Differences in aerosol chemistry at a regional background site in Hong Kong before and during the COVID-19 pandemic.

Restrictions on human-related activities implemented in Hong Kong to curb the spread of the coronavirus disease 2019 (COVID-19) pandemic provided an opportunity to investigate the anthropogenic impact on organic aerosols (OA) composition. In this study, we conducted a comparative analysis of online measurements of non-refractory submicron particulate matters (NR-PM1) at a regional background site in Hong Kong, covering the periods before the COVID-19 control (November 2018) and during the COVID-19 control (October to November 2020), to investigate changes in OA sources and formation mechanisms. Among the measured NR-PM1 components, organics were the most dominant species with an average percentage of 51.0 ± 0.5 %, exceeding pre-control levels of 44.0 ± 0.7 %. Moreover, 88 % of the organics were attributed to oxygenated OA (OOA). Diurnal variations of all bulk components in NR-PM1 consistently showed afternoon peaks, indicating photochemical processes during COVID-19 control. Similar to the pre-restriction period, the positive matrix factorization (PMF) model showed that OOA was composed of three factors, including two less-oxidized oxygenated factors (LO-OOA1 and LO-OOA2) and one more-oxidized oxygenated factor (MO-OOA). The contribution of the LO-OOA2 factor remained small and stable during both sampling campaigns, which might imply background levels of OOA at this site. The formation of the two predominant components of organics (e.g., LO-OOA1 and MO-OOA) was further discussed. Compared with before control, observational evidence showed that the levels of MO-OOA exceeded LO-OOA1 during the control period, and the average concentration of odd oxygen (Ox = ozone + nitrogen dioxide) increased by 53 % during the COVID-19 control. Besides, the results showed that both LO-OOA1 and MO-OOA exhibited similar diurnal variations to Ox, and their concentrations generally enhanced with increasing Ox levels. This suggested that the formation of OOA was closely related to the photochemical oxidation processes when anthropogenic emissions were reduced. By correlating LO-OOA1 and MO-OOA with speciated OA markers, we found that the formation of LO-OOA1 remained associated with anthropogenic sources, while biogenic emissions contributed to the formation of MO-OOA during the COVID-19 control. Our findings highlight the interplay between emissions, atmospheric conditions, and aerosol composition, providing valuable insights to guide strategic decisions for future air quality improvement.

Pollution-Derived Br2 Boosts Oxidation Power of the Coastal Atmosphere.

The bromine atom (Br•) has been known to destroy ozone (O3) and accelerate the deposition of toxic mercury (Hg). However, its abundance and sources outside the polar regions are not well-known. Here, we report significant levels of molecular bromine (Br2)─a producer of Br•─observed at a coastal site in Hong Kong, with an average noontime mixing ratio of 5 ppt. Given the short lifetime of Br2 (∼1 min at noon), this finding reveals a large Br2 daytime source. On the basis of laboratory and field evidence, we show that the observed daytime Br2 is generated by the photodissociation of particulate nitrate (NO3-) and that the reactive uptake of dinitrogen pentoxide (N2O5) on aerosols is an important nighttime source. Model-calculated Br• concentrations are comparable with that of the OH radical─the primary oxidant in the troposphere, accounting for 24% of the oxidation of isoprene, a 13% increase in net O3 production, and a nearly 10-fold increase in the production rate of toxic HgII. Our findings reveal that reactive bromines play a larger role in the atmospheric chemistry and air quality of polluted coastal and maritime areas than previously thought. Our results also suggest that tightening the control of emissions of two conventional pollutants (NOx and SO2)─thereby decreasing the levels of nitrate and aerosol acidity─would alleviate halogen radical production and its adverse impact on air quality.

Secondary organic aerosol formation at an urban background site on the coastline of South China: Precursors and aging processes.

Understanding the formation mechanisms of secondary organic aerosols (SOA) is an arduous task in atmospheric chemistry. In November 2018, a sampling campaign was conducted at an urban background site in Hong Kong for characterization of secondary air pollution. A high-resolution time-of-flight aerosol mass spectrometer was used to monitor the compositions of non-refractory submicron particulate matters (NR-PM1), and multiple online instruments provided us with comprehensive auxiliary data. Organic aerosol (OA) constituted the largest fraction (43.8%) of NR-PM1, and 86.5% of the organics was contributed by the oxygenated OA (OOA, secondary components). Formation mechanisms of a dominant and more variable component of the less-oxidized OOA (labelled as LO-OOA1 in this study) and the more-oxidized OOA (MO-OOA) were explored. Based on the multilinear regression with molecular markers of OA (e.g., hydroxybenzonic acids and 2,3-dihydroxy-4-oxopentanoic acid), we presumed that anthropogenic organic compounds, especially aromatics, were the most likely precursors of LO-OOA1. MO-OOA correlated well with odd oxygen (Ox), and its concentration responded positively to the increase of liquid water content (LWC) in NR-PM1, indicating that the formation of MO-OOA involved photochemical oxidation and aqueous processes. It exhibited the best correlation with malic acid which can be formed through the oxidation of various precursors. Moreover, it was plausible that LO-OOA1 was further oxidized to MO-OOA through aqueous processes, as indicated by the consistent diurnal variations of MO-OOA to LO-OOA1 ratio and LWC. This study highlights the important roles of anthropogenic emissions and aqueous processes in SOA formation in coastal areas downwind of cities.

Emission characteristics, sources, and airborne fate of speciated organics in particulate matters in a Hong Kong residence.

A growing number of studies warn of the adverse health effects of indoor particulate matters (PM). However, little is known about the molecular compositions and emission characteristics of PM-bound organics (OM) indoors, a critical group of species with highest concentration and complexity in indoor PM. In a Hong Kong residence where prescribed activities were performed with normal frequency and intensity, we found that the activities significantly elevated not only the total concentration but also the fraction of OM in indoor PM. However, the concentration of the total PM-bound OM outdoors (10.3 ± 0.7 µg/m3 ) surpassed that for the indoor counterpart during the undisturbed period (8.2 ± 0.1 µg/m3 ), that is, period when there was no activity with high emission of PM but the residual effects of previous activities might remain. Emissions of indoor activities involving combustion or high-temperature processes significantly elevated the indoor-to-outdoor (I/O) ratios for a majority of organic species. In addition, gas-to-particle partitioning, secondary formation, carrying-over (residues of pollutants in the air), and re-emission also modulated the I/O ratios of some compounds. Chemically comprehensive emission profiles of speciated organics were obtained for 5 indoor activities in the residence. While the indoor contribution to PM-bound OM was estimated to be not higher than 13.1% during the undisturbed period, carrying-over and/or re-emission seemed to exist for certain compounds emitted from cigarette smoking and incense burning. This study enhances knowledge on emissions and airborne fate of speciated organics in indoor PM.

Real-time molecular characterization of air pollutants in a Hong Kong residence: Implication of indoor source emissions and heterogeneous chemistry.

Due to the high health risks associated with indoor air pollutants and long-term exposure, indoor air quality has received increasing attention. In this study, we put emphasis on the molecular composition, source emissions, and chemical aging of air pollutants in a residence with designed activities mimicking ordinary Hong Kong homes. More than 150 air pollutants were detected at molecular level, 87 of which were quantified at a time resolution of not less than 1 hour. The indoor-to-outdoor ratios were higher than 1 for most of the primary air pollutants, due to emissions of indoor activities and indoor backgrounds (especially for aldehydes). In contrast, many secondary air pollutants exhibited higher concentrations in outdoor air. Painting ranked first in aldehyde emissions, which also caused great enhancement of aromatics. Incense burning had the highest emissions of particle-phase organics, with vanillic acid and syringic acid as markers. The other noteworthy fingerprints enabled by online measurements included linoleic acid, cholesterol, and oleic acid for cooking, 2,5-dimethylfuran, stigmasterol, iso-/anteiso-alkanes, and fructose isomers for smoking, C28 -C34 even n-alkanes for candle burning, and monoterpenes for the use of air freshener, cleaning agents, and camphor oil. We showed clear evidence of chemical aging of cooking emissions, giving a hint of indoor heterogeneous chemistry. This study highlights the value of organic molecules measured at high time resolutions in enhancing our knowledge on indoor air quality.

In Situ Measurements of Molecular Markers Facilitate Understanding of Dynamic Sources of Atmospheric Organic Aerosols.

Reducing the amount of organic aerosol (OA) is crucial to mitigation of particulate pollution in China. We present time and air-origin dependent variations of OA markers and source contributions at a regionally urban background site in South China. The continental air contained primary OA markers indicative of source categories, such as levoglucosan, fatty acids, and oleic acid. Secondary OA (SOA) markers derived from isoprene and monoterpenes also exhibited higher concentrations in continental air, due to more emissions of their precursors from terrestrial ecosystems and facilitation of anthropogenic sulfate for monoterpenes SOA. The marine air and continental-marine mixed air had more abundant hydroxyl dicarboxylic acids (OHDCA), with anthropogenic unsaturated organics as potential precursors. However, OHDCA formation in continental air was likely attributable to both biogenic and anthropogenic precursors. The production efficiency of OHDCA was highest in marine air, related to the presence of sulfur dioxide and/or organic precursors in ship emissions. Regional biomass burning (BB) was identified as the largest contributor of OA in continental air, with contributions fluctuating from 8% to 74%. In contrast, anthropogenic SOA accounted for the highest fraction of OA in marine (37 ± 4%) and mixed air (31 ± 3%), overriding the contributions from BB. This study demonstrates the utility of molecular markers for discerning OA pollution sources in the offshore marine atmosphere, where continental and marine air pollutants interact and atmospheric oxidative capacity may be enhanced.