitrate/ΔNO y reaching ~0.1, ~0.3, and ~0.3. For five selected cases, the model reasonably simulated O 3 formation but underestimated PAN formation. No significant evolution of OA mass or BrC absorption was observed. However, a consistent increase in oxygen‐to‐carbon (O/C) ratios of OA indicated that OA oxidation in the agricultural fire plumes was much faster than in urban and forest fire plumes. Finally, total annual SO 2 , NO x , and CO emissions from agricultural fires in Arkansas, Louisiana, Mississippi, and Missouri were estimated (within a factor of ~2) to be equivalent to ~2% SO 2 from coal combustion and ~1% NO x and ~9% CO from mobile sources.

Abstract. Chemical components of organic aerosol (OA) selectively absorb light at short wavelengths. In this study, the prevalence, sources, and optical importance of this so-called brown carbon (BrC) aerosol component are investigated throughout the North American continental tropospheric column during a summer of extensive biomass burning. Spectrophotometric absorption measurements on extracts of bulk aerosol samples collected from an aircraft over the central USA were analyzed to directly quantify BrC abundance. BrC was found to be prevalent throughout the 1 to 12 km altitude measurement range, with dramatic enhancements in biomass-burning plumes. BrC to black carbon (BC) ratios, under background tropospheric conditions, increased with altitude, consistent with a corresponding increase in the absorption Ångström exponent (AAE) determined from a three-wavelength particle soot absorption photometer (PSAP). The sum of inferred BC absorption and measured BrC absorption at 365 nm was within 3 % of the measured PSAP absorption for background conditions and 22 % for biomass burning. A radiative transfer model showed that BrC absorption reduced top-of-atmosphere (TOA) aerosol forcing by ~ 20 % in the background troposphere. Extensive radiative model simulations applying this study background tropospheric conditions provided a look-up chart for determining radiative forcing efficiencies of BrC as a function of a surface-measured BrC : BC ratio and single scattering albedo (SSA). The chart is a first attempt to provide a tool for better assessment of brown carbon's forcing effect when one is limited to only surface data. These results indicate that BrC is an important contributor to direct aerosol radiative forcing.

A 6-week study was conducted at the University of Colorado Art Museum, during which volatile organic compounds (VOCs), carbon dioxide (CO2), ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), other trace gases, and submicron aerosol were measured continuously. These measurements were then analyzed using a box model to quantify the rates of major processes that transformed the composition of the air. VOC emission factors were quantified for museum occupants and their activities. The deposition of VOCs to surfaces was quantified across a range of VOC saturation vapor concentrations ( C*) and Henry's Law constants ( H) and determined to be a major sink for VOCs with C* < 108 μg m-3 and H > 102 M atm-1. The reaction rates of VOCs with O3, OH radicals, and nitrate (NO3) radicals were quantified, with unsaturated and saturated VOCs having oxidation lifetimes of >5 and >15 h, making deposition to surfaces and ventilation the dominant VOC sinks in the museum. O3 loss rates were quantified inside a museum gallery, where reactions with surfaces, NO, occupants, and NO2 accounted for 62%, 31%, 5%, and 2% of the O3 sink. The measured concentrations of acetic acid, formic acid, NO2, O3, particulate matter, sulfur dioxide, and total VOCs were below the guidelines for museums.

Abstract. Hundreds of gas- and particle-phase organic acids were measured in a rural ponderosa pine forest in Colorado, USA, during BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics &amp;amp; Nitrogen – Rocky Mountain Biogenic Aerosol Study). A recently developed micro-orifice volatilization impactor high-resolution time-of-flight chemical ionization mass spectrometer (MOVI-HRToF-CIMS) using acetate (CH3C(O)O−) as the reagent ion was used to selectively ionize and detect acids semicontinuously from 20 to 30 August 2011, with a measurement time resolution of ~1.5 h. At this site 98% of the organic acid mass is estimated to be in the gas phase, with only ~2% in the particle phase. We investigated gas–particle partitioning, quantified as the fraction in the particle phase (Fp), of C1–C18 alkanoic acids, six known terpenoic acids, and bulk organic acids vs. carbon number. Data were compared to the absorptive partitioning model and suggest that bulk organic acids at this site follow absorptive partitioning to the organic aerosol mass. The rapid response (&lt;1–2 h) of partitioning to temperature changes for bulk acids suggests that kinetic limitations to equilibrium are minor, which is in contrast to conclusions of some recent laboratory and field studies, possibly due to lack of very low ambient relative humidities at this site. Time trends for partitioning of individual and groups of acids were mostly captured by the model, with varying degrees of absolute agreement. Species with predicted substantial fractions in both the gas and particle phases show better absolute agreement, while species with very low predicted fractions in one phase often show poor agreement, potentially due to thermal decomposition, inlet adsorption, or other issues. Partitioning to the aqueous phase is predicted to be smaller than to the organic phase for alkanoic and bulk acids, and has different trends with time and carbon number than observed experimentally. This is due to the limited additional functionalization observed for the bulk acids. Partitioning to water appears to only play a role for the most oxidized acids during periods of high aerosol liquid water. Based on measurement–model comparison we conclude that species carbon number and oxygen content, together with ambient temperature, control the volatility of organic acids and are good predictors for partitioning at this site. Partitioning of bulk acids is more consistent with model predictions for hydroxy acids, hydroperoxyacids, or polyacids, and less so for keto acids.

Abstract. Aircraft observations of meteorological, trace gas, and aerosol properties were made during May–September 2013 in the southeastern United States (US) under fair-weather, afternoon conditions with well-defined planetary boundary layer structure. Optical extinction at 532 nm was directly measured at relative humidities (RHs) of ∼ 15, ∼ 70, and ∼ 90 % and compared with extinction calculated from measurements of aerosol composition and size distribution using the κ-Köhler approximation for hygroscopic growth. The calculated enhancement in hydrated aerosol extinction with relative humidity, f(RH), calculated by this method agreed well with the observed f(RH) at ∼ 90 % RH. The dominance of organic aerosol, which comprised 65 ± 10 % of particulate matter with aerodynamic diameter &lt; 1 µm in the planetary boundary layer, resulted in relatively low f(RH) values of 1.43 ± 0.67 at 70 % RH and 2.28 ± 1.05 at 90 % RH. The subsaturated κ-Köhler hygroscopicity parameter κ for the organic fraction of the aerosol must have been &lt; 0.10 to be consistent with 75 % of the observations within uncertainties, with a best estimate of κ = 0.05. This subsaturated κ value for the organic aerosol in the southeastern US is broadly consistent with field studies in rural environments. A new, physically based, single-parameter representation was developed that better described f(RH) than did the widely used gamma power-law approximation.

Abstract. Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100 µg m−3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0 × 10−13 cm3 molec−1 s−1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (&gt; 1 × 1012 molec cm−3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59 ± 0.33 in SE US and γOH = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

Abstract Most intensive field studies investigating aerosols have been conducted in summer, and thus, wintertime aerosol sources and chemistry are comparatively poorly understood. An aerosol mass spectrometer was flown on the National Science Foundation/National Center for Atmospheric Research C‐130 during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) 2015 campaign in the northeast United States. The fraction of boundary layer submicron aerosol that was organic aerosol (OA) was about a factor of 2 smaller than during a 2011 summertime study in a similar region. However, the OA measured in WINTER was almost as oxidized as OA measured in several other studies in warmer months of the year. Fifty‐eight percent of the OA was oxygenated (secondary), and 42% was primary (POA). Biomass burning OA (likely from residential heating) was ubiquitous and accounted for 33% of the OA mass. Using nonvolatile POA, one of two default secondary OA (SOA) formulations in GEOS‐Chem (v10‐01) shows very large underpredictions of SOA and O/C (5×) and overprediction of POA (2×). We strongly recommend against using that formulation in future studies. Semivolatile POA, an alternative default in GEOS‐Chem, or a simplified parameterization (SIMPLE) were closer to the observations, although still with substantial differences. A case study of urban outflow from metropolitan New York City showed a consistent amount and normalized rate of added OA mass (due to SOA formation) compared to summer studies, although proceeding more slowly due to lower OH concentrations. A box model and SIMPLE perform similarly for WINTER as for Los Angeles, with an underprediction at ages &lt;6 hr, suggesting that fast chemistry might be missing from the models.

Abstract. Losses of gas-phase compounds or delays on their transfer through tubing are important for atmospheric measurements and also provide a method to characterize and quantify gas–surface interactions. Here we expand recent results by comparing different types of Teflon and other polymer tubing, as well as glass, uncoated and coated stainless steel and aluminum, and other tubing materials by measuring the response to step increases and decreases in organic compound concentrations. All polymeric tubings showed absorptive partitioning behavior with no dependence on humidity or concentration, with PFA Teflon tubing performing best in our tests. Glass and uncoated and coated metal tubing showed very different phenomenology due to adsorptive partitioning to a finite number of surface sites. Strong dependencies on compound concentration, mixture composition, functional groups, humidity, and memory effects were observed for glass and uncoated and coated metals, which (except for Silonite-coated stainless steel) also always caused longer delays than Teflon for the compounds and concentrations tested. Delays for glass and uncoated and coated metal tubing were exacerbated at low relative humidity but reduced for RH &gt;20 %. We find that conductive PFA and Silonite tubing perform best among the materials tested for gas-plus-particle sampling lines, combining reduced gas-phase delays with good particle transmission.

Abstract. The spatial distribution and properties of submicron organic aerosol (OA) are among the key sources of uncertainty in our understanding of aerosol effects on climate. Uncertainties are particularly large over remote regions of the free troposphere and Southern Ocean, where very few data have been available and where OA predictions from AeroCom Phase II global models span 2 to 3 orders of magnitude, greatly exceeding the model spread over source regions. The (nearly) pole-to-pole vertical distribution of non-refractory aerosols was measured with an aerosol mass spectrometer onboard the NASA DC-8 aircraft as part of the Atmospheric Tomography (ATom) mission during the Northern Hemisphere summer (August 2016) and winter (February 2017). This study presents the first extensive characterization of OA mass concentrations and their level of oxidation in the remote atmosphere. OA and sulfate are the major contributors by mass to submicron aerosols in the remote troposphere, together with sea salt in the marine boundary layer. Sulfate was dominant in the lower stratosphere. OA concentrations have a strong seasonal and zonal variability, with the highest levels measured in the lower troposphere in the summer and over the regions influenced by biomass burning from Africa (up to 10 µg sm−3). Lower concentrations (∼0.1–0.3 µg sm−3) are observed in the northern middle and high latitudes and very low concentrations (&lt;0.1 µg sm−3) in the southern middle and high latitudes. The ATom dataset is used to evaluate predictions of eight current global chemistry models that implement a variety of commonly used representations of OA sources and chemistry, as well as of the AeroCom-II ensemble. The current model ensemble captures the average vertical and spatial distribution of measured OA concentrations, and the spread of the individual models remains within a factor of 5. These results are significantly improved over the AeroCom-II model ensemble, which shows large overestimations over these regions. However, some of the improved agreement with observations occurs for the wrong reasons, as models have the tendency to greatly overestimate the primary OA fraction and underestimate the secondary fraction. Measured OA in the remote free troposphere is highly oxygenated, with organic aerosol to organic carbon (OA ∕ OC) ratios of ∼2.2–2.8, and is 30 %–60 % more oxygenated than in current models, which can lead to significant errors in OA concentrations. The model–measurement comparisons presented here support the concept of a more dynamic OA system as proposed by Hodzic et al. (2016), with enhanced removal of primary OA and a stronger production of secondary OA in global models needed to provide better agreement with observations.

Abstract. Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenic emissions of organic compounds, constitutes a substantial fraction of the mass of submicron aerosol in populated areas around the world and contributes to poor air quality and premature mortality. However, the precursor sources of ASOA are poorly understood, and there are large uncertainties in the health benefits that might accrue from reducing anthropogenic organic emissions. We show that the production of ASOA in 11 urban areas on three continents is strongly correlated with the reactivity of specific anthropogenic volatile organic compounds. The differences in ASOA production across different cities can be explained by differences in the emissions of aromatics and intermediate- and semi-volatile organic compounds, indicating the importance of controlling these ASOA precursors. With an improved model representation of ASOA driven by the observations, we attribute 340 000 PM2.5-related premature deaths per year to ASOA, which is over an order of magnitude higher than prior studies. A sensitivity case with a more recently proposed model for attributing mortality to PM2.5 (the Global Exposure Mortality Model) results in up to 900 000 deaths. A limitation of this study is the extrapolation from cities with detailed studies and regions where detailed emission inventories are available to other regions where uncertainties in emissions are larger. In addition to further development of institutional air quality management infrastructure, comprehensive air quality campaigns in the countries in South and Central America, Africa, South Asia, and the Middle East are needed for further progress in this area.

Abstract. Volatility and viscosity are important properties of organic aerosols (OA), affecting aerosol processes such as formation, evolution, and partitioning of OA. Volatility distributions of ambient OA particles have often been measured, while viscosity measurements are scarce. We have previously developed a method to estimate the glass transition temperature (Tg) of an organic compound containing carbon, hydrogen, and oxygen. Based on analysis of over 2400 organic compounds including oxygenated organic compounds, as well as nitrogen- and sulfur-containing organic compounds, we extend this method to include nitrogen- and sulfur-containing compounds based on elemental composition. In addition, parameterizations are developed to predict Tg as a function of volatility and the atomic oxygen-to-carbon ratio based on a negative correlation between Tg and volatility. This prediction method of Tg is applied to ambient observations of volatility distributions at 11 field sites. The predicted Tg values of OA under dry conditions vary mainly from 290 to 339 K and the predicted viscosities are consistent with the results of ambient particle-phase-state measurements in the southeastern US and the Amazonian rain forest. Reducing the uncertainties in measured volatility distributions would improve predictions of viscosity, especially at low relative humidity. We also predict the Tg of OA components identified via positive matrix factorization of aerosol mass spectrometer (AMS) data. The predicted viscosity of oxidized OA is consistent with previously reported viscosity of secondary organic aerosols (SOA) derived from α-pinene, toluene, isoprene epoxydiol (IEPOX), and diesel fuel. Comparison of the predicted viscosity based on the observed volatility distributions with the viscosity simulated by a chemical transport model implies that missing low volatility compounds in a global model can lead to underestimation of OA viscosity at some sites. The relation between volatility and viscosity can be applied in the molecular corridor or volatility basis set approaches to improve OA simulations in chemical transport models by consideration of effects of particle viscosity in OA formation and evolution.

Lamps emitting at 222 nm have attracted recent interest for germicidal ultraviolet disinfection ("GUV222"). Their impact on indoor air quality is considered negligible. In this study, ozone formation is observed for eight different lamps from five manufacturers, in amounts an order of magnitude larger than previous reports. Most lamps produce O3 in amounts close to the first-principles calculation, with, e.g., a generation rate of 22 ppb h–1 for Ushio B1 modules in a 21 m3 chamber. Much more O3 is produced by lamps when optical filters are removed for tests and by an undesired internal electrical discharge. A test in an office shows an increase of ∼6.5 ppb during lamp-on periods, consistent with a simple model with the O3 generation rate, ventilation, and O3 losses. We demonstrate the use of a photolytic tracer (CBr4) to quantify the averaged GUV222 fluence rate in a room. An important consequence of O3 production by GUV222 is particulate matter (PM) formation, which may have significant negative health impacts. To limit GUV222-created indoor pollution, new guidelines should be developed and lower fluence rates should be used if possible, especially under low-ventilation conditions. Low-cost sensors for O3 and PM were not useful for investigating GUV222-induced chemistry.

We describe measurements of NO 2 , total peroxy nitrates (ΣPNs), total alkyl nitrates (ΣANs), and HNO 3 using thermal dissociation followed by laser‐induced fluorescence detection of NO 2 at three continental locations. The ΣAN observations are unique and provide novel constraints on atmospheric photochemistry. At a rural site in California, measurements over a full annual cycle show that ΣANs are routinely 10–20% of NO y . At this rural site, at a suburban site in California and an urban site in Houston, Texas, both the absolute concentration of ΣANs and the fraction of the higher oxides of nitrogen (NO z ) represented by ΣANs are greater than or equal to values reported in any prior observations. Although the contrast with prior observations is striking, we show that large abundances of ΣANs are consistent with simple chemical models of tropospheric ozone production and with the few prior comprehensive model studies. We also show that ΣANs are a large part, if not all, of the “missing NO y ” reported in many prior experiments and emphasize that the ratios of ΣANs/NO z and of O 3 /ΣANs are especially useful for evaluating chemical models and comparing observations at different sites.

Abstract Emissions of SO 2 in the United States have declined since the early 1990s, resulting in a decrease in aerosol sulfate mass in the Southeastern U.S. of −4.5(±0.9)% yr −1 between 1992 and 2013. Organic aerosol mass, the other major aerosol component in the Southeastern U.S., has decreased more slowly despite concurrent emission reductions in anthropogenic precursors. Summertime measurements in rural Alabama quantify the change in aerosol light extinction as a function of aerosol composition and relative humidity. Application of this relationship to composition data from 2001 to 2013 shows that a −1.1(±0.7)% yr −1 decrease in extinction can be attributed to decreasing aerosol water mass caused by the change in aerosol sulfate/organic ratio. Calculated reductions in extinction agree with regional trends in ground‐based and satellite‐derived aerosol optical depth. The diurnally averaged summertime surface radiative effect has changed by 8.0 W m −2 , with 19% attributed to the decrease in aerosol water.

Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of volatile organic compounds (VOCs) emitted by anthropogenic and biogenic sources, are a poorly understood but substantial component of atmospheric particles. In this study, we examined the chemical and physical properties of SOA at Bakersfield, California, a site influenced by anthropogenic and terrestrial biogenic emissions. Factor analysis was applied to the infrared and mass spectra of fine particles to identify sources and atmospheric processing that contributed to the organic mass (OM). We found that OM accounted for 56% of submicron particle mass, with SOA components contributing 80% to 90% of OM from 15 May to 29 June 2010. SOA formed from alkane and aromatic compounds, the two major classes of vehicle‐emitted hydrocarbons, accounted for 65% OM (72% SOA). The alkane and aromatic SOA components were associated with 200 nm to 500 nm accumulation mode particles, likely from condensation of daytime photochemical products of VOCs. In contrast, biogenic SOA likely formed from condensation of secondary organic vapors, produced from NO 3 radical oxidation reactions during nighttime hours, on 400 nm to 700 nm sized primary particles, and accounted for less than 10% OM. Local petroleum operation emissions contributed 13% to the OM, and the moderate O/C (0.2) of this factor suggested it was largely of secondary origin. Approximately 10% of organic aerosols in submicron particles were identified as either vegetative detritus (10%) or cooking activities (7%), from Fourier transform infrared spectroscopic and aerosol mass spectrometry measurements, respectively. While the mass spectra of several linearly independent SOA components were nearly identical and external source markers were needed to separate them, each component had distinct infrared spectrum, likely associated with the source‐specific VOCs from which they formed.

Abstract. The Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics &amp;amp; Nitrogen (BEACHON) project seeks to understand the feedbacks and inter-relationships between hydrology, biogenic emissions, carbon assimilation, aerosol properties, clouds and associated feedbacks within water-limited ecosystems. The Manitou Experimental Forest Observatory (MEFO) was established in 2008 by the National Center for Atmospheric Research to address many of the BEACHON research objectives, and it now provides a fixed field site with significant infrastructure. MEFO is a mountainous, semi-arid ponderosa pine-dominated forest site that is normally dominated by clean continental air but is periodically influenced by anthropogenic sources from Colorado Front Range cities. This article summarizes the past and ongoing research activities at the site, and highlights some of the significant findings that have resulted from these measurements. These activities include - soil property measurements; - hydrological studies; - measurements of high-frequency turbulence parameters; - eddy covariance flux measurements of water, energy, aerosols and carbon dioxide through the canopy; - determination of biogenic and anthropogenic volatile organic compound emissions and their influence on regional atmospheric chemistry; - aerosol number and mass distributions; - chemical speciation of aerosol particles; - characterization of ice and cloud condensation nuclei; - trace gas measurements; and - model simulations using coupled chemistry and meteorology. In addition to various long-term continuous measurements, three focused measurement campaigns with state-of-the-art instrumentation have taken place since the site was established, and two of these studies are the subjects of this special issue: BEACHON-ROCS (Rocky Mountain Organic Carbon Study, 2010) and BEACHON-RoMBAS (Rocky Mountain Biogenic Aerosol Study, 2011).

Abstract. Real-time measurements of inorganic (sulfate, nitrate, ammonium, chloride and black carbon (BC)) and organic submicron aerosols (particles with an aerodynamic diameter of less than 1 μm) from a continental background site (Montsec, MSC, 1570 m a.s.l.) in the western Mediterranean Basin (WMB) were conducted for 10 months (July 2011–April 2012). An aerosol chemical speciation monitor (ACSM) was co-located with other online and offline PM1 measurements. Analyses of the hourly, diurnal, and seasonal variations are presented here, for the first time, for this region. Seasonal trends in PM1 components are attributed to variations in evolution of the planetary boundary layer (PBL) height, air mass origin, and meteorological conditions. In summer, the higher temperature and solar radiation increases convection, enhancing the growth of the PBL and the transport of anthropogenic pollutants towards high altitude sites. Furthermore, the regional recirculation of air masses over the WMB creates a continuous increase in the background concentrations of PM1 components and causes the formation of reservoir layers at relatively high altitudes. The combination of all these atmospheric processes results in a high variability of PM1 components, with poorly defined daily patterns, except for the organic aerosols (OA). OA was mostly composed (up to 90%) of oxygenated organic aerosol (OOA), split in two types: semivolatile (SV-OOA) and low-volatility (LV-OOA), the rest being hydrocarbon-like OA (HOA). The marked diurnal cycles of OA components regardless of the air mass origin indicates that they are not only associated with anthropogenic and long-range-transported secondary OA (SOA) but also with recently produced biogenic SOA. Very different conditions drive the aerosol phenomenology in winter at MSC. The thermal inversions and the lower vertical development of the PBL leave MSC in the free troposphere most of the day, being affected by PBL air masses only after midday, when the mountain breezes transport emissions from the adjacent valleys and plains to the top of the mountain. This results in clear diurnal patterns of both organic and inorganic concentrations. OA was also mainly composed (71%) of OOA, with contributions from HOA (5%) and biomass burning OA (BBOA; 24%). Moreover, in winter sporadic long-range transport from mainland Europe is observed. The results obtained in the present study highlight the importance of SOA formation processes at a remote site such as MSC, especially in summer. Additional research is needed to characterize the sources and processes of SOA formation at remote sites.

Abstract In situ aerosol particle measurements were conducted during 21 NASA DC‐8 flights in the Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys field campaign over the United States, Canada, Pacific Ocean, and Gulf of Mexico. For the first time, this study reports rapid, size‐resolved hygroscopic growth and real refractive index (RI at 532 nm) data between the surface and upper troposphere in a variety of air masses including wildfires, agricultural fires, biogenic, marine, and urban outflow. The Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe (DASH‐SP) quantified size‐resolved diameter growth factors (GF = D p ,wet / D p ,dry ) that are used to infer the hygroscopicity parameter κ . Thermokinetic simulations were conducted to estimate the impact of partial particle volatilization within the DASH‐SP across a range of sampling conditions. Analyses of GF and RI data as a function of air mass origin, dry size, and altitude are reported, in addition to κ values for the inorganic and organic fractions of aerosol. Average RI values are found to be fairly constant (1.52–1.54) for all air mass categories. An algorithm is used to compare size‐resolved DASH‐SP GF with bulk scattering f (RH = 80%) data obtained from a pair of nephelometers, and the results show that the two can only be reconciled if GF is assumed to decrease with increasing dry size above 400 nm (i.e., beyond the upper bound of DASH‐SP measurements). Individual case studies illustrate variations of hygroscopicity as a function of dry size, environmental conditions, altitude, and composition.

Exchange of atmospheric organic compounds between gas and particle phases is important in the production and chemistry of particle-phase mass but is poorly understood due to a lack of simultaneous measurements in both phases of individual compounds. Measurements of particle- and gas-phase organic compounds are reported here for the southeastern United States and central Amazonia. Polyols formed from isoprene oxidation contribute 8% and 15% on average to particle-phase organic mass at these sites but are also observed to have substantial gas-phase concentrations contrary to many models that treat these compounds as nonvolatile. The results of the present study show that the gas-particle partitioning of approximately 100 known and newly observed oxidation products is not well explained by environmental factors (e.g., temperature). Compounds having high vapor pressures have higher particle fractions than expected from absorptive equilibrium partitioning models. These observations support the conclusion that many commonly measured biogenic oxidation products may be bound in low-volatility mass (e.g., accretion products, inorganic-organic adducts) that decomposes to individual compounds on analysis. However, the nature and extent of any such bonding remains uncertain. Similar conclusions are reach for both study locations, and average particle fractions for a given compound are consistent within ∼25% across measurement sites.

Atmospheric organic compounds are central to key chemical processes that influence air quality, ecological health, and climate. However, longstanding difficulties in predicting important quantities such as organic aerosol formation and oxidant lifetimes indicate that our understanding of atmospheric organic chemistry is fundamentally incomplete, probably due in part to the presence of organic species that are unmeasured using standard analytical techniques. Here we present measurements of a wide range of atmospheric organic compounds—including previously unmeasured species—taken concurrently at a single site (a ponderosa pine forest during summertime) by five state-of-the-art mass spectrometric instruments. The combined data set provides a comprehensive characterization of atmospheric organic carbon, covering a wide range in chemical properties (volatility, oxidation state, and molecular size), and exhibiting no obvious measurement gaps. This enables the first construction of a measurement-based local organic budget, highlighting the high emission, deposition, and oxidation fluxes in this environment. Moreover, previously unmeasured species, including semivolatile and intermediate-volatility organic species (S/IVOCs), account for one-third of the total organic carbon, and (within error) provide closure on both OH reactivity and potential secondary organic aerosol formation. Atmospheric organic compounds are central to key chemical processes that influence air quality. Concurrent measurements of a wide range of these compounds, including previously unmeasured ones, provide closure on OH reactivity.

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

Abstract. During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ∼ 0. 15 is consistent with the largely uniform and high O : C value (∼ 0. 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O : C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O : C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the κ value with O : C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O : C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O : C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O : C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in κorg with O : C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between κorg and O : C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

Abstract. Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m−3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O:C up to O:C∼1.0, and then decreased as O:C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C=C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

Abstract We examine the distribution and fate of nitrogen oxides (NO x ) in the lower troposphere over the Northeast United States (NE US) using aircraft observations from the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign in February–March 2015, as well as the GEOS‐Chem chemical transport model and concurrent ground‐based observations. We find that the National Emission Inventory from the U.S. Environmental Protection Agency is consistent with WINTER observations of total reactive nitrogen ( T NO y ) to within 10% on average, in contrast to the significant overestimate reported in past studies under warmer conditions. Updates to the dry deposition scheme and dinitrogen pentoxide (N 2 O 5 ) reactive uptake probability, ɣ(N 2 O 5 ), result in an improved simulation of gas‐phase nitric acid (HNO 3 ) and submicron particulate nitrate (pNO 3 − ), reducing the longstanding factor of 2–3 overestimate in wintertime HNO 3 + pNO 3 − to a 50% positive bias. We find a NO x lifetime against chemical loss and deposition of 22 hr in the lower troposphere over the NE US. Chemical loss of NO x is dominated by N 2 O 5 hydrolysis (58% of loss) and reaction with OH (33%), while 7% of NO x leads to the production of organic nitrates. Wet and dry deposition account for 55% and 45% of T NO y deposition over land, respectively. We estimate that 42% of the NO x emitted is exported from the NE US boundary layer during winter, mostly in the form of HNO 3 + pNO 3 − (40%) and NO x (38%).

Abstract. Aerosol hygroscopicity describes the ability of a particle to take up water and form a cloud droplet. Modeling studies have shown sensitivity of precipitation-producing cloud systems to the availability of aerosol particles capable of serving as cloud condensation nuclei (CCN), and hygroscopicity is a key parameter controlling the number of available CCN. Continental aerosol is typically assumed to have a representative hygroscopicity parameter, κ, of 0.3; however, in remote locations this value can be lower due to relatively large mass fractions of organic components. To further our understanding of aerosol properties in remote areas, we measured size-resolved aerosol chemical composition and hygroscopicity in a forested, mountainous site in Colorado during the six-week BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen–Rocky Mountain Biogenic Aerosol Study) campaign. This campaign followed a year-long measurement period at this site, and results from the intensive campaign shed light on the previously reported seasonal cycle in aerosol hygroscopicity. New particle formation events were observed routinely at this site and nucleation mode composition measurements indicated that the newly formed particles were predominantly organic. These events likely contribute to the dominance of organic species at smaller sizes, where aerosol organic mass fractions were between 70 and 90%. Corresponding aerosol hygroscopicity was observed to be in the range κ = 0.15–0.22, with hygroscopicity increasing with particle size. Aerosol chemical composition measured by an aerosol mass spectrometer and calculated from hygroscopicity measurements agreed very well during the intensive study, with an assumed value of κorg = 0.13 resulting in the best agreement.

Abstract. Ambient pine forest air was oxidized by OH, O3, or NO3 radicals using an oxidation flow reactor (OFR) during the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen – Rocky Mountain Biogenic Aerosol Study) campaign to study biogenic secondary organic aerosol (SOA) formation and organic aerosol (OA) aging. A wide range of equivalent atmospheric photochemical ages was sampled, from hours up to days (for O3 and NO3) or weeks (for OH). Ambient air processed by the OFR was typically sampled every 20–30 min, in order to determine how the availability of SOA precursor gases in ambient air changed with diurnal and synoptic conditions, for each of the three oxidants. More SOA was formed during nighttime than daytime for all three oxidants, indicating that SOA precursor concentrations were higher at night. At all times of day, OH oxidation led to approximately 4 times more SOA formation than either O3 or NO3 oxidation. This is likely because O3 and NO3 will only react with gases containing C = C bonds (e.g., terpenes) to form SOA but will not react appreciably with many of their oxidation products or any species in the gas phase that lacks a C = C bond (e.g., pinonic acid, alkanes). In contrast, OH can continue to react with compounds that lack C = C bonds to produce SOA. Closure was achieved between the amount of SOA formed from O3 and NO3 oxidation in the OFR and the SOA predicted to form from measured concentrations of ambient monoterpenes and sesquiterpenes using published chamber yields. This is in contrast to previous work at this site (Palm et al., 2016), which has shown that a source of SOA from semi- and intermediate-volatility organic compounds (S/IVOCs) 3.4 times larger than the source from measured VOCs is needed to explain the measured SOA formation from OH oxidation. This work suggests that those S/IVOCs typically do not contain C = C bonds. O3 and NO3 oxidation produced SOA with elemental O : C and H : C similar to the least-oxidized OA observed in local ambient air, and neither oxidant led to net mass loss at the highest exposures, in contrast to OH oxidation. An OH exposure in the OFR equivalent to several hours of atmospheric aging also produced SOA with O : C and H : C values similar to ambient OA, while higher aging (days–weeks) led to formation of SOA with progressively higher O : C and lower H : C (and net mass loss at the highest exposures). NO3 oxidation led to the production of particulate organic nitrates (pRONO2), while OH and O3 oxidation (under low NO) did not, as expected. These measurements of SOA formation provide the first direct comparison of SOA formation potential and chemical evolution from OH, O3, and NO3 oxidation in the real atmosphere and help to clarify the oxidation processes that lead to SOA formation from biogenic hydrocarbons.

Abstract. Biogenic volatile organic compounds (BVOCs) from the Amazon forest region represent the largest source of organic carbon emissions to the atmosphere globally. These BVOC emissions dominantly consist of volatile and intermediate-volatility terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). We collected quartz filter samples with 12 h time resolution and performed hourly in situ measurements with a semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) at a rural site (T3) located to the west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon2014/5) field campaign to measure intermediate-volatility and semi-volatile BVOCs and their oxidation products during the wet and dry seasons. We speciated and quantified 30 sesquiterpenes and 4 diterpenes with mean concentrations in the range 0.01–6.04 ng m−3 (1–670 ppqv). We estimate that sesquiterpenes contribute approximately 14 and 12 % to the total reactive loss of O3 via reaction with isoprene or terpenes during the wet and dry seasons, respectively. This is reduced from ∼ 50–70 % for within-canopy reactive O3 loss attributed to the ozonolysis of highly reactive sesquiterpenes (e.g., β-caryophyllene) that are reacted away before reaching our measurement site. We further identify a suite of their oxidation products in the gas and particle phases and explore their role in biogenic SOA formation in the central Amazon region. Synthesized authentic standards were also used to quantify gas- and particle-phase oxidation products derived from β-caryophyllene. Using tracer-based scaling methods for these products, we roughly estimate that sesquiterpene oxidation contributes at least 0.4–5 % (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. By comparing our field data to laboratory-based sesquiterpene oxidation experiments we confirm that more than 40 additional observed compounds produced through sesquiterpene oxidation are present in Amazonian SOA, warranting further efforts towards more complete quantification.

Abstract Although urban NO x lifetimes have been examined extensively during summertime conditions, wintertime NO x chemistry has been comparatively less studied. We use measurements of NO x and its oxidation products from the aircraft‐based WINTER (Wintertime INvestigation of Transport, Emissions, and Reactivity) experiment over the northeastern United States during February–March 2015 to describe the NO x lifetime during conditions when days are shorter, actinic flux is reduced, and temperatures are colder. By analyzing regional outflow from the East Coast, we show that NO x is long lived during the winter, with a longer daytime lifetime (29 hr) than nighttime lifetime (6.3 hr). We demonstrate that wintertime NO x emissions have an overall lifetime controlled by the nighttime conversion of NO x to nitric acid (HNO 3 ) via N 2 O 5 heterogeneous chemistry, and we discuss constraints on the rates of NO x conversion to HNO 3 . Additionally, analysis of the nighttime O x budget suggests that approximately 15% of O 3 is lost overnight through N 2 O 5 production and subsequent reaction with aerosol to form HNO 3 .

Abstract. Nighttime reaction of nitrate radicals (NO3) with biogenic volatile organic compounds (BVOC) has been proposed as a potentially important but also highly uncertain source of secondary organic aerosol (SOA). The southeastern United States has both high BVOC and nitrogen oxide (NOx) emissions, resulting in a large model-predicted NO3-BVOC source of SOA. Coal-fired power plants in this region constitute substantial NOx emissions point sources into a nighttime atmosphere characterized by high regionally widespread concentrations of isoprene. In this paper, we exploit nighttime aircraft observations of these power plant plumes, in which NO3 radicals rapidly remove isoprene, to obtain field-based estimates of the secondary organic aerosol yield from NO3 + isoprene. Observed in-plume increases in nitrate aerosol are consistent with organic nitrate aerosol production from NO3 + isoprene, and these are used to determine molar SOA yields, for which the average over nine plumes is 9 % (±5 %). Corresponding mass yields depend on the assumed molecular formula for isoprene-NO3-SOA, but the average over nine plumes is 27 % (±14 %), on average larger than those previously measured in chamber studies (12 %–14 % mass yield as ΔOA ∕ ΔVOC after oxidation of both double bonds). Yields are larger for longer plume ages. This suggests that ambient aging processes lead more effectively to condensable material than typical chamber conditions allow. We discuss potential mechanistic explanations for this difference, including longer ambient peroxy radical lifetimes and heterogeneous reactions of NO3-isoprene gas phase products. More in-depth studies are needed to better understand the aerosol yield and oxidation mechanism of NO3 radical + isoprene, a coupled anthropogenic–biogenic source of SOA that may be regionally significant.

Abstract. Recent work has quantified the delay times in measurements of volatile organic compounds (VOCs) caused by the partitioning between the gas phase and the surfaces of the inlet tubing and instrument itself. In this study we quantify wall partitioning effects on time responses and transmission of multifunctional, semivolatile, and intermediate-volatility organic compounds (S/IVOCs) with saturation concentrations (C∗) between 100 and 104 µg m−3. The instrument delays of several chemical ionization mass spectrometer (CIMS) instruments increase with decreasing C∗, ranging from seconds to tens of minutes, except for the NO3- CIMS where it is always on the order of seconds. Six different tubing materials were tested. Teflon, including PFA, FEP, and conductive PFA, performs better than metals and Nafion in terms of both delay time and transmission efficiency. Analogous to instrument responses, tubing delays increase as C∗ decreases, from less than a minute to &gt;100 min. The delays caused by Teflon tubing vs. C∗ can be modeled using the simple chromatography model of Pagonis et al. (2017). The model can be used to estimate the equivalent absorbing mass concentration (Cw) of each material, and to estimate delays under different flow rates and tubing dimensions. We also include time delay measurements from a series of small polar organic and inorganic analytes in PFA tubing measured by CIMS. Small polar molecules behave differently than larger organic ones, with their delays being predicted by their Henry's law constants instead of their C∗, suggesting the dominance of partitioning to small amounts of water on sampling surfaces as a result of their polarity and acidity properties. PFA tubing has the best performance for gas-only sampling, while conductive PFA appears very promising for sampling S/IVOCs and particles simultaneously. The observed delays and low transmission both affect the quality of gas quantification, especially when no direct calibration is available. Improvements in sampling and instrument response are needed for fast atmospheric measurements of a wide range of S/IVOCs (e.g., by aircraft or for eddy covariance). These methods and results are also useful for more general characterization of surface–gas interactions.

Abstract The partitioning of low- and semi-volatile organic compounds into and out of particles significantly influences secondary organic aerosol formation and evolution. Most atmospheric models treat partitioning as an equilibrium between gas and particle phases, despite few direct measurements and a large range of uncertain mass accommodation coefficients (α). Here we directly measure the dynamic, isothermal partitioning of specific organic compounds using mass spectrometry in a Teflon chamber. Measurements are conducted under dry and humid conditions using seeds of different properties that are atmospherically relevant. α values determined independently from gas- and particle-phase observations are consistent and average 0.88 ± 0.33 for all the studied seeds and probe gases. Our results also imply fast mixing, within ~200 s, between dry α-pinene/O 3 SOA and the oxidized compounds. These results indicate that mass transfer limitations in the atmosphere may be less important than some recent studies suggest.

Abstract. We have developed a field-deployable gas chromatograph (GC) with thermal desorption preconcentration (TDPC), which is demonstrated here with automatic detector switching between two high-resolution time-of-flight mass spectrometers (TOF-MSs) for in situ measurements of volatile organic compounds (VOCs). This system provides many analytical advances, including acquisition of fast time–response data in tandem with molecular speciation and two types of mass spectral information for each resolved GC peak: molecular ion identification from Vocus proton transfer reaction (PTR) TOF-MS and fragmentation pattern from electron ionization (EI) TOF-MS detection. This system was deployed during the 2018 ATHLETIC campaign at the University of Colorado Dal Ward Athletic Center in Boulder, Colorado, where it was used to characterize VOC emissions in the indoor environment. The addition of the TDPC-GC increased the Vocus sensitivity by a factor of 50 due to preconcentration over a 6 min GC sample time versus direct air sampling with the Vocus, which was operated with a time resolution of 1 Hz. The GC-TOF methods demonstrated average limits of detection of 1.6 ppt across a range of monoterpenes and aromatics. Here, we describe the method to use the two-detector system to conclusively identify a range of VOCs including hydrocarbons, oxygenates, and halocarbons, along with detailed results including the quantification of anthropogenic monoterpenes, where limonene accounted for 47 %–80 % of the indoor monoterpene composition. We also report the detection of dimethylsilanediol (DMSD), an organosiloxane degradation product, which was observed with dynamic temporal behavior distinct from volatile organosiloxanes (e.g., decamethylcyclopentasiloxane, D5 siloxane). Our results suggest DMSD is produced from humidity-dependent heterogeneous reactions occurring on surfaces in the indoor environment, rather than formed through gas-phase oxidation of volatile siloxanes.

Abstract. Aerosol intercomparisons are inherently complex as they convolve instrument-dependent detection efficiencies vs. size (which often change with pressure, temperature, or humidity) and variations in the sampled aerosol population, in addition to differences in chemical detection principles (e.g., inorganic-only nitrate vs. inorganic plus organic nitrate for two instruments). The NASA Atmospheric Tomography Mission (ATom) spanned four separate aircraft deployments which sampled the remote marine troposphere from 86∘ S to 82∘ N over different seasons with a wide range of aerosol concentrations and compositions. Aerosols were quantified with a set of carefully characterized and calibrated instruments, some based on particle sizing and some on composition measurements. This study aims to provide a critical evaluation of inlet transmissions impacting aerosol intercomparisons, and of aerosol quantification during ATom, with a focus on the aerosol mass spectrometer (AMS). The volume determined from physical sizing instruments (aerosol microphysical properties, AMP, 2.7 nm to 4.8 µm optical diameter) is compared in detail with that derived from the chemical measurements of the AMS and the single particle soot photometer (SP2). Special attention was paid to characterize the upper end of the AMS size-dependent transmission with in-field calibrations, which we show to be critical for accurate comparisons across instruments with inevitably different size cuts. Observed differences between campaigns emphasize the importance of characterizing AMS transmission for each instrument and field study for meaningful interpretation of instrument comparisons. Good agreement (regression slope =0.949 and 1.083 for ATom-1 and ATom-2, respectively; SD =0.003) was found between the composition-based volume (including AMS-quantified sea salt) and that derived from AMP after applying the AMS inlet transmission. The AMS captured, on average, 95±15 % of the standard PM1 volume (referred to as the URG Corp. standard cut 1 µm cyclone operated at its nominal efficiency). These results support the absence of significant unknown biases and the appropriateness of the accuracy estimates for AMS total mass and volume for the mostly aged air masses encountered in ATom. The particle size ranges (and their altitude dependence) that are sampled by the AMS and complementary composition instruments (such as soluble acidic gases and aerosol, SAGA, and particle analysis by laser mass spectrometry, PALMS) are investigated to inform their use in future studies.

Abstract The inorganic fraction of fine particles affects numerous physicochemical processes in the atmosphere. However, there is large uncertainty in its burden and composition due to limited global measurements. Here, we present observations from eleven different aircraft campaigns from around the globe and investigate how aerosol pH and ammonium balance change from polluted to remote regions, such as over the oceans. Both parameters show increasing acidity with remoteness, at all altitudes, with pH decreasing from about 3 to about −1 and ammonium balance decreasing from almost 1 to nearly 0. We compare these observations against nine widely used chemical transport models and find that the simulations show more scatter (generally R 2 &lt; 0.50) and typically predict less acidic aerosol in the most remote regions. These differences in observations and predictions are likely to result in underestimating the model-predicted direct radiative cooling effect for sulfate, nitrate, and ammonium aerosol by 15–39%.

Abstract. Organic nitrate (RONO2) formation in the atmosphere represents a sink of NOx (NOx = NO + NO2) and termination of the NOx/HOx (HOx = HO2 + OH) ozone formation and radical propagation cycles, can act as a NOx reservoir transporting reactive nitrogen, and contributes to secondary organic aerosol formation. While some fraction of RONO2 is thought to reside in the particle phase, particle-phase organic nitrates (pRONO2) are infrequently measured and thus poorly understood. There is an increasing prevalence of aerosol mass spectrometer (AMS) instruments, which have shown promise for determining the quantitative total organic nitrate functional group contribution to aerosols. A simple approach that relies on the relative intensities of NO+ and NO2+ ions in the AMS spectrum, the calibrated NOx+ ratio for NH4NO3, and the inferred ratio for pRONO2 has been proposed as a way to apportion the total nitrate signal to NH4NO3 and pRONO2. This method is increasingly being applied to field and laboratory data. However, the methods applied have been largely inconsistent and poorly characterized, and, therefore, a detailed evaluation is timely. Here, we compile an extensive survey of NOx+ ratios measured for various pRONO2 compounds and mixtures from multiple AMS instruments, groups, and laboratory and field measurements. All data and analysis presented here are for use with the standard AMS vaporizer. We show that, in the absence of pRONO2 standards, the pRONO2 NOx+ ratio can be estimated using a ratio referenced to the calibrated NH4NO3 ratio, a so-called “Ratio-of-Ratios” method (RoR = 2.75 ± 0.41). We systematically explore the basis for quantifying pRONO2 (and NH4NO3) with the RoR method using ground and aircraft field measurements conducted over a large range of conditions. The method is compared to another AMS method (positive matrix factorization, PMF) and other pRONO2 and related (e.g., total gas + particle RONO2) measurements, generally showing good agreement/correlation. A broad survey of ground and aircraft AMS measurements shows a pervasive trend of higher fractional contribution of pRONO2 to total nitrate with lower total nitrate concentrations, which generally corresponds to shifts from urban-influenced to rural/remote regions. Compared to ground campaigns, observations from all aircraft campaigns showed substantially lower pRONO2 contributions at midranges of total nitrate (0.01–0.1 up to 2–5 µg m−3), suggesting that the balance of effects controlling NH4NO3 and pRONO2 formation and lifetimes – such as higher humidity, lower temperatures, greater dilution, different sources, higher particle acidity, and pRONO2 hydrolysis (possibly accelerated by particle acidity) – favors lower pRONO2 contributions for those environments and altitudes sampled.

In this study, physical and chemical properties of ultrafine aerosol particles are investigated at an urban site in Bakersfield, California, during the CalNex 2010 (California Research at the Nexus of Air Quality and Climate Change) campaign in May and June. Ultrafine particle measurements include particle number size distributions by a scanning Differential Mobility Analyzer (DMA) and size resolved aerosol chemical composition determined with a High‐Resolution Time‐of‐Flight Aerosol Mass Spectrometer (HR‐ToF‐AMS). Growth events of ultrafine particles were observed on most days and had a very regular pattern. A nucleation mode centered at ∼20 nm appeared in the morning and grew to 40–100 nm throughout the day. Microphysical modeling and size‐resolved HR‐ToF‐AMS concentrations showed that organic components provided most of the particle growth in the ultrafine mode, and sulfate provided on most days only a minor contribution to the mass of this mode. The ultrafine particle mass was largely dominated by organics (77%), and was at maximum during the afternoon. Elemental carbon (EC) and the AMS tracer C 4 H 9 + for hydrocarbon‐like organic aerosol (HOA) peaked in the early morning during rush hour, indicative of primary emissions. The fact that the particle number concentration peaked in the afternoon, when EC was at minimum, indicates that the midday increase in number concentration was likely due to new particle formation. The potential importance of solar radiation, the condensation sink of vapor on existing particles, concentrations of OH, O 3 , SO 2 , NH 3 , and VOCs for both condensational growth and new particle formation is evaluated based on the covariation of these parameters with ultrafine mass. The results suggest that the ultrafine particles are from secondary sources that are co‐emitted or co‐produced with glyoxal and formaldehyde.

Abstract. Carboxylic acids are present in substantial quantities in atmospheric particles, and they play an important role in the physical and chemical properties of aerosol particles. During measurements in coastal California in the summer of 2009, carboxylic acid functional groups were exclusively associated with a fossil fuel combustion factor derived from factor analysis of Fourier transform infrared spectroscopic measurements and closely correlated with oxygenated organic factors from aerosol mass spectrometry measurements. The high fraction of acid groups and the high ratio of oxygen to carbon in this factor suggest that this factor is composed of secondary organic aerosol (SOA) products of combustion emissions from the upwind industrial region (the ports of Los Angeles and Long Beach). Another indication of the photochemically-driven secondary formation of this combustion-emitted organic mass (OM) was the daytime increase in the concentrations of acid groups and the combustion factors. This daytime increase closely tracked the O3 mixing ratio with a correlation coefficient of 0.7, indicating O3 was closely associated with the SOA maximum and thus likely the oxidant that resulted in acid group formation. Using a pseudo-Lagrangian framework to interpret this daytime increase of carboxylic acid groups and the combustion factors, we estimate that the carboxylic acid groups formed in a 12-h daytime period of one day ("Today's SOA") accounted for 25–33 % of the measured carboxylic acid group mass, while the remaining 67–75 % (of the carboxylic acid group mass) was likely formed 1–3 days previously (the "Background SOA"). A similar estimate of the daytime increase in the combustion factors suggests that "Today's SOA" and the "Background SOA" respectively contributed 25–50 % and 50–75 % of the combustion factor (the "Total SOA"), for a "Total SOA" contribution to the OM of 60 % for the project average. Further, size-resolved spectrometric and spectroscopic characterization of the particle OM indicate that the majority of the OM formed by condensation of gas-phase oxidation products. This unique set of measurements and methods to quantify and characterize photochemically and ozone-linked carboxylic acid group formation provide independent and consistent assessments of the secondary fraction of OM, which could result from second generation products of the oxidation of gas-phase alkane (molecules).

In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.

Limitations in the chemical characterization of tropospheric organic aerosol (OA) continue to impede attempts to fully understand its chemical sources and sinks. To assess the role of organic nitrates in OA, we used a new thermal dissociation‐laser induced fluorescence‐based (TD‐LIF) technique to obtain a high‐time‐resolution record of total aerosol organic nitrates (hereafter ΣANs aer ) at the Bakersfield, CA supersite during the 2010 CalNex campaign. The TD‐LIF measurements compare well with Fourier transform infrared measurements from collocated filter samples. These measurements show that ΣANs are a ubiquitous component of the OA with the –ONO 2 subunit comprising on average 4.8% of the OA mass. Scaling this fraction by an estimate of the organic backbone mass yields an estimate that 17–23% of OA molecules contain nitrate functional groups. Measurements of both total ΣAN (gas + aerosol) and ΣAN aer show that on average 21% of ΣANs are in the condensed phase, suggesting atmospheric organic nitrates have similar volatilities to analogous non‐nitrate oxidized organic compounds. The fraction of ΣAN that is in the condensed phase increases with total OA concentration, providing direct evidence from the atmosphere that absorptive partitioning into OA has some control over the ΣAN phase partitioning. The specific molecular identity of the ΣAN is incompletely understood. Both biogenic hydrocarbons and long chain alkanes are calculated to be significant sources of low volatility nitrates in Bakersfield, and ultra performance liquid chromatography coupled to an electrospray ionization high‐resolution quadrupole time‐of‐flight mass spectrometer measurements confirm the existence of particulate nitrooxy organosulfates derived from gas‐phase oxidation of both isoprene and monoterpenes.

Abstract. Direct measurements of N2O5 reactivity on ambient aerosol particles were made during September 2009 at the Scripps Institution of Oceanography (SIO) Pier facility located in La Jolla, CA. N2O5 reactivity measurements were made using a custom flow reactor and the particle modulation technique alongside measurements of aerosol particle size distributions and non-refractory composition. The pseudo-first order rate coefficients derived from the particle modulation technique and the particle surface area concentrations were used to determine the population average N2O5 reaction probability, γ(N2O5), approximately every 50 min. Insufficient environmental controls within the instrumentation trailer led us to restrict our analysis primarily to nighttime measurements. Within this subset of data, γ(N2O5) ranged from &lt;0.001 to 0.029 and showed significant day-to-day variations. We compare these data to a recent parameterization that utilizes aerosol composition measurements and an aerosol thermodynamics model. The parameterization captures several aspects of the measurements with similar general trends over the time series. However, the parameterization persistently overestimates the measurements by a factor of 1.5–3 and does not illustrate the same extent of variability. Assuming chloride is internally mixed across the particle population leads to the largest overestimates. Removing this assumption only partially reduces the discrepancies, suggesting that other particle characteristics that can suppress γ(N2O5) are important, such as organic coatings or non-aqueous particles. The largest apparent driver of day-to-day variability in the measured γ(N2O5) at this site was the particle nitrate loading, as inferred from both the measured particle composition and the parameterizations. The relative change in measured γ(N2O5) as a function of particle nitrate loading appears to be consistent with expectations based on laboratory data, providing direct support for the atmospheric importance of the so-called "nitrate effect".

Abstract. Vertical profiles of submicron aerosol from in situ aircraft-based measurements were used to construct aggregate profiles of chemical, microphysical, and optical properties. These vertical profiles were collected over the southeastern United States (SEUS) during the summer of 2013 as part of two separate field studies: the Southeast Nexus (SENEX) study and the Study of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). Shallow cumulus convection was observed during many profiles. These conditions enhance vertical transport of trace gases and aerosol and create a cloudy transition layer on top of the sub-cloud mixed layer. The trace gas and aerosol concentrations in the transition layer were modeled as a mixture with contributions from the mixed layer below and the free troposphere above. The amount of vertical mixing, or entrainment of air from the free troposphere, was quantified using the observed mixing ratio of carbon monoxide (CO). Although the median aerosol mass, extinction, and volume decreased with altitude in the transition layer, they were ~10 % larger than expected from vertical mixing alone. This enhancement was likely due to secondary aerosol formation in the transition layer. Although the transition layer enhancements of the particulate sulfate and organic aerosol (OA) were both similar in magnitude, only the enhancement of sulfate was statistically significant. The column integrated extinction, or aerosol optical depth (AOD), was calculated for each individual profile, and the transition layer enhancement of extinction typically contributed less than 10 % to the total AOD. Our measurements and analysis were motivated by two recent studies that have hypothesized an enhanced layer of secondary aerosol aloft to explain the summertime enhancement of AOD (2–3 times greater than winter) over the southeastern United States. The first study attributes the layer aloft to secondary organic aerosol (SOA) while the second study speculates that the layer aloft could be SOA or secondary particulate sulfate. In contrast to these hypotheses, the modest enhancement we observed in the transition layer was not dominated by OA and was not a large fraction of the summertime AOD.

Abstract DAURE (Determination of the Sources of Atmospheric Aerosols in Urban and Rural Environments in the Western Mediterranean) was a multidisciplinary international field campaign aimed at investigating the sources and meteorological controls of particulate matter in the Western Mediterranean Basin (WMB). Measurements were simultaneously performed at an urban‐coastal (Barcelona, BCN) and a rural‐elevated (Montseny, MSY) site pair in NE Spain during winter and summer. State‐of‐the‐art methods such as 14 C analysis, proton‐transfer reaction mass spectrometry, and high‐resolution aerosol mass spectrometry were applied for the first time in the WMB as part of DAURE. WMB regional pollution episodes were associated with high concentrations of inorganic and organic species formed during the transport to inland areas and built up at regional scales. Winter pollutants accumulation depended on the degree of regional stagnation of an air mass under anticyclonic conditions and the planetary boundary layer height. In summer, regional recirculation and biogenic secondary organic aerosols (SOA) formation mainly determined the regional pollutant concentrations. The contribution from fossil sources to organic carbon (OC) and elemental carbon (EC) and hydrocarbon‐like organic aerosol concentrations were higher at BCN compared with MSY due to traffic emissions. The relative contribution of nonfossil OC was higher at MSY especially in summer due to biogenic emissions. The fossil OC/EC ratio at MSY was twice the corresponding ratio at BCN indicating that a substantial fraction of fossil OC was due to fossil SOA. In winter, BCN cooking emissions were identified as an important source of modern carbon in primary organic aerosol.

Abstract. Aerosol mass spectrometers (AMSs) and Aerosol Chemical Speciation Monitors (ACSMs) commercialized by Aerodyne are widely used to measure the non-refractory species in submicron particles. With the standard vapourizer (SV) that is installed in all commercial instruments to date, the quantification of ambient aerosol mass concentration requires the use of the collection efficiency (CE) to correct for the loss of particles due to bounce. A new capture vapourizer (CV) has been designed to reduce the need for a bounce-related CE correction. Two high-resolution AMS instruments, one with a SV and one with a CV, were operated side by side in the laboratory. Four standard species, NH4NO3, NaNO3, (NH4)2SO4 and NH4Cl, which typically constitute the majority of the mass of ambient submicron inorganic species, are studied. The effect of vapourizer temperature (Tv ∼ 200–800 °C) on the detected fragments, CE and size distributions are investigated. A Tv of 500–550 °C for the CV is recommended. In the CV, CE was identical (around unity) for more volatile species (e.g. NH4NO3) and comparable to or higher than the SV for less-volatile species (e.g. (NH4)2SO4), demonstrating an improvement in CE for laboratory inorganic species in the CV. The detected relative intensities of fragments of NO3 and SO4 species observed with the CV are different from those observed with the SV, and are consistent with additional thermal decomposition arising from the increased residence time and multiple collisions. Increased residence times with the CV also lead to broader particle size distribution measurements than with the SV. A method for estimating whether pure species will be detected in AMS sizing mode is proposed. Production of CO2(g) from sampled nitrate on the vapourizer surface, which has been reported for the SV, is negligible for the CV for NH4NO3 and comparable to the SV for NaNO3. . We observe an extremely consistent fragmentation for ammonium compared to very large changes for the associated anions. Together with other evidence, this indicates that it is unlikely that a major fraction of inorganic species vapourizes as intact salts in the AMS.

Abstract Using chemical ionization mass spectrometry to detect particle‐phase acids and aerosol mass spectrometry (AMS) measurements from Colorado, USA, and two studies in Hyytiälä, Finland, we quantify the fraction of organic aerosol (OA) mass that is composed of molecules with acid functional groups ( f acid ). Molecules containing one or more carboxylic acid functionality contributed approximately 29% (45–51%) of the OA mass in Colorado (Finland). Organic acid mass concentration correlates well with AMS m/z 44 (primarily CO 2 + ), a commonly used marker for highly oxidized aerosol. Using the average empirical relationship between AMS m/z 44 and organic acids in these three studies, together with m/z 44 data from 29 continental northern hemispheric (NH) AMS data sets, we estimate that molecules containing carboxylic acid functionality constitute on average 28% (range 10–50%) of NH continental OA mass with typically higher values at rural/remote sites and during summer and lower values at urban sites and during winter.

Secondary organic aerosols (SOA) are a major contributor to fine particulate mass and wield substantial influences on the Earth’s climate and human health. Despite extensive research in recent years, many of the fundamental processes of SOA formation and evolution remain poorly understood. Most atmospheric aerosol models use gas/particle equilibrium partitioning theory as a default treatment of gas-aerosol transfer, despite questions about potentially large kinetic effects. We have conducted fundamental SOA formation experiments in a Teflon environmental chamber using a novel method. A simple chemical system produces a very fast burst of low-volatility gas-phase products, which are competitively taken up by liquid organic seed particles and Teflon chamber walls. Clear changes in the species time evolution with differing amounts of seed allow us to quantify the particle uptake processes. We reproduce gas- and aerosol-phase observations using a kinetic box model, from which we quantify the aerosol mass accommodation coefficient (α) as 0.7 on average, with values near unity especially for low volatility species. α appears to decrease as volatility increases. α has historically been a very difficult parameter to measure with reported values varying over 3 orders of magnitude. We use the experimentally constrained model to evaluate the correction factor (Φ) needed for chamber SOA mass yields due to losses of vapors to walls as a function of species volatility and particle condensational sink. Φ ranges from 1–4.

Aerosols in the central Amazon downwind of a city contain considerable concentrations of organic sulfate derived from isoprene, correlating with inorganic aerosol sulfate.

The chemical composition of indoor air at the University of Colorado, Boulder art museum was measured by a suite of gas- and particle-phase instruments. Over 80% of the total observed organic carbon (TOOC) mass (100 μg m-3) consisted of reduced compounds (carbon oxidation state, OSC < -0.5) with high volatility (log10 C* > 7) and low carbon number (nC < 6). The museum TOOC was compared to other indoor and outdoor locations, which increased according to the following trend: remote < rural ≤ urban < indoor ≤ megacity. The museum TOOC was comparable to a university classroom and 3× less than residential environments. Trends in the total reactive flux were remote < indoor < rural < urban < megacity. High volatile organic compound (VOC) concentrations compensated low oxidant concentrations indoors to result in an appreciable reactive flux. Total hydroxyl radical (OH), ozone (O3), nitrate radical (NO3), and chlorine atom (Cl) reactivities for each location followed a similar trend to TOOC. High human occupancy events increased all oxidant reactivities in the museum by 65-125%. The lifetimes of O3, NO3, OH, and Cl reactivities were 13 h, 15 h, 23 days, and 189 days, respectively, corresponding to over 88% of indoor VOC oxidant reactivity being consumed outdoors after ventilation.

Abstract. Urbanization and deforestation have important impacts on atmospheric particulate matter (PM) over Amazonia. This study presents observations and analysis of PM1 concentration, composition, and optical properties in central Amazonia during the dry season, focusing on the anthropogenic impacts. The primary study site was located 70 km downwind of Manaus, a city of over 2 million people in Brazil, as part of the GoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol mass spectrometer (AMS) provided data on PM1 composition, and aethalometer measurements were used to derive the absorption coefficient babs,BrC of brown carbon (BrC) at 370 nm. Non-refractory PM1 mass concentrations averaged 12.2 µg m−3 at the primary study site, dominated by organics (83 %), followed by sulfate (11 %). A decrease in babs,BrC was observed as the mass concentration of nitrogen-containing organic compounds decreased and the organic PM1 O:C ratio increased, suggesting atmospheric bleaching of the BrC components. The organic PM1 was separated into six different classes by positive-matrix factorization (PMF), and the mass absorption efficiency Eabs associated with each factor was estimated through multivariate linear regression of babs,BrC on the factor loadings. The largest Eabs values were associated with urban (2.04±0.14 m2 g−1) and biomass-burning (0.82±0.04 to 1.50±0.07 m2 g−1) sources. Together, these sources contributed at least 80 % of babs,BrC while accounting for 30 % to 40 % of the organic PM1 mass concentration. In addition, a comparison of organic PM1 composition between wet and dry seasons revealed that only part of the 9-fold increase in mass concentration between the seasons can be attributed to biomass burning. Biomass-burning factor loadings increased by 30-fold, elevating its relative contribution to organic PM1 from about 10 % in the wet season to 30 % in the dry season. However, most of the PM1 mass (&gt;60 %) in both seasons was accounted for by biogenic secondary organic sources, which in turn showed an 8-fold seasonal increase in factor loadings. A combination of decreased wet deposition and increased emissions and oxidant concentrations, as well as a positive feedback on larger mass concentrations are thought to play a role in the observed increases. Furthermore, fuzzy c-means clustering identified three clusters, namely “baseline”, “event”, and “urban” to represent different pollution influences during the dry season. The baseline cluster, representing the dry season background, was associated with a mean mass concentration of 9±3 µg m−3. This concentration increased on average by 3 µg m−3 for both the urban and the event clusters. The event cluster, representing an increased influence of biomass burning and long-range transport of African volcanic emissions, was characterized by remarkably high sulfate concentrations. The urban cluster, representing the influence of Manaus emissions on top of the baseline, was characterized by an organic PM1 composition that differed from the other two clusters. The differences discussed suggest a shift in oxidation pathways as well as an accelerated oxidation cycle due to urban emissions, in agreement with findings for the wet season.

Indoor AirVolume 31, Issue 5 p. 1323-1339 ORIGINAL ARTICLE Quantification and source characterization of volatile organic compounds from exercising and application of chlorine-based cleaning products in a university athletic center Zachary Finewax, Corresponding Author Zachary.finewax@colorado.edu orcid.org/0000-0003-4225-5303 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USA Correspondence Zachary Finewax, Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado, Boulder, Colorado 80309, USA. Email: Zachary.finewax@colorado.eduSearch for more papers by this authorDemetrios Pagonis, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorMegan S. Claflin, Aerodyne Research Inc, Billerica, MA, USASearch for more papers by this authorAnne V. Handschy, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorWyatt L. Brown, orcid.org/0000-0003-3016-8958 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorOlivia Jenks, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorBenjamin A. Nault, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorDouglas A. Day, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorBrian M. Lerner, Aerodyne Research Inc, Billerica, MA, USASearch for more papers by this authorJose L. Jimenez, orcid.org/0000-0001-6203-1847 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorPaul J. Ziemann, orcid.org/0000-0001-7419-0044 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorJoost A. de Gouw, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this author Zachary Finewax, Corresponding Author Zachary.finewax@colorado.edu orcid.org/0000-0003-4225-5303 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USA Correspondence Zachary Finewax, Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado, Boulder, Colorado 80309, USA. Email: Zachary.finewax@colorado.eduSearch for more papers by this authorDemetrios Pagonis, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorMegan S. Claflin, Aerodyne Research Inc, Billerica, MA, USASearch for more papers by this authorAnne V. Handschy, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorWyatt L. Brown, orcid.org/0000-0003-3016-8958 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorOlivia Jenks, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorBenjamin A. Nault, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorDouglas A. Day, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorBrian M. Lerner, Aerodyne Research Inc, Billerica, MA, USASearch for more papers by this authorJose L. Jimenez, orcid.org/0000-0001-6203-1847 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorPaul J. Ziemann, orcid.org/0000-0001-7419-0044 Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this authorJoost A. de Gouw, Cooperative Institute for Research in Environmental Sciences (CIRES, University of Colorado, Boulder, CO, USA Department of Chemistry, University of Colorado, Boulder, CO, USASearch for more papers by this author First published: 18 December 2020 https://doi.org/10.1111/ina.12781Citations: 2Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat Abstract Humans spend approximately 90% of their time indoors, impacting their own air quality through occupancy and activities. Human VOC emissions indoors from exercise are still relatively uncertain, and questions remain about emissions from chlorine-based cleaners. To investigate these and other issues, the ATHLETic center study of Indoor Chemistry (ATHLETIC) campaign was conducted in the weight room of the Dal Ward Athletic Center at the University of Colorado Boulder. Using a Vocus Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (Vocus PTR-TOF), an Aerodyne Gas Chromatograph (GC), an Iodide-Chemical Ionization Time-of-Flight Mass Spectrometer (I-CIMS), and Picarro cavity ringdown spectrometers, we alternated measurements between the weight room and supply air, allowing for determination of VOC, NH3, H2O, and CO2 emission rates per person (emission factors). Human-derived emission factors were higher than previous studies of measuring indoor air quality in rooms with individuals at rest and correlated with increased CO2 emission factors. Emission factors from personal care products (PCPs) were consistent with previous studies and typically decreased throughout the day. In addition, N-chloraldimines were observed in the gas phase after the exercise equipment was cleaned with a dichlor solution. The chloraldimines likely originated from reactions of free amino acids with HOCl on gym surfaces. Open Research Peer Review The peer review history for this article is available at https://publons.com/publon/10.1111/ina.12781. Citing Literature Supporting Information Filename Description ina12781-sup-0001-SupInfo.docWord document, 1.3 MB Supplementary Material Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. Volume31, Issue5September 2021Pages 1323-1339 RelatedInformation

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.

Oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) formation potential of ambient air in Guangzhou, China was investigated using a field-deployed oxidation flow reactor (OFR). The OFR was used to mimic hours to weeks of atmospheric exposure to hydroxyl (OH) radicals within the 2-3 min residence time. A comprehensive investigation on the variation of VOCs and OVOCs as a function of OH exposure is shown. Substantial formation of organic acids and nitrogen-containing OVOC species were observed. Maximum SOA formation in the OFR was observed following 1-4 equiv days' OH exposure. SOA produced from known/measured VOC/IVOC precursors such as single-ring aromatics and long-chain alkanes can account for 52-75% of measured SOA under low NOx and 26-60% under high NOx conditions based on laboratory SOA yield parametrizations. To our knowledge, this is the first time that the contribution (8-20%) of long-chain (C8-C20) alkane oxidation to OFR SOA formation was quantified from direct measurement. By additionally estimating contribution from unmeasured semivolatile and intermediate volatility compounds (S/IVOCs) that are committed with C8-C20 alkanes, 64-100% of the SOA formation observed in the OFR can be explained, signifying the important contribution of S/IVOCs such as large cyclic alkanes to ambient SOA.

Abstract. Glyoxal (CHOCHO), the simplest dicarbonyl in the troposphere, is a potential precursor for secondary organic aerosol (SOA) and brown carbon (BrC) affecting air quality and climate. The airborne measurement of CHOCHO concentrations during the KORUS-AQ (KORea–US Air Quality study) campaign in 2016 enables detailed quantification of loss mechanisms pertaining to SOA formation in the real atmosphere. The production of this molecule was mainly from oxidation of aromatics (59 %) initiated by hydroxyl radical (OH). CHOCHO loss to aerosol was found to be the most important removal path (69 %) and contributed to roughly ∼ 20 % (3.7 µg sm−3 ppmv−1 h−1, normalized with excess CO) of SOA growth in the first 6 h in Seoul Metropolitan Area. A reactive uptake coefficient (γ) of ∼ 0.008 best represents the loss of CHOCHO by surface uptake during the campaign. To our knowledge, we show the first field observation of aerosol surface-area-dependent (Asurf) CHOCHO uptake, which diverges from the simple surface uptake assumption as Asurf increases in ambient condition. Specifically, under the low (high) aerosol loading, the CHOCHO effective uptake rate coefficient, keff,uptake, linearly increases (levels off) with Asurf; thus, the irreversible surface uptake is a reasonable (unreasonable) approximation for simulating CHOCHO loss to aerosol. Dependence on photochemical impact and changes in the chemical and physical aerosol properties “free water”, as well as aerosol viscosity, are discussed as other possible factors influencing CHOCHO uptake rate. Our inferred Henry's law coefficient of CHOCHO, 7.0×108 M atm−1, is ∼ 2 orders of magnitude higher than those estimated from salting-in effects constrained by inorganic salts only consistent with laboratory findings that show similar high partitioning into water-soluble organics, which urges more understanding on CHOCHO solubility under real atmospheric conditions.

Abstract. Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen-species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured onboard the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2 with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of -296 ± 51 g kg-1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per ppmv of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv-1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol.

Abstract. Obtaining quantitative information from real-time soft-ionization aerosol instruments such as an Extractive Electrospray time-of-flight Mass Spectrometer (EESI) can be challenging, due to many individual species having different, and often hard to predict, sensitivities. Directly calibrating is time-consuming and relevant standards are often hard to obtain. In addition, the molecular identities of many of the sampled species may be ambiguous. Bulk OA sensitivities are sometimes used to estimate molecular sensitivities, but different types of OA can have bulk sensitivities that vary by a factor of ~10. A system to separate the compounds present in complex samples can enable their direct calibration. Here, high performance liquid chromatography (HPLC) followed by aerosol formation via atomization was combined with online, 1 Hz measurements to calibrate the EESI and a High Resolution Aerosol Mass Spectrometer (AMS) for compounds present in a secondary organic aerosol (SOA) mixture. Pure compounds were used to test the method and characterize its uncertainties. Pure compound calibration factors were consistent within ±20 % for direct atomization vs. HPLC separation, which is far superior to the orders of magnitude sensitivity differences that are possible with EESI. For species that were not well separated by chromatography, Positive Matrix Factorization (PMF) based on AMS spectra was used to test its ability to separate overlapping species. In two test cases, further separation was achieved using PMF, but derived sensitivities from direct and HPLC calibrations varied by up to a factor of 2.

Abstract. Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of −296 ± 51 g kg−1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv−1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol.

Abstract Heterogeneous chemical cycles of pyrogenic nitrogen and halides influence tropospheric ozone and affect the stratosphere during extreme Pyrocumulonimbus (PyroCB) events. We report field‐derived N 2 O 5 uptake coefficients, γ (N 2 O 5 ), and ClNO 2 yields, φ (ClNO 2 ), from two aircraft campaigns observing fresh smoke in the lower and mid troposphere and processed/aged smoke in the upper troposphere and lower stratosphere (UTLS). Derived φ (ClNO 2 ) varied across the full 0–1 range but was typically &lt;0.5 and smallest in a PyroCB (&lt;0.05). Derived γ (N 2 O 5 ) was low in agricultural smoke (0.2–3.6 × 10 −3 ), extremely low in mid‐tropospheric wildfire smoke (0.1 × 10 −3 ), but larger in PyroCB processed smoke (0.7–5.0 × 10 −3 ). Aged biomass burning aerosol in the UTLS had a higher γ (N 2 O 5 ) of 17 × 10 −3 that increased with sulfate and liquid water, but that was 1–2 orders of magnitude lower than values for aqueous sulfuric aerosol used in stratospheric models.

Abstract To quantify the volatility of organic aerosols (OA), a comprehensive campaign was conducted in the Chinese megacity. Volatility distributions of OA and particle‐phase organic nitrate (pON) were estimated based on five methods: (a) empirical method and (b) kinetic model based on the measurement of a thermodenuder (TD) coupled with an aerosol mass spectrometer; (c) Formula‐based SIMPOL model‐driven method; (d) Element‐based estimations using molecular formula measurements of OA; and (e) gas/particle partitioning. Our results demonstrate that the ambient OA volatility distribution shows good agreement between the two heating methods and the formula‐based method when assuming ambient OA was mainly composed of organic nitrate (pON), organic sulfate and acid groups using the SIMPOL model. However, the element‐based method tends to overestimate the volatility of OA compared to the above three methods, suggesting large uncertainties in the parameterizations or in the representativeness of the molecular measurements that need further refinement. The volatility of ambient OA is generally lower than that of the laboratory‐derived secondary OA, emphasizing the impact of aging. A large fraction at the higher and lower volatility ranges (approximately log C* ≤ −9 and ≥2 μg m −3 ) was found for pON, implying the importance of both extremely low volatile and semi‐volatile species. Overall, this study evaluates different methods for volatility estimation and gives new insight into the volatility of OA and pON in urban areas.

Abstract. Observations of speciated nitrogen oxides, namely NO2, total peroxy nitrates (ΣPNs), total alkyl nitrates (ΣANs), and HNO3 by thermal dissociation laser induced fluorescence (TD-LIF), and supporting chemical and meteorological measurements at Big Hill (1860 m), a high elevation site in California's Sierra Nevada Mountains, are described. From May through October, terrain-driven winds in the region routinely bring air from Sacramento, 100 km southwest of the site, upslope over oak and pine forests to Big Hill during the day, while at night, the site often samples clean, dry air characteristic of the free troposphere. Winter differs mainly in that the meteorology does not favour the buildup of Sacramento's pollution over the Sierra Nevada range, and the urban-influenced air that is seen has been less affected by biogenic VOC emissions, resulting in longer lifetime for NO2 and a predominance of the inorganic forms of nitrogen oxides. Summertime observations at Big Hill can be compared with those from Granite Bay, a Sacramento suburb, and from the University of California's Blodgett Forest Research Station to examine the evolution of nitrogen oxides and ozone within the urban plume. Nitrogen oxide radicals (NO and NO2), which dominate total nitrogen oxides (NOy) at Granite Bay, are rapidly converted into HNO3, ΣPNs, and ΣANs, such that these compounds contribute 29, 30, and 21% respectively to the NOy budget in the plume at Big Hill. Nevertheless, the decreasing concentrations of NO2 as the plume is advected to Big Hill lead to decreases in the production rate of HNO3 and ozone. The data also demonstrate the role that temperature plays in sequestering NO2 into peroxy nitrates, effectively decreasing the rate of ozone production. The important contribution of ΣANs to NOy in the region suggests that they should be considered with regards to export of NOy from the boundary layer. Nocturnal observations of airmasses characteristic of the free troposphere showed lower NOy concentrations, which were dominated by HNO3 with a relatively small contribution from the organic nitrates.

In Winter 2009 an intensive experimental campaign (DAURE) was conducted in an urban site (Barcelona) and in an elevated rural background station (Montseny) in the western Mediterranean basin. During this period three main scenarios were identified based on distinct meteorological conditions: A) temperature inversion, B) cloudy days in normal conditions, and C) intense sea breeze. Filter samples of the submicron fraction (PM1) collected during these scenarios were analysed for organic tracer compounds to gain insight into the composition, sources, formation and processing of aerosol organic matter in the region under contrasting conditions. The results were compared to on-line Aerosol Mass Spectrometry (AMS) measurements. Scenario A conditions had the highest pollution concentrations in Barcelona (traffic and secondary aerosol formation) and lowest in Montseny whose sampling station remained above the mixing layer. Under scenario B the biomass burning contribution was highest in Montseny, reflecting nearby biomass burning sources. Under scenario C, the traffic-related contributions were highest in Montseny and lowest in Barcelona in comparison to the other samples, reflecting the enhanced pollution transport to Montseny and greater dilution in Barcelona. In this scenario, secondary organic aerosol was highest in Montseny. Molecular marker data and AMS source apportionment showed strong to moderate correlation for a) dicarboxylic acids and oxygenated organic aerosol, b) levoglucosan and biomass burning organic aerosol and c) Σn-alkanes and hydrocarbon-like organic aerosol.

Abstract. Measurements of cloud condensation nuclei (CCN), aerosol size distributions, and submicron aerosol composition were made as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign during spring 2006. Measurements were conducted from an aircraft platform over the northeastern Pacific and western North America with a focus on how the transport and evolution of Asian pollution across the Pacific Ocean affected CCN properties. A broad range of air masses were sampled and here we focus on three distinct air mass types defined geographically: the Pacific free troposphere (FT), the marine boundary layer (MBL), and the polluted continental boundary layer in the California Central Valley (CCV). These observations add to the few observations of CCN in the FT. CCN concentrations showed a large range of concentrations between air masses, however CCN activity was similar for the MBL and CCV (κ~0.2–0.25). FT air masses showed evidence of long-range transport from Asia and CCN activity was consistently higher than for the boundary layer air masses. Bulk chemical measurements predicted CCN activity reasonably well for the CCV and FT air masses. Decreasing trends in κ with organic mass fraction were observed for the combination of the FT and CCV air masses and can be explained by the measured soluble inorganic chemical components. Changes in hygroscopicity associated with differences in the non-refractory organic composition were too small to be distinguished from the simultaneous changes in inorganic ion composition in the FT and MBL, although measurements for the large organic fractions (0.6–0.8) found in the CCV showed values of the organic fraction hygroscopicity consistent with other polluted regions (κorg~0.1–0.2). A comparison of CCN-derived κ (for particles at the critical diameter) to H-TDMA-derived κ (for particles at 100 nm diameter) showed similar trends, however the CCN-derived κ values were significantly higher.

Abstract. The atmospheric chemistry of isoprene contributes to the production of a substantial mass fraction of the particulate matter (PM) over tropical forests. Isoprene epoxydiols (IEPOX) produced in the gas phase by the oxidation of isoprene under HO2-dominant conditions are subsequently taken up by particles, thereby leading to production of secondary organic PM. The present study investigates possible perturbations to this pathway by urban pollution. The measurement site in central Amazonia was located 4 to 6 h downwind of Manaus, Brazil. Measurements took place from February through March 2014 of the wet season, as part of the GoAmazon2014/5 experiment. Mass spectra of organic PM collected with an Aerodyne Aerosol Mass Spectrometer were analyzed by positive-matrix factorization. One resolved statistical factor (IEPOX-SOA factor) was associated with PM production by the IEPOX pathway. The IEPOX-SOA factor loadings correlated with independently measured mass concentrations of tracers of IEPOX-derived PM, namely C5-alkene triols and 2-methyltetrols (R = 0. 96 and 0.78, respectively). The factor loading, as well as the ratio f of the loading to organic PM mass concentration, decreased under polluted compared to background conditions. For an increase in NOy concentration from 0.5 to 2 ppb, the factor loading and f decreased by two to three fold. Overall, sulfate concentration explained 37 % of the variability in the factor loading. After segregation of factor loading into subsets based on NOy concentration, the sulfate concentration explained up to 75 % of the variability. Considering both factors, the data sets show that the suppressing effects of increased NO concentrations dominated over the enhancing effects of higher sulfate concentrations. The pollution from Manaus elevated NOy concentrations more significantly than sulfate concentrations relative to background conditions. In this light, increased emissions of nitrogen oxides, as anticipated for some scenarios of Amazonian economic development, could significantly alter pathways of PM production that presently prevail over the tropical forest, implying changes to air quality and regional climate.

We present results of the first intercomparison of real-time instruments for gas/particle partitioning of organic species. Four recently-developed instruments that directly measure gas/particle partitioning in near-real time were deployed in Centreville, Alabama during the Southern Oxidant Aerosol Study (SOAS) in 2013. Two instruments were filter inlet for gases and aerosols high-resolution chemical ionization mass spectrometers (FIGAERO-HRToF-CIMS) with acetate (A-CIMS) and iodide (I-CIMS) ionization sources, respectively; the third was a semi-volatile thermal desorption aerosol GC-MS (SV-TAG); and the fourth was a high-resolution thermal desorption proton-transfer reaction mass spectrometer (HR-TD-PTRMS). Signals from these instruments corresponding to several organic acids were chosen for comparison. The campaign average partitioning fractions show good correlation. A similar level of agreement with partitioning theory is observed. Thus the intercomparison exercise shows promise for these new measurements, as well as some confidence on the measurement of low versus high particle-phase fractions. However, detailed comparison show several systematic differences that lie beyond estimated measurement errors. These differences may be due to at least eight different effects: (1) underestimation of uncertainties under low signal-to-noise; (2) inlet and/or instrument adsorption/desorption of gases; (3) differences in particle size ranges sampled; (4) differences in the methods used to quantify instrument backgrounds; (5) errors in high-resolution fitting of overlapping ion groups; (6) differences in the species included in each measurement due to different instrument sensitivities; and differences in (7) negative or (8) positive thermal decomposition (or ion fragmentation) artifacts. The available data are insufficient to conclusively identify the reasons, but evidence from these instruments and available data from an ion mobility spectrometer shows the particular importance of effects 6–8 in several cases. This comparison highlights the difficulty of this measurement and its interpretation in a complex ambient environment, and the need for further improvements in measurement methodologies, including isomer separation, and detailed study of the possible factors leading to the observed differences. Further intercomparisons under controlled laboratory and field conditions are strongly recommended.Copyright © 2017 American Association for Aerosol Research

Abstract. Aircraft observations of meteorological, trace gas, and aerosol properties were made between May and September 2013 in the southeastern United States (US). Regionally representative aggregate vertical profiles of median and interdecile ranges of the measured parameters were constructed from 37 individual aircraft profiles made in the afternoon when a well-mixed boundary layer with typical fair-weather cumulus was present (Wagner et al., 2015). We use these 0–4 km aggregate profiles and a simple model to calculate the sensitivity of aerosol optical depth (AOD) to changes in dry aerosol mass, relative humidity, mixed-layer height, the central diameter and width of the particle size distribution, hygroscopicity, and dry and wet refractive index, while holding the other parameters constant. The calculated sensitivity is a result of both the intrinsic sensitivity and the observed range of variation in these parameters. These observationally based sensitivity studies indicate that the relationship between AOD and dry aerosol mass in these conditions in the southeastern US can be highly variable and is especially sensitive to relative humidity (RH). For example, calculated AOD ranged from 0.137 to 0.305 as the RH was varied between the 10th and 90th percentile profiles with dry aerosol mass held constant. Calculated AOD was somewhat less sensitive to aerosol hygroscopicity, mean size, and geometric standard deviation, σg. However, some chemistry–climate models prescribe values of σg substantially larger than we or others observe, leading to potential high biases in model-calculated AOD of ∼ 25 %. Finally, AOD was least sensitive to observed variations in dry and wet aerosol refractive index and to changes in the height of the well-mixed surface layer. We expect these findings to be applicable to other moderately polluted and background continental air masses in which an accumulation mode between 0.1–0.5 µm diameter dominates aerosol extinction.

Yields of secondary organic aerosol (SOA) formation from oxidation of volatile organic compounds are measured in laboratory chambers and then applied in regional and global models. Gas-phase losses to large Teflon-walled environmental chambers have been recently shown to reduce SOA yields. Historically, most chambers have operated in batch mode. Increasingly, however, continuous flow (CF) mode is being used, in which reactants and products are continuously introduced and exhausted from the chamber. Recent literature reports indicate a belief that SOA yields measured in CF chambers are not affected by gas-phase wall losses (GWL). Here, we use an experimentally-constrained box model to show that gas-phase wall losses impact both types of chambers when run under similar conditions. We find CF experiments do mitigate some effects of gas-phase wall losses after long (>2 days) experiment run times, but they have significant losses for typical literature experiment times of 1 day. However, this mitigation phenomenon is an experiment- and mechanism-dependent, and GWL still affects the absolute SOA yield. Finally, we show that at condensation sink values higher than the wall loss rate a lack of change in yield vs seed surface area does not necessarily indicate whether GWL affects the experiment and does not suggest the magnitude.