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Organosulfur compounds are found to be ubiquitous in atmospheric aerosols – a majority of which are expected to be organosulfates (OSs). Given the atmospheric abundance of OSs, and their potential to form a variety of reaction products upon aging, it is imperative to study the transformation kinetics and chemistry of OSs to better elucidate their atmospheric fates and impacts. In this work, we investigated the chemical transformation of an α-pinene-derived organosulfate (C10H17O5SNa, αpOS-249) through heterogeneous OH oxidation at a relative humidity of 50 % in an oxidation flow reactor (OFR). The aerosol-phase reaction products were characterized using high-performance liquid chromatography–electrospray ionization–high-resolution mass spectrometry and ion chromatography. By monitoring the decay rates of αpOS-249, the effective heterogeneous OH reaction rate was measured to be (6.72±0.55)×10-13 cm3 molecule−1 s−1. This infers an atmospheric lifetime of about 2 weeks at an average OH concentration of 1.5×106 molecules cm−3. Product analysis shows that OH oxidation of αpOS-249 can yield more oxygenated OSs with a nominal mass-to-charge ratio (m/z) at 247 (C10H15O5S−), 263 (C10H15O6S−), 265 (C10H17O6S−), 277 (C10H13O7S−), 279 (C10H15O7S−), and 281 (C10H17O7S−). The formation of fragmentation products, including both small OSs (C ) and inorganic sulfates, is found to be insignificant. These observations suggest that functionalization reactions are likely the dominant processes and that multigenerational oxidation possibly leads to formation of products with one or two hydroxyl and carbonyl functional groups adding to αpOS-249. Furthermore, all product ions except m/z=277 have been detected in laboratory-generated α-pinene-derived secondary organic aerosols as well as in atmospheric aerosols. Our results reveal that OSs freshly formed from the photochemical oxidation of α-pinene could react further to form OSs commonly detected in atmospheric aerosols through heterogeneous OH oxidation. Overall, this study provides more insights into the sources, transformation, and fate of atmospheric OSs.

Coarse particulate matter (i.e. PM with an aerodynamic diameter between 2.5 and 10 µm – PM2.5 and PM10 – or PMcoarse) has been increasingly recognized for its importance in PM10 regulation because of its growing proportion in PM10 and the accumulative evidence for its adverse health impact. In this work, we present comprehensive PMcoarse speciation results obtained through a 1-year-long (January 2020–February 2021) joint PM10 and PM2.5 chemical speciation study in Hong Kong, a coastal and highly urbanized city in southern China. The annual average concentration of PMcoarse is 14.9 ± 8.6 µg m−3 (± standard deviation), accounting for 45 % of PM10 (32.9 ± 18.5 µg m−3). The measured chemical components explain ∼75 % of the PMcoarse mass. The unexplained part is contributed by unmeasured geological components and residue liquid water content, supported through analyses by positive matrix factorization (PMF) and the thermodynamic equilibrium model ISORROPIA II. The PMcoarse mass is apportioned to four sources resolved by PMF, namely soil dust/industrial and coal combustion, construction dust/copper-rich emissions, fresh sea salt, and an aged sea salt factor containing secondary inorganic aerosols (mostly nitrate). The PMcoarse concentration and source composition exhibit a distinct seasonal variation, a result mainly driven by the source areas the air masses have travelled through as revealed by back-trajectory analysis. In summer when the site is dominated by marine air mass, PMcoarse is the lowest (average = 8.1 µg m−3) and sea salt the largest contributor (47 %), followed by the two dust factors (36 % in total). In winter when the site receives air mass mainly from the northern continental region, PMcoarse concentration triples (24.8 µg m−3), with the two dust factors contributing three quarters of the aerosol mass. The potential dust source areas are mapped using the concentration-weighted trajectory technique, showing either the Greater Bay Area or the greater part of southern China as the origin of fugitive dust emissions leading to elevated ambient PMcoarse loadings in Hong Kong. This study, the first of this kind in our region, provides highly relevant guidance for other locations with similar monitoring needs. Additionally, the study findings point to the need for further research on the sources, transport, aerosol processes, and health effects of PMcoarse.

Vehicular emissions contribute a significant portion to fine particulate matter (PM2.5) air pollution in urban areas. Knowledge of the relative contribution of gasoline- versus diesel-powered vehicles is highly relevant for policymaking, and yet there is a lack of an effective observation-based method to determine this quantity, especially for its robust tracking over a period of years. In this work, we present an approach to track separate contributions of gasoline and diesel vehicles through the positive matrix factorization (PMF) analysis of online monitoring data measurable by relatively inexpensive analytical instruments. They are PM2.5 organic and elemental carbon (OC and EC), C2–C9 volatile organic compounds (VOCs) (e.g., pentanes, benzene, xylenes, etc.), and nitrogen oxide concentrations. The method was applied to monitoring data spanning more than 6 years between 2011 and 2017 in a roadside environment in Hong Kong. We found that diesel vehicles accounted for ∼70 %–90 % of the vehicular PM2.5 (PMvehicle) over the years and the remainder from gasoline vehicles. The diesel PMvehicle during truck- and bus-dominated periods showed declining trends simultaneous with control efforts targeted at diesel commercial vehicles and franchised buses in the intervening period. The combined PMvehicle from diesel and gasoline vehicles by PMF agrees well with an independent estimate by the EC-tracer method, both confirming PMvehicle contributed significantly to the PM2.5 in this urban environment (∼4–8 µg m−3, representing 30 %–60 % in summer and 10 %–20 % in winter). Our work shows that the long-term monitoring of roadside VOCs and PM2.5 OC and EC is effective for tracking gaseous and PM pollutants from different vehicle categories. This work also demonstrates the value of an evidence-based approach in support of effective control policy formulation.