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During the past decades, the source apportionment of organic aerosol (OA) in ambient air has been improving substantially. The database of source retrieval model-resolved mass spectral profiles for different sources has been built with the aerosol mass spectrometer (AMS). However, distinguishing similar sources (such as wildfires and residential wood burning) remains challenging, as the hard ionization of the AMS mostly fragments compounds and therefore cannot capture detailed molecular information. Recent mass spectrometer technologies of soft ionization and high mass resolution have allowed for aerosol characterization at the molecular formula level. In this study, we systematically estimated the emission factors and characterized the primary OA (POA) chemical composition with the AMS and the extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) for the first time from a variety of solid fuels, including beech logs, spruce and pine logs, spruce and pine branches and needles, straw, cow dung, and plastic bags. The emission factors of organic matter estimated by the AMS and hydrocarbon gases estimated by the total hydrocarbon analyzer are 16.2 ± 10.8 g kg−1 and 30.3 ± 8.5 g kg−1 for cow dung burning, which is generally higher than that of wood (beech, spruce, and pine), straw, and plastic bag burning (in the range from 1.1 to 6.2 g kg−1 and 14.1 to 19.3 g kg−1). The POA measured by the AMS shows that the f60 (mass fraction of m/z 60) varies from 0.003 to 0.04 based on fuel types and combustion efficiency for wood (beech, spruce, and pine) and cow dung burning. On a molecular level, the dominant compound of POA from wood, straw, and cow dung is C6H10O5 (mainly levoglucosan), contributing ∼ 7 % to ∼ 30 % of the total intensity, followed by C8H12O6 with fractions of ∼ 2 % to ∼ 9 %. However, as they are prevalent in all burning of biomass material, they cannot act as tracers for the specific sources. By using the Mann–Whitney U test among the studied fuels, we find specific potential new markers for these fuels from the measurement of the AMS and EESI-TOF. Markers from spruce and pine burning are likely related to resin acids (e.g., compounds with 20–21 carbon atoms). The product from the pyrolysis of hardwood lignins is found especially in beech log burning. Nitrogen-containing species are selected markers primarily for cow dung open burning. These markers in the future will provide support for the source apportionment.

Atmospheric pollution in urban regions is highly influenced by oxidants due to their important role in the formation of secondary organic aerosol (SOA) and smog. These include the nitrate radical (NO3), which is typically considered a nighttime oxidant, and the chlorine radical (Cl), an extremely potent oxidant that can be released in the morning in chloride-rich environments as a result of nocturnal build-up of nitryl chloride (ClNO2). Chloride makes up a higher percentage of particulate matter in Delhi than has been observed anywhere else in the world, which results in Cl having an unusually strong influence in this city. Here, we present observations and model results revealing that atmospheric chemistry in Delhi exhibits an unusual diel cycle that is controlled by high concentrations of NO during the night. As a result of this, the formation of both NO3 and dinitrogen pentoxide (N2O5), a precursor of ClNO2 and thus Cl, are suppressed at night and increase to unusually high levels during the day. Our results indicate that a substantial reduction in nighttime NO has the potential to increase both nocturnal oxidation via NO3 and the production of Cl during the day.

Aerosol particles have an important role in Earth's radiation balance and climate, both directly and indirectly through aerosol–cloud interactions. Most aerosol particles in the atmosphere are weakly charged, affecting both their collision rates with ions and neutral molecules, as well as the rates by which they are scavenged by other aerosol particles and cloud droplets. The rate coefficients between ions and aerosol particles are important since they determine the growth rates and lifetimes of ions and charged aerosol particles, and so they may influence cloud microphysics, dynamics, and aerosol processing. However, despite their importance, very few experimental measurements exist of charged aerosol collision rates under atmospheric conditions, where galactic cosmic rays in the lower troposphere give rise to ion pair concentrations of around 1000 cm−3. Here we present measurements in the CERN CLOUD chamber of the rate coefficients between ions and small ( nm) aerosol particles containing up to 9 elementary charges, e. We find the rate coefficient of a singly charged ion with an oppositely charged particle increases from 2.0 (0.4–4.4) × 10−6 cm3 s−1 to 30.6 (24.9–45.1) × 10−6 cm3 s−1 for particles with charges of 1 to 9 e, respectively, where the parentheses indicate the ±1σ uncertainty interval. Our measurements are compatible with theoretical predictions and show excellent agreement with the model of Gatti and Kortshagen (2008).

Currently, the complete chemical characterization of nanoparticles (< 100 nm) represents an analytical challenge, since these particles are abundant in number but have negligible mass. Several methods for particle-phase characterization have been recently developed to better detect and infer more accurately the sources and fates of sub-100 nm particles, but a detailed comparison of different approaches is missing. Here we report on the chemical composition of secondary organic aerosol (SOA) nanoparticles from experimental studies of α-pinene ozonolysis at −50, −30, and −10 ∘C and intercompare the results measured by different techniques. The experiments were performed at the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). The chemical composition was measured simultaneously by four different techniques: (1) thermal desorption–differential mobility analyzer (TD–DMA) coupled to a NO3- chemical ionization–atmospheric-pressure-interface–time-of-flight (CI–APi–TOF) mass spectrometer, (2) filter inlet for gases and aerosols (FIGAERO) coupled to an I− high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS), (3) extractive electrospray Na+ ionization time-of-flight mass spectrometer (EESI-TOF), and (4) offline analysis of filters (FILTER) using ultra-high-performance liquid chromatography (UHPLC) and heated electrospray ionization (HESI) coupled to an Orbitrap high-resolution mass spectrometer (HRMS). Intercomparison was performed by contrasting the observed chemical composition as a function of oxidation state and carbon number, by estimating the volatility and comparing the fraction of volatility classes, and by comparing the thermal desorption behavior (for the thermal desorption techniques: TD–DMA and FIGAERO) and performing positive matrix factorization (PMF) analysis for the thermograms. We found that the methods generally agree on the most important compounds that are found in the nanoparticles. However, they do see different parts of the organic spectrum. We suggest potential explanations for these differences: thermal decomposition, aging, sampling artifacts, etc. We applied PMF analysis and found insights of thermal decomposition in the TD–DMA and the FIGAERO.

Abstract Solar flares are one of the severest solar activities that have important effects on near-Earth space. Previous studies have shown that flight arrival delays increase as a result of solar flares, but the intrinsic mechanism behind this relationship is still unknown. In this study, we conducted a comprehensive analysis of flight departure delays during 57 solar X-ray events by using a huge amount of flight data (~ 5 × 106 records) gathered over a 5-year period. It is found that the average flight departure delay time during solar X-ray events increased by 20.68% (7.67 min) compared to quiet periods. Our analysis also revealed apparent time and latitude dependencies, with flight delays being more serious on the dayside than on the nightside and longer (shorter) delays tending to occur in lower (higher) latitude airports during solar X-ray events. Furthermore, our results suggest that the intensity of solar flares (soft X-ray flux) and the Solar Zenith Angle directly modulate flight departure delay time and delay rate. These results indicate that communication interferences caused by solar flares directly affect flight departure delays. This work expands our conventional understanding of the impacts of solar flares on human society and provides new insights for preventing or coping with flight delays.

Abstract Although the sun is really far away from us, some solar activities could still influence the performance and reliability of space-borne and ground-based technological systems on Earth. Those time-varying conditions in space caused by the sun are also called solar storm or space weather. It is known that aviation activities can be affected during solar storms, but the exact effects of space weather on aviation are still unclear. Especially how the flight delays, the top topic concerned by most people, will be affected by space weather has never been thoroughly researched. By analyzing huge amount of flight data (~ 4 × 106 records), for the first time, we quantitatively investigate the flight delays during space weather events. It is found that compared to the quiet periods, the average arrival delay time and 30-min delay rate during space weather events are significantly increased by 81.34% and 21.45% respectively. The evident negative correlation between the yearly flight regularity rate and the yearly mean total sunspot number during 22 years also confirms such correlation. Further studies show that the flight delay time and delay rate will monotonically increase with the geomagnetic field fluctuations and ionospheric disturbances. These results indicate that the interferences in communication and navigation during space weather events may be the most probable reason accounting for the increased flight delays. The above analyses expand the traditional field of space weather research and could also provide us with brand new views for improving the flight delay predications.

Source apportionment studies have struggled to quantitatively link secondary organic aerosols (SOAs) to their precursor sources due largely to instrument limitations. For example, aerosol mass spectrometer (AMS) provides quantitative measurements of the total SOA fraction but lacks the chemical resolution to resolve most SOA sources. In contrast, instruments based on soft ionisation techniques, such as extractive electrospray ionisation mass spectrometry (EESI, e.g. the EESI time-of-flight mass spectrometer, EESI-TOF), have demonstrated the resolution to identify specific SOA sources but provide only a semi-quantitative apportionment due to uncertainties in the dependence of instrument sensitivity on molecular identity. We address this challenge by presenting a method for positive matrix factorisation (PMF) analysis on a single dataset which includes measurements from both AMS and EESI-TOF instruments, denoted “combined PMF” (cPMF). Because each factor profile includes both AMS and EESI-TOF components, the cPMF analysis maintains the source resolution capability of the EESI-TOF while also providing quantitative factor mass concentrations. Therefore, the bulk EESI-TOF sensitivity to each factor can also be directly determined from the analysis. We present metrics for ensuring that both instruments are well represented in the solution, a method for optionally constraining the profiles of factors that are detectable by one or both instruments, and a protocol for uncertainty analysis. As a proof of concept, the cPMF analysis was applied to summer and winter measurements in Zurich, Switzerland. Factors related to biogenic and wood-burning-derived SOAs are quantified, as well as POA sources such as wood burning, cigarette smoke, cooking, and traffic. The retrieved EESI-TOF factor-dependent sensitivities are consistent with both laboratory measurements of SOA from model precursors and bulk sensitivity parameterisations based on ion chemical formulae. The cPMF analysis shows that, with the standalone EESI-TOF PMF, in which factor-dependent sensitivities are not accounted for, some factors are significantly under- or overestimated. For example, when factor-dependent sensitivities are not considered in the winter dataset, the SOA fraction is underestimated by ∼25 % due to the high EESI-TOF sensitivity to components of primary biomass burning such as levoglucosan. In the summer dataset, where both SOA and total OA are dominated by monoterpene oxidation products, the uncorrected EESI-TOF underestimates the fraction of daytime SOA relative to nighttime SOA (in which organonitrates and less oxygenated CxHyOz molecules are enhanced). Although applied here to an AMS and EESI-TOF pairing, cPMF is suitable for the general case of a multi-instrument dataset, thereby providing a framework for exploiting semi-quantitative, high-resolution instrumentation for quantitative source apportionment.

In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution, especially during winter. Comprehensive knowledge of the composition and sources of the organic aerosol (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary OA (POA) and showed that secondary OA (SOA) played a major role but were unable to resolve specific SOA sources. We address the latter through the first field deployment of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer (AMS). Measurements were conducted during the winter of 2018/19, and positive matrix factorization (PMF) was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning OA (BBOA-1 and BBOA-2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LO-OOA). On average, 40 % of the total OA mass was apportioned to the secondary factors. The SOA contribution to total OA mass varied greatly between the daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %, 21:00–04:00 LT). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin: aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA-dominated factors were related to the total AMS SOA (i.e. MO-OOA + LO-OOA) by multiple linear regression (MLR). Aromatic SOA was the major SOA component during the daytime, with a 55.2 % contribution to total SOA mass (42.4 % contribution to total OA). Its contribution to total SOA, however, decreased to 25.4 % (7.9 % of total OA) during the nighttime. This factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA accounted for 18.4 % of total SOA mass (14.2 % of total OA) during the daytime and 36.1 % of total SOA mass (11.2 % of total OA) during the nighttime. Aged biomass burning and mixed urban SOA accounted for 15.2 % and 11.0 % of total SOA mass (11.7 % and 8.5 % of total OA mass), respectively, during the daytime and 15.4 % and 22.9 % of total SOA mass (4.8 % and 7.1 % of total OA mass), respectively, during the nighttime. A simple dilution–partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed daytime concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production, likely from the oxidation of locally emitted volatile organic compounds (VOCs). In contrast, biogenic SOA was related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study show that in Delhi, the nighttime high concentrations are caused by POA emissions led by traffic and biomass burning and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction. Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the daytime suggests an increased OA toxicity and health-related consequences for the general public.

Online characterization of aerosol composition at the near-molecular level is key to understanding chemical reaction mechanisms, kinetics, and sources under various atmospheric conditions. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) is capable of detecting a wide range of organic oxidation products in the particle phase in real time with minimal fragmentation. Quantification can sometimes be hindered by a lack of available commercial standards for aerosol constituents, however. Good correlations between the EESI-TOF and other aerosol speciation techniques have been reported, though no attempts have yet been made to parameterize the EESI-TOF response factor for different chemical species. Here, we report the first parameterization of the EESI-TOF response factor for secondary organic aerosol (SOA) at the near-molecular level based on its elemental composition. SOA was formed by ozonolysis of monoterpene or OH oxidation of aromatics inside an oxidation flow reactor (OFR) using ammonium nitrate as seed particles. A Vocus proton-transfer reaction mass spectrometer (Vocus-PTR) and a high-resolution aerosol mass spectrometer (AMS) were used to determine the gas-phase molecular composition and the particle-phase bulk chemical composition, respectively. The EESI response factors towards bulk SOA coating and the inorganic seed particle core were constrained by intercomparison with the AMS. The highest bulk EESI response factor was observed for SOA produced from 1,3,5-trimethylbenzene, followed by those produced from d-limonene and o-cresol, consistent with previous findings. The near-molecular EESI response factors were derived from intercomparisons with Vocus-PTR measurements and were found to vary from 103 to 106 ion counts s−1 ppb−1, mostly within ±1 order of magnitude of their geometric mean of 104.6 ion counts s−1 ppb−1. For aromatic SOA components, the EESI response factors correlated with molecular weight and oxygen content and inversely correlated with volatility. The near-molecular response factors mostly agreed within a factor of 20 for isomers observed across the aromatics and biogenic systems. Parameterization of the near-molecular response factors based on the measured elemental formulae could reproduce the empirically determined response factor for a single volatile organic compound (VOC) system to within a factor of 5 for the configuration of our mass spectrometers. The results demonstrate that standard-free quantification using the EESI-TOF is possible.

Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

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

Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 ∘C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 ∘C to 0.7 % at −50 ∘C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at −50 ∘C compared with 25 ∘C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

Delhi, India, is the second most populated city in the world and routinely experiences some of the highest particulate matter concentrations of any megacity on the planet, posing acute challenges to public health (World Health Organization, 2018). However, the current understanding of the sources and dynamics of PM pollution in Delhi is limited. Measurements at the Delhi Aerosol Supersite (DAS) provide long-term chemical characterization of ambient submicron aerosol in Delhi, with near-continuous online measurements of aerosol composition. Here we report on source apportionment based on positive matrix factorization (PMF), conducted on 15 months of highly time-resolved speciated submicron non-refractory PM1 (NR-PM1) between January 2017 and March 2018. We report on seasonal variability across four seasons of 2017 and interannual variability using data from the two winters and springs of 2017 and 2018. We show that a modified tracer-based organic component analysis provides an opportunity for a real-time source apportionment approach for organics in Delhi. Phase equilibrium modeling of aerosols using the extended aerosol inorganics model (E-AIM) predicts equilibrium gas-phase concentrations and allows evaluation of the importance of the ventilation coefficient (VC) and temperature in controlling primary and secondary organic aerosol. We also find that primary aerosol dominates severe air pollution episodes, and secondary aerosol dominates seasonal averages.

Delhi, India, routinely experiences some of the world's highest urban particulate matter concentrations. We established the Delhi Aerosol Supersite study to provide long-term characterization of the ambient submicron aerosol composition in Delhi. Here we report on 1.25 years of highly time-resolved speciated submicron particulate matter (PM1) data, including black carbon (BC) and nonrefractory PM1 (NR-PM1), which we combine to develop a composition-based estimate of PM1 (“C-PM1” = BC + NR-PM1) concentrations. We observed marked seasonal and diurnal variability in the concentration and composition of PM1 owing to the interactions of sources and atmospheric processes. Winter was the most polluted period of the year, with average C-PM1 mass concentrations of ∼210 µg m−3. The monsoon was hot and rainy, consequently making it the least polluted (C-PM1 ∼50 µg m−3) period. Organics constituted more than half of the C-PM1 for all seasons and times of day. While ammonium, chloride, and nitrate each were ∼10 % of the C-PM1 for the cooler months, BC and sulfate contributed ∼5 % each. For the warmer periods, the fractional contribution of BC and sulfate to C-PM1 increased, and the chloride contribution decreased to less than 2 %. The seasonal and diurnal variation in absolute mass loadings were generally consistent with changes in ventilation coefficients, with higher concentrations for periods with unfavorable meteorology – low planetary boundary layer height and low wind speeds. However, the variation in C-PM1 composition was influenced by temporally varying sources, photochemistry, and gas–particle partitioning. During cool periods when wind was from the northwest, episodic hourly averaged chloride concentrations reached 50–100 µg m−3, ranking among the highest chloride concentrations reported anywhere in the world. We estimated the contribution of primary emissions and secondary processes to Delhi's submicron aerosol. Secondary species contributed almost 50 %–70 % of Delhi's C-PM1 mass for the winter and spring months and up to 60 %–80 % for the warmer summer and monsoon months. For the cooler months that had the highest C-PM1 concentrations, the nighttime sources were skewed towards primary sources, while the daytime C-PM1 was dominated by secondary species. Overall, these findings point to the important effects of both primary emissions and more regional atmospheric chemistry on influencing the extreme particle concentrations that impact the Delhi megacity region. Future air quality strategies considering Delhi's situation in both a regional and local context will be more effective than policies targeting only local, primary air pollutants.

Chlorine-initiated oxidation of n-alkanes (C8−12) under high-nitrogen oxide conditions was investigated. Observed secondary organic aerosol yields (0.16 to 1.65) are higher than those for OH-initiated oxidation of C8−12 alkanes (0.04 to 0.35). A high-resolution time-of-flight chemical ionization mass spectrometer coupled to a Filter Inlet for Gases and AEROsols (FIGAERO–CIMS) was used to characterize the gas- and particle-phase molecular composition. Chlorinated organics were observed, which likely originated from chlorine addition to the double bond present on the heterogeneously produced dihydrofurans. A two-dimensional thermogram representation was developed to visualize the composition and relative volatility of organic aerosol components using unit-mass resolution data. Evidence of oligomer formation and thermal decomposition was observed. Aerosol yield and oligomer formation were suppressed under humid conditions (35 % to 67 % RH) relative to dry conditions (under 5 % RH). The temperature at peak desorption signal, Tmax, a proxy for aerosol volatility, was shown to change with aerosol filter loading, which should be constrained when evaluating aerosol volatilities using the FIGAERO–CIMS. Results suggest that long-chain anthropogenic alkanes could contribute significantly to ambient aerosol loading over their atmospheric lifetime.

Recent studies have found concentrations of reactive chlorine species to be higher than expected, suggesting that atmospheric chlorine chemistry is more extensive than previously thought. Chlorine radicals can interact with hydroperoxy (HOx) radicals and nitrogen oxides (NOx) to alter the oxidative capacity of the atmosphere. They are known to rapidly oxidize a wide range of volatile organic compounds (VOCs) found in the atmosphere, yet little is known about secondary organic aerosol (SOA) formation from chlorine-initiated photooxidation and its atmospheric implications. Environmental chamber experiments were carried out under low-NOx conditions with isoprene and chlorine as primary VOC and oxidant sources. Upon complete isoprene consumption, observed SOA yields ranged from 7 to 36 %, decreasing with extended photooxidation and SOA aging. Formation of particulate organochloride was observed. A high-resolution time-of-flight chemical ionization mass spectrometer was used to determine the molecular composition of gas-phase species using iodide–water and hydronium–water cluster ionization. Multi-generational chemistry was observed, including ions consistent with hydroperoxides, chloroalkyl hydroperoxides, isoprene-derived epoxydiol (IEPOX), and hypochlorous acid (HOCl), evident of secondary OH production and resulting chemistry from Cl-initiated reactions. This is the first reported study of SOA formation from chlorine-initiated oxidation of isoprene. Results suggest that tropospheric chlorine chemistry could contribute significantly to organic aerosol loading.