Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H₃O⁺ chemical ionization, and NO⁺ chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90 % of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (I⁻ CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R², of > 0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire.

To investigate the seasonal characteristics of submicron aerosol (PM₁) in Beijing urban areas, a high‐resolution time‐of‐flight aerosol‐mass‐spectrometer (HR‐ToF‐AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM₁ (60–84 µg m⁻³) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM₁ mass concentrations were stable and repeatable. Eighty‐two percent of the PM₁ mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM₁ mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM₁ including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45–67% of OA in summer and 22–50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13–24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon‐like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m⁻³) in winter. The POA/ΔCO ratios in winter and summer are 11 and 16 µg m⁻³ ppm⁻¹, respectively, similar to ratios from western cities. Higher OOA/O_x (= NO₂ + O₃) ratio (0.49 µg m⁻³ ppb⁻¹) in winter study than these ratios from western cities (0.03–0.16 µg m⁻³ ppb⁻¹) was observed, which may be due to the aqueous reaction or extra SOA formation contributed by semivolatile organic compounds from various primary sources (e.g., BBOA or CCOA) in Beijing. The evolution of oxygen to carbon ratio (O/C) with photochemical age allows to estimate an equivalent rate constant for chemical aging of OA in summer as k_OH ~ 4.1 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, which is of the same order as obtained in other anthropogenic influenced areas and may be useful for OA modeling.

Volatile organic compounds (VOCs) were measured online at an urban site in Beijing in August–September 2010. Diurnal variations of various VOC species indicate that VOCs concentrations were influenced by photochemical removal with OH radicals for reactive species and secondary formation for oxygenated VOCs (OVOCs). A photochemical age‐based parameterization method was applied to characterize VOCs chemistry. A large part of the variability in concentrations of both hydrocarbons and OVOCs was explained by this method. The determined emission ratios of hydrocarbons to acetylene agreed within a factor of two between 2005 and 2010 measurements. However, large differences were found for emission ratios of some alkanes and C8 aromatics between Beijing and northeastern United States secondary formation from anthropogenic VOCs generally contributed higher percentages to concentrations of reactive aldehydes than those of inert ketones and alcohols. Anthropogenic primary emissions accounted for the majority of ketones and alcohols concentrations. Positive matrix factorization (PMF) was also used to identify emission sources from this VOCs data set. The four resolved factors were three anthropogenic factors and a biogenic factor. However, the anthropogenic factors are attributed here to a common source at different stages of photochemical processing rather than three independent sources. Anthropogenic and biogenic sources of VOCs concentrations were not separated completely in PMF. This study indicates that photochemistry of VOCs in the atmosphere complicates the information about separated sources that can be extracted from PMF and the influence of photochemical processing must be carefully considered in the interpretation of source apportionment studies based upon PMF.