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.

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.

Estimating organic aerosol emissions from cooking in winter over the Pearl River Delta region, China.

Cooking is an important source of organic aerosols (OA), particularly in urban areas, but it has not been explicitly included in current emission inventories in China. This study estimated the organic aerosol emissions from cooking during winter over the Pearl River Delta (PRD) region, China. Using the retrieved hourly cooking organic aerosol (COA) concentrations at two sites in Hong Kong and Guangzhou, population density, and daily per capita COA emissions, we determined the spatial and temporal distribution of COA emissions over the PRD region based on two approaches by treating COA as non-volatile (NVCOA) and semi-volatile (SVCOA), respectively. By using the estimated COA emissions and the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) model, we reproduced the diurnal cycles of COA concentrations at the PolyU site in Hong Kong and Panyu site in Guangzhou. We also resolved the different patterns of COA between weekdays and weekends. The mean COA concentration during wintertime over the urban areas of the PRD region was 0.7 µg m-3 and 0.9 µg m-3 for the NVCOA and SVCOA cases, respectively, contributing 5.1% and 6.9% to the urban OA concentrations. The total COA emissions in winter over the PRD region were estimated to be 3.5 × 108 g month-1 and 3.8 × 108 g month-1 for the NVCOA and SVCOA cases, respectively, adding 34.8% and 37.8% to the total primary organic aerosol emissions. Considering COA emissions in the model increased the mean regional OA concentrations by 4.6% and 7.4% for the NVCOA and SVCOA cases, respectively. Our study therefore highlights the importance of cooking activities to OA concentrations in winter over the PRD region.

Primary emissions and secondary production of organic aerosols from heated animal fats.

Cooking is an important source of primary organic aerosol (POA) in urban areas, and it may also generate abundant non-methane organic gases (NMOGs), which form oxidized organic aerosol (OOA) after atmospheric oxidation. Edible fats play an important role in a balanced diet and are part of various types of cooking. We conducted laboratory studies to examine the primary emissions of POA and NMOGs and OOA formation using an oxidation flow reactor (OFR) for three animal fats (i.e., lard, beef and chicken fats) heated at two different temperatures (160 and 180 °C). Positive matrix factorization (PMF) revealed that OOA formed together with POA loss after photochemical aging, suggesting the conversion of some POA to OOA. The maximum OOA production rates (PRs) from heated animal fats, occurring under OH exposures (OHexp) of 8.3-15 × 1010 molecules cm-3 s, ranged from 8.9 to 24.7 µg min-1, 1.6-14.5 times as high as initial POA emission rates (ERs). NMOG emissions from heated animal fats were dominated by aldehydes, which contributed 14-71% of the observed OOA. We estimated that cooking-related OOA could contribute to as high as ~10% of total organic aerosol (OA) in an urban area in Hong Kong, where cooking OA (COA) dominated the POA. This study provides insights into the potential contribution of cooking to urban OOA, which might be especially pronounced when cooking contributions dominate the primary emissions.

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.

Atmospheric fate of peroxyacetyl nitrate in suburban Hong Kong and its impact on local ozone pollution.

Peroxyacetyl nitrate (PAN) is an important reservoir of atmospheric nitrogen, modulating reactive nitrogen cycle and ozone (O3) formation. To understand the origins of PAN, a field measurement was conducted at Tung Chung site (TC) in suburban Hong Kong from October to November 2016. The average level of PAN was 0.63 ±â€¯0.05 ppbv, with a maximum of 7.30 ppbv. Higher PAN/O3 ratio (0.043-0.058) was captured on episodes, i.e. when hourly maximum O3 exceeded 80 ppbv, than on non-episodes (0.01), since O3 production was less efficient than PAN when there was an elevation of precursors (i.e. volatile organic compounds (VOCs) and nitrogen oxide (NOx)). Model simulations revealed that oxidations of acetaldehyde (65.3 ±â€¯2.3%), methylglyoxal (MGLY, 12.7 ±â€¯1.2%) and other oxygenated VOCs (OVOCs) (8.0 ±â€¯0.6%), and radical cycling (12.2 ±â€¯0.8%) were the major production pathways of peroxyacetyl (PA) radical, while local PAN formation was controlled by both VOCs and nitrogen dioxide (NO2). Among all VOC species, carbonyls made the highest contribution (59%) to PAN formation, followed by aromatics (26%) and biogenic VOCs (BVOCs) (10%) through direct oxidation/decomposition. Besides, active VOCs (i.e. carbonyls, aromatics, BVOCs and alkenes/alkynes) could stimulate hydroxyl (OH) production, thus indirectly facilitating the PAN formation. Apart from primary emissions, carbonyls were also generated from oxidation of first-generation precursors, i.e., hydrocarbons, of which xylenes contributed the most to PAN production. Furthermore, PAN formation suppressed local O3 formation at a rate of 2.84 ppbv/ppbv, when NO2, OH and hydroperoxy (HO2) levels decreased and nitrogen monoxide (NO) value enhanced. Namely, O3 was reduced by 2.84 ppbv per ppbv PAN formation. Net O3 production rate was weakened (∼36%) due to PAN photochemistry, so as each individual production and loss pathway. The findings advanced our knowledge of atmospheric PAN and its impact on O3 production.

Secondary Organic Aerosol Formation from Urban Roadside Air in Hong Kong.

Motor vehicle emissions are an important but poorly constrained source of secondary organic aerosol (SOA). Here, we investigated in situ SOA formation from urban roadside air in Hong Kong during winter time using an oxidation flow reactor (OFR), with equivalent atmospheric oxidation ranging from several hours to several days. The campaign-average mass enhancement of OA, nitrate, sulfate, and ammonium upon OFR aging was 7.0, 7.2, 0.8, and 2.6 µg m-3, respectively. To investigate the sources of SOA formation potential, we performed multilinear regression analysis between measured peak SOA concentrations from OFR and the concentrations of toluene that represent motor vehicle emissions and cooking OA from positive matrix factorization (PMF) analysis of ambient OA. Traffic-related SOA precursors contributed 92.3%, 92.4%, and 83.1% to the total SOA formation potential during morning rush hours, noon and early afternoon, and evening meal time, respectively. The SOA production factor (PF) was approximately 5.2 times of primary OA (POA) emission factor (EF) and the secondary particulate matter (PM) PF was approximately 2.6 times of primary particles EF. This study highlights the potential benefit of reducing secondary PM production from motor vehicle emissions in mitigating PM pollutions.

Continuous effectiveness of replacing catalytic converters on liquified petroleum gas-fueled vehicles in Hong Kong.

To mitigate the concentrations of air pollutants in the atmosphere, an intervention program of replacing the converters of liquefied petroleum gas (LPG) fueled vehicles was implemented by the Hong Kong government between October 2013 and April 2014. Data of ambient volatile organic compounds (VOCs) and other trace gases continuously monitored from September 2012 to April 2017 at a roadside site were used to evaluate the continuous effectiveness of the replaced catalytic converters on the reduction of air pollutants. The measurement data showed that LPG-related VOCs (propane and n/i-butanes) and several trace gases (CO, NO and NO2) decreased significantly from before to after the program (p < 0.01). To further assess the efficiency of the program, five periods covering before the program, during the program, 1st year after the program, 2nd year after the program and 3rd year after the program were categorized. The values of propane and n/i-butanes decreased from Period-1 (before the program) to Period-2 (during the program), and from Period-2 to Periods 3-5 (after the program) (p < 0.01). In addition, the reduction rates of propane and n/i-butanes remained high and constant in Periods 3-5, suggesting that either had the vehicle owners themselves routinely replaced the converters at suitable interval afterwards, or were their vehicles caught by a remote sensing program checking excessive emissions. Source apportionment analysis indicated that LPG-fueled vehicular emissions were the top contributor to ambient VOCs in the roadside environment while the VOCs emitted from LPG-fueled vehicles indeed decreased at a rate of 4.21 ±â€¯2.38 ppbv/year (average ±â€¯95% confidence interval) from Period-1 to Period-5 (p < 0.01). Furthermore, the photochemical box model simulations revealed that the net negative contribution of VOCs and NOx emitted from LPG-fueled vehicles to O3 production strengthened at a rate of 1.9 × 10-2 pptv/day from Period-1 to Period-5 (p < 0.01). The findings proved the continuous effectiveness of the intervention program, and are of help to future control strategies in Hong Kong.