Organosulfur compounds (OSCs) are important components of fine particulate matter (PM2.5); however, little information is available on OSCs in urban regions due to their chemical complexity, especially for novel species such as aromatic sulfonates. To supplement the detection technique and systematically identify OSCs, in this study we developed a nontargeted approach based on gas chromatography and high-resolution mass spectrometry (GC-HRMS) to screen OSCs in PM2.5 of urban Beijing and provide field evidence for their source and formation mechanism. 76 OSCs were found through mass difference of sulfur isotopes and characteristic sulfur-containing fragments. 6 species were confirmed as aromatic sulfonates by authentic standards. 32 OSCs showed higher levels in the heating season, presumably because of the intensive emission, especially from coal combustion. While certain species, with 2-sulfobenzoic acid as the representative, were 2.6-times higher in the non-heating season than in the heating season. Such species were significantly correlated with ozone and aerosol liquid water content (r = 0.2–0.8, p < 0.05), implying an oxidation-involved aqueous-phase formation in the atmosphere. In addition, with an average proportion of ∼95 % of the total sulfobenzoic acids, the predominance of the 2-substitution product over its isomers of 3- or 4-sulfobenzoic acid suggests a more plausible mechanism of radical-initiated reaction of phthalic acid followed by sulfonation, with atmospheric reactivity indicated by ozone and temperature as the determining factor. This study provided not only a nontargeted approach for OSCs in ambient PM2.5, but also field evidence on their secondary formation proposed in previous simulation studies.

Abstract Accurate estimates of aerosol refractive index (RI) are critical for modeling aerosol-radiation interaction, yet this information is limited for ambient organic aerosols, leading to large uncertainties in estimating aerosol radiative effects. We present a semi-empirical model that predicts the real RI n of organic aerosol material from its widely measured oxygen-to-carbon (O:C) and hydrogen-to-carbon (H:C) elemental ratios. The model was based on the theoretical framework of Lorenz-Lorentz equation and trained with n-values at 589 nm () of 160 pure compounds. The predictions can be expanded to predict n-values in a wide spectrum between 300 and 1,200 nm. The model was validated with newly measured and literature datasets of n-values for laboratory secondary organic aerosol (SOA) materials. Uncertainties of predictions for all SOA samples are within 5%. The model suggests that -values of organic aerosols may vary within a relatively small range for typical O:C and H:C values observed in the atmosphere.

Abstract Organic aerosol particles are oxidized by atmospheric oxidants. These particles are occasionally internally mixed with solid materials such as soot and inorganic crystals. However, potential impacts of the particles' mixing states on chemical reactivity have rarely been investigated. This study investigated the influence of the existence of crystalline ammonium sulfate on chemical reactivity of oleic acid particles with ozone for the temperature range of −20°C to +35°C using an aerosol flow tube reactor. The chemical compositions of the resulting particles were monitored using online instruments for deriving the reactive uptake coefficients (γ) of ozone by oleic acid. The values of γ were not significantly influenced by the existence of ammonium sulfate when the temperature of the reactor was higher than the melting point of oleic acid (∼13°C). The values of γ were unmeasurably small for the lower temperature range when oleic acid particles were internally mixed with crystalline ammonium sulfate. No significant change in γ was observed for the temperature range down to −13°C when the inorganic salt was absent, likely due to the formation of supercooled liquid. The difference in chemical reactivity can be explained by the occurrence of heterogeneous nucleation induced by inorganic seed.

Abstract Different adverse health effects of submicron (PM1) and fine particles (PM2.5) may be attributed to their chemical differences, requiring a better understanding of size-resolved composition. Herein, extensive online measurements were conducted across seasons in Beijing by two aerosol mass spectrometers, one of which alternately sampled PM1 and PM2.5. Source apportionment of organic aerosol (OA) indicated that traffic- and cooking-related OA together accounted for ∼20%−30% of the OA mass in PM2.5, showing insignificant seasonal variations. Coal-combustion and biomass-burning-related OA had minor contributions. The two secondary OA (SOA) factors together accounted for 59%−73% of the OA mass in PM2.5. The mass distributions of particulate components in PM1 and PM2.5 varied greatly across seasons. Secondary formation played a key role in particle size growth during cold seasons. During severe hazes with high aerosol liquid water content (ALWC), the supermicron mass fraction (MF1−2.5) of secondary components reached ∼40%−50% while those for primary OA remained at ∼20%. Heterogeneous uptake, aqueous processing, and dissolution likely all contributed to the enhanced concentration of secondary components, and the former two were perhaps more important. The increase of MF1−2.5 for secondary components with increasing ALWC in spring was less than that in winter, possibly due to the shorter duration of stagnant conditions limiting secondary formation. Early autumn showed higher MF1−2.5 values than cold seasons with insignificant changes as ALWC varied, plausibly explained by intensive new particle formation hindering persistent particle growth. Our results highlight the importance of heterogeneous uptake and aqueous processing in distributing SOA in supermicron mode in polluted areas.

Most ambitious climate change mitigation pathways indicate multifold bioenergy expansion to support the energy transition, which may trigger increased biomass imports from major bioenergy-consuming regions. However, the potential global land-use change and sustainability trade-offs alongside the bioenergy trade remain poorly understood. Here, we apply the Global Biosphere Management Model (GLOBIOM) to investigate and compare the effects of different increasing bioenergy import strategies in line with the 1.5℃-compatible bioenergy demand in China, which is projected to represent 30% of global bioenergy consumption by the middle of the century. The results show that sourcing additional bioenergy from different world regions could pose heterogeneous impacts on the local and global land systems, with implications on food security, greenhouse gas emissions, and water and fertilizer demand. In the worst cases under strict trade settings, relying on biomass import may induce up to 25% of unmanaged forests converted to managed ones in the supplying regions, while in an open trade environment, increasing bioenergy imports would drastically change the trade flows of staple agricultural or forestry products, which would further bring secondary land-use changes in other world regions. Nevertheless, an economically optimized biomass import portfolio for China has the potential to reduce global overall sustainability trade-offs with food security and emission abatement. However, these benefits vary with indicator and time and are conditional on stricter land-use regulations. Our findings thus shed new light on the design of bioenergy trade strategies and the associated land-use regulations in individual countries in the era of deep decarbonization.