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To better understand precursors of dicarboxylic acids in ambient secondary organic aerosol (SOA), we studied C4–C9 dicarboxylic acids present in SOA formed from the oxidation of toluene, naphthalene, α-pinene, and isoprene. C4–C9 dicarboxylic acids present in SOA were analyzed by offline derivatization gas chromatography–mass spectrometry. We revealed that C4 dicarboxylic acids including succinic acid, maleic acid, fumaric acid, malic acid, DL-tartaric acid, and meso-tartaric acid are produced by the photooxidation of toluene. Since meso-tartaric acid barely occurs in nature, it is a potential aerosol tracer of photochemical reaction products. In SOA particles from toluene, we also detected a compound and its isomer with similar mass spectra to methyltartaric acid standard; the compound and the isomer are tentatively identified as 2,3-dihydroxypentanedioic acid isomers. The ratio of detected C4–C5 dicarboxylic acids to total toluene SOA mass had no significant dependence on the initial VOC/NOx condition. Trace levels of maleic acid and fumaric acid were detected during the photooxidation of naphthalene. Malic acid was produced from the oxidation of α-pinene and isoprene. A trace amount of succinic acid was detected in the SOA produced from the oxidation of isoprene.

Organic aerosol (OA) and its constituent particulate organic nitrate (pON) are critical factors affecting air quality and climate, yet their sources and transformation processes remain poorly understood. Machine learning (ML) excels at identifying nonlinear relationships among features, and in this study, interpretable ML is employed to identify the key factors governing OA and pON formation during an autumn field campaign in Beijing. Results demonstrate that both aerosol liquid water content (ALWC) and aerosol surface area are two primary factors governing the formation of OA and pON. Specifically, OA formation was predominantly driven by ALWC that is associated with aqueous‐phase processes or gas‐liquid partitioning, particularly during severe pollution episodes. pON formation was constrained by aerosol surface area, indicating the vital contribution of gas‐to‐particle partitioning from low volatility vapors or interface processes of precursors. Our results provide new insights into OA formation mechanisms.

Atmospheric volatile organic compounds (VOCs) measurement was carried out using gas chromatography-flame ionization detector (GC-FID) technique (Airmo VOCs online analyzer) in a typical urban area in Beijing from April 2014 to January 2015. Ambient levels, variation characteristics and influential factors contributing to the formation of near-ground-ozone and secondary organic aerosols as well as health risk assessment of VOCs were analyzed. Based on these analyses, the important VOC species that should be given more attention for pollution control were identified and the source apportionment of VOCs was made. Suggestions for VOCs pollution control countermeasures were put forward. The annual average concentration of 84 VOCs was 119 μg·m−3 and the hourly mean concentration was 9.11–567 μg·m−3. Ambient level of VOCs in Beijing has been alleviated in recent years, but is still severe compared to some other cities. VOCs with the largest proportion were alkanes in spring and halogenated hydrocarbons in summer, autumn and winter. The variation of 84 VOCs concentrations was consistent with that of the ambient air quality index, indicating that VOCs had a strong influence on ambient air quality. Influenced by the concentration and activity of VOCs, the largest contribution to ozone formation potential and secondary organic aerosol formation potential came from alkenes and aromatic hydrocarbons, respectively. Five VOCs species such as benzene pose carcinogenic risk to exposed populations. Contrary to some previous studies, benzene was found to have potential cancer risk in some urban areas in China. The main sources of VOCs in the study area were vehicle exhaust, solvent usage, and industrial processes. In order to improve air quality in Beijing and reduce the infection rate of air pollutant related diseases, it is necessary to strengthen the control the emission of VOCs from those three sources.

Furans are a major class of volatile organic compounds emitted from biomass burning. Their high reactivity with atmospheric oxidants leads to the formation of secondary organic aerosol (SOA), including secondary brown carbon (BrC) that can affect global climate via interactions with solar radiation. Here, we investigate the optical properties and chemical composition of SOA generated via photooxidation of furfural, 2‐methylfuran, and 3‐methylfuran under dry (RH < 5%) and humid (RH ∼ 50%) conditions in the presence of nitrogen oxides (NOx) and ammonium sulfate seed aerosol. Dry furfural oxidation has the greatest BrC formation, including reduced nitrogen‐containing organic compounds (NOCs) in SOA, which are dominated by amines and amides formed from reactions between carbonyls and ammonia/ammonium. Based on the products detected, we propose novel formation pathways of NOCs in furfural photooxidation, which can contribute to BrC via accretion reactions during the photochemical aging of biomass burning plumes. Plain Language Summary Biomass burning is a substantial source of both gas‐ and particle‐phase carbon to the atmosphere, including light‐absorbing aerosol known as brown carbon. Brown carbon can be emitted directly from combustion activities and also formed through the oxidation of gas‐phase carbon, known as secondary brown carbon. In this study, we investigate secondary brown aerosol formation from furans (chemicals with a five‐membered aromatic ring with four carbon atoms and one oxygen atom), one of the major classes of gaseous compounds emitted from biomass burning. We find that furfural is an important subset of furans that generates substantial brown carbon during oxidation, with corresponding formation of nitrogen‐containing organic compounds. Key Points Photooxidation of furans in the presence of NOx and ammonium sulfate aerosol leads to secondary brown carbon formation Optical properties of secondary brown carbon from furfural photooxidation are comparable to ambient biomass burning observations Reduced nitrogen species are associated with brown carbon formation from furfural photooxidation and are enhanced under dry conditions

The San Joaquin Valley (SJV) in California experiences persistent air-quality problems associated with elevated particulate matter (PM) concentrations due to anthropogenic emissions, topography, and meteorological conditions. Thus it is important to unravel the various sources and processes that affect the physicochemical properties of PM in order to better inform pollution abatement strategies and improve parameterizations in air-quality models. During January and February 2013, a ground supersite was installed at the Fresno–Garland California Air Resources Board (CARB) monitoring station, where comprehensive, real-time measurements of PM and trace gases were performed using instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an Ionicon proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) as part of the NASA Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign. The average submicron aerosol (PM1) concentration was 31.0 µg m−3 and the total mass was dominated by organic aerosols (OA, 55 %), followed by ammonium nitrate (35 %). High PM pollution events were commonly associated with elevated OA concentrations, mostly from primary sources. Organic aerosols had average atomic oxygen-to-carbon (O / C), hydrogen-to-carbon (H / C), and nitrogen-to-carbon (N / C) ratios of 0.42, 1.70, and 0.017, respectively. Six distinct sources of organic aerosol were identified from positive matrix factorization (PMF) analysis of the AMS data: hydrocarbon-like OA (HOA; 9 % of total OA, O / C  =  0.09) associated with local traffic, cooking OA (COA; 18 % of total OA, O / C  =  0.19) associated with food cooking activities, two biomass burning OA (BBOA1: 13 % of total OA, O / C  =  0.33; BBOA2: 20 % of total OA, O / C  =  0.60) most likely associated with residential space heating from wood combustion, and semivolatile oxygenated OA (SV-OOA; 16 % of total OA, O / C  =  0.63) and low-volatility oxygenated OA (LV-OOA; 24 % of total OA, O / C  =  0.90) formed via chemical reactions in the atmosphere. Large differences in aerosol chemistry at Fresno were observed between the current campaign (winter 2013) and a previous campaign in winter 2010, most notably that PM1 concentrations were nearly 3 times higher in 2013 than in 2010. These variations were attributed to differences in the meteorological conditions, which influenced primary emissions and secondary aerosol formation. In particular, COA and BBOA concentrations were greater in 2013 than 2010, where colder temperatures in 2013 likely resulted in increased biomass burning activities. The influence from a nighttime formed residual layer that mixed down in the morning was found to be much more intense in 2013 than 2010, leading to sharp increases in ground-level concentrations of secondary aerosol species including nitrate, sulfate, and OOA, in the morning between 08:00 and 12:00 PST. This is an indication that nighttime chemical reactions may have played a more important role in 2013. As solar radiation was stronger in 2013 the higher nitrate and OOA concentrations in 2013 could also be partly due to greater photochemical production of secondary aerosol species. The greater solar radiation and larger range in temperature in 2013 also likely led to both SV-OOA and LV-OOA being observed in 2013 whereas only a single OOA factor was identified in 2010.

The RHAPS (Redox-Activity And Health-Effects Of Atmospheric Primary And Secondary Aerosol) project was launched in 2019 with the major objective of identifying specific properties of the fine atmospheric aerosol from combustion sources that are responsible for toxicological effects and can be used as new metrics for health-related outdoor pollution studies. In this paper, we present the overall methodology of RHAPS and introduce the phenomenology and the first data observed. A comprehensive physico-chemical aerosol characterization has been achieved by means of high-time resolution measurements (e.g., number size distributions, refractory chemical components, elemental composition) and low-time resolution analyses (e.g., oxidative potential, toxicological assays, chemical composition). Preliminary results indicate that, at the real atmospheric conditions observed (i.e., daily PM1 from less than 4 to more than 50 μg m−3), high/low mass concentrations of PM1, as well as black carbon (BC) and water soluble Oxidative Potential (WSOP,) do not necessarily translate into high/low toxicity. Notably, these findings were observed during a variety of atmospheric conditions and aerosol properties and with different toxicological assessments. Findings suggest a higher complexity in the relations observed between atmospheric aerosol and toxicological endpoints that go beyond the currently used PM1 metrics. Finally, we provide an outlook to companion papers where data will be analyzed in more detail, with the focus on source apportionment of PM1 and the role of source emissions on aerosol toxicity, the OP as a predictive variable for PM1 toxicity, and the related role of SOA possessing redox-active capacity, exposure-response relationships for PM1, and air quality models to forecast PM1 toxicity.

Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl–VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 × 105 molecules cm-3 from ClNO2 alone, peaking at 09:30 LT and up to 8.4 × 105 molecules cm-3 when including the supporting inorganic halogen measurements.Cl–VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.

This study investigates the atmospheric formation and sinks of HONO and HNO3 and their contribution to secondary PM2.5 formation in Daejeon (urban) and Iksan (suburban), South Korea. Continuous observations revealed distinct concentration patterns: Iksan exhibited elevated ammonia and nitrate levels associated with agricultural activities and biomass burning, while Daejeon showed higher NOx concentrations driven by traffic and industrial sources. Positive Matrix Factorization (PMF) analysis indicated that secondary formation was the dominant contributor to PM2.5 at both sites, with biomass burning exerting an additional influence in Iksan. Among observed precursors, HNO3 showed the highest conversion to aerosol nitrate, highlighting aerosol-phase reactions as its primary sink, followed by dry deposition. Seasonal analysis demonstrated that HONO loss was largely controlled by photolysis in summer. Externally transported aerosols contributed more than locally formed particles at both sites, emphasizing the role of regional background pollution. These findings provide a scientific basis for region-specific air quality strategies that combine local precursor control with the management of long-range transport.

Isoprene oxidation by nitrate radical (NO3) is a potentially important source of secondary organic aerosol (SOA). It is suggested that the second or later-generation products are the more substantial contributors to SOA. However, there are few studies investigating the multi-generation chemistry of isoprene-NO3 reaction, and information about the volatility of different isoprene nitrates, which is essential to evaluate their potential to form SOA and determine their atmospheric fate, is rare. In this work, we studied the reaction between isoprene and NO3 in the SAPHIR chamber (Jülich) under near-atmospheric conditions. Various oxidation products were measured by a high-resolution time-of-flight chemical ionization mass spectrometer using Br− as the reagent ion. Most of the products detected are organic nitrates, and they are grouped into monomers (C4 and C5 products) and dimers (C10 products) with 1–3 nitrate groups according to their chemical composition. Most of the observed products match expected termination products observed in previous studies, but some compounds such as monomers and dimers with three nitrogen atoms were rarely reported in the literature as gas-phase products from isoprene oxidation by NO3. Possible formation mechanisms for these compounds are proposed. The multi-generation chemistry of isoprene and NO3 is characterized by taking advantage of the time behavior of different products. In addition, the vapor pressures of diverse isoprene nitrates are calculated by different parametrization methods. An estimation of the vapor pressure is also derived from their condensation behavior. According to our results, isoprene monomers belong to intermediate-volatility or semi-volatile organic compounds and thus have little effect on SOA formation. In contrast, the dimers are expected to have low or extremely low volatility, indicating that they are potentially substantial contributors to SOA. However, the monomers constitute 80 % of the total explained signals on average, while the dimers contribute less than 2 %, suggesting that the contribution of isoprene NO3 oxidation to SOA by condensation should be low under atmospheric conditions. We expect a SOA mass yield of about 5 % from the wall-loss- and dilution-corrected mass concentrations, assuming that all of the isoprene dimers in the low- or extremely low-volatility organic compound (LVOC or ELVOC) range will condense completely.

Secondary organic aerosols (SOA), a subset of organic aerosols that are chemically produced in the atmosphere, are included in climate modeling calculations using very simple parameterizations. Estimates on their shortwave forcing on climate span almost two orders of magnitude, being potentially comparable to sulfate direct forcing. In the longwave, a neglected part of the spectrum when it comes to SOA, the direct SOA forcing could exceed that of sulfate and black carbon, although in absolute values it is much weaker than the shortwave forcing. Critical for these estimates is the vertical distribution of the climate active agents, pointing to SOA temperature-dependent volatility. Over the last few years, research also revealed the highly oxidized character of organic aerosol and its chemical aging in the atmosphere that partially leads to the formation of brown carbon, an absorbing form of organic aerosol. This review summarizes critical advances in the understanding of SOA behavior and properties relevant to direct climate forcing and puts them in perspective with regard to primary organic aerosol and brown carbon. These findings also demonstrate an emerging dynamic picture of organic aerosol that has not yet been integrated in climate modeling. The challenges for the coming years in order to reduce uncertainties in the direct organic aerosol climate impact are discussed. High priority for future model development should be given to the dynamic link between “white” and “brown” organic aerosol and between primary and secondary organic aerosol. The SOA temperature-dependent volatility parameterizations and wavelength-dependent refractive index should be also included.