Exploring secondary aerosol formation associated with elemental carbon in the lower free troposphere.

The variability of element carbon (EC) mixed with secondary species significantly complicates the assessment of its environmental impact, reflecting the complexity and diversity of EC-containing particles' composition and morphology during their ascent and regional transport. While the catalytic role of EC in secondary aerosol formation is recognized, the effects of heterogeneous chemistry on secondary species formation within diverse EC particle types are not thoroughly understood, particularly in the troposphere. Alpine sites offer a prime environment to explore EC properties post-transport from the ground to the free troposphere. Consequently, we conducted a comprehensive study on the genesis of secondary aerosols in EC-containing particles at Mt. Hua (altitude: 2069 m) from 1 May to 10 July, using a single particle aerosol mass spectrometer (SPAMS). Our analysis identified six major EC particle types, with EC-K, EC-SN, and EC-NaK particles accounting for 27.6 %, 27.0 %, and 19.6 % of the EC particle population, respectively. The concentration-weighted trajectory (CWT) indicated that the lower free troposphere over Mt. Hua is significantly affected by anthropogenic emissions at ground-level, predominantly from northwestern and eastern China. Atmospheric interactions are crucial in generating high sulfate levels in EC-SN and EC-OC particles (> 70 %) and notable nitrate levels in EC-K, EC-BB, and EC-Fe particles (> 80 %). The observed high chloride content in EC-OC particles (56 ± 32 %) might enhance chlorine's reactivity with organic compounds via heterogeneous reactions within the troposphere. Distinct diurnal cycles for sulfate and nitrate are mainly driven by varying transport dynamics and formation processes, showing minimal dependency on EC particle types. Enhanced nocturnal oxalate conversion in EC-Fe particles is likely due to the aqueous oxidation of precursors, with Fe-catalyzed Fenton reactions enhancing OH radical production. This investigation provides critical insights into EC's role in secondary aerosol development during its transport in the lower free troposphere.

[Components Characteristic and Source Apportionment of Fine Particulate Matter in Transition Period of Heating Season in Xi'an with High Time Resolution].

Influenced by heating, the concentration of atmospheric fine particulate matter (PM2.5) rises in autumn and winter in northern cities. In this study, Q-ACSM, AE33, and Xact 625 were used to carry out online monitoring of PM2.5 chemical components with high time resolution in Xi'an from October 25 to November 17, 2019, to analyze the characteristics of PM2.5 pollution during the transition period of the heating season. Additionally, we analyzed the sources of PM2.5 in combination with the positive matrix factorization model. The results showed that the average PM2.5 concentration during the observation period was (78.3 ± 38.5) µg·m-3, and the main chemical components were organic matter (OA), secondary inorganic ions (SIA), and dust, which accounted for 38.7%, 31.6%, and 21.2%, respectively. The average concentrations of sulfate, nitrate, and ammonium were (4.0 ± 3.1), (14.9 ± 13.7), and (5.8 ± 4.8) µg·m-3, and the average concentrations of the major metals potassium, calcium, and iron were (1.0 ± 0.4), (1.5 ± 1.1), and (1.4 ± 0.9) µg·m-3. Black carbon, chloride ions, and trace elements contributed relatively little to PM2.5 (5.7%, 1.3%, and 1.5%, respectively). In the pollution development and maintenance stage, the concentration of OA and SIA increased by 137.7% to 537.0%, whereas in the pollution dissipation stage, only the concentration of dust gradually increased. The source apportionment results showed that secondary sources, biomass burning, dust, vehicle emission, industrial emission, and coal combustion were the main sources of PM2.5 during the observation period, contributing 29.1%, 21.1%, 15.3%, 12.9%, 11.4%, and 10.2%, respectively. The contribution rate of secondary sources and biomass burning was higher in the pollution development and maintenance stage, and dust was higher in the pollution dissipation stage.

Major source categories of PM2.5 oxidative potential in wintertime Beijing and surroundings based on online dithiothreitol-based field measurements.

Fine particulate matter (PM2.5) causes millions of premature deaths each year worldwide. Oxidative potential (OP) has been proposed as a better metric for aerosol health effects than PM2.5 mass concentration alone. In this study, we report for the first time online measurements of PM2.5 OP in wintertime Beijing and surroundings based on a dithiothreitol (DTT) assay. These measurements were combined with co-located PM chemical composition measurements to identify the main source categories of aerosol OP. In addition, we highlight the influence of two distinct pollution events on aerosol OP (spring festival celebrations including fireworks and a severe regional dust storm). Source apportionment coupled with multilinear regression revealed that primary PM and oxygenated organic aerosol (OOA) were both important sources of OP, accounting for 41 ± 12 % and 39 ± 10 % of the OPvDTT (OP normalized by the sampled air volume), respectively. The small remainder was attributed to fireworks and dust, mainly resulting from the two distinct pollution events. During the 3.5-day spring festival period, OPvDTT spiked to 4.9 nmol min-1 m-3 with slightly more contribution from OOA (42 ± 11 %) and less from primary PM (31 ± 15 %). During the dust storm, hourly-averaged PM2.5 peaked at a very high value of 548 µg m-3 due to the dominant presence of dust-laden particles (88 % of total PM2.5). In contrast, only mildly elevated OPvDTT values (up to 1.5 nmol min-1 m-3) were observed during this dust event. This observation indicates that variations in OPvDTT cannot be fully explained using PM2.5 alone; one must also consider the chemical composition of PM2.5 when studying aerosol health effects. Our study highlights the need for continued pollution control strategies to reduce primary PM emissions, and more in-depth investigations into the source origins of OOA, to minimize the health risks associated with PM exposure in Beijing.

Heterogeneous characteristics and absorption enhancement of refractory black carbon in an urban city of China.

In this study, field measurement was conducted using an integrated online monitoring system to characterize heterogeneous properties and light absorption of refractory black carbon (rBC). rBC particles are mainly from the incomplete combustion of carbonaceous fuels. With the data collected from a single particle soot photometer, thickly coated (BCkc) and thinly coated (BCnc) particles are characterized with their lag times. With different responses to the precipitation, a dramatical decline of 83 % in the number concentration of BCkc is shown after rainfall, while that of BCnc decreases by 39 %. There is a contrast in core size distribution that BCkc is always with larger particle sizes but has smaller core mass median diameters (MMD) than BCnc. The mean rBC-containing particle mass absorption cross-section (MAC) is 6.70 ± 1.52 m2 g-1, while the corresponding rBC core is 4.90 ± 1.02 m2 g-1. Interestingly, there are wide variations in the core MAC values which range by 57 % from 3.79 to 5.95 m2 g-1, which are also closely related to those of the whole rBC-containing particles with a Pearson correlation of 0.58 (p < 0.01). Errors would be made if we eliminate the discrepancies and set the core MAC as a constant when calculating absorption enhancement (Eabs). In this study, the mean Eabs is 1.37 ± 0.11 while the source apportionment shows that there are five contributors of Eabs including secondary aging (37 %), coal combustion (26 %), fugitive dust (15 %), biomass burning (13 %) and traffic-related emissions (9 %). Secondary aging is found to be the highest contributor due to the liquid phase reactions in formations of secondary inorganic aerosol. Our study characterizes property diversities and provides insights into the sources impacting the light absorption of rBC and will be helpful for controlling it in the future.

High time-resolution source apportionment and health risk assessment for PM2.5-bound elements at an industrial city in northwest China.

To better respond to heavy air pollution, the local government of Baoji City, a traditionally industry dominated city in northwest China, released several warning levels between December 2019 and January 2020. The system aims to provide a more efficient control of pollution sources. In this study, a high-time resolution measurement of PM2.5-bound elements was applied to capture the diurnal-scale dynamic processes associated with major pollution activities in northwest China. A series of elements were quantified and used for source apportionment using the positive matrix factorization (PMF) model. Combined with the local characteristics, nine sources were resolved with contributions in descending order: fugitive dust (36.6 %), biomass burning (20.1 %), traffic-related (10.4 %), coal combustion (10.0 %), titanium alloy smelting (7.2 %), As-related industry (6.9 %), Zn-related industry (5.6 %), molybdenum alloy smelting (2.5 %), and Cr-related industry (0.7 %). The health risk assessment indicated non-carcinogenic risks for Mn and carcinogenic risks for As and Cr in both adults and children. The cumulative non-carcinogenic risk for the elements was 3.2 times the safety threshold, while the carcinogenic risk (CR) was 6.8 and 27 times the acceptable levels for children and adults, respectively. For source-resolved risks, As- and Cr-related industry emissions showed the highest carcinogenic risk. Five of the nine resolved sources for adults have CR values 1.4 and 9.7 times the acceptable level. This study provides valuable information for developing targeted strategies to control air pollutants and protect public health.

Optical properties of mountain primary and secondary brown carbon aerosols in summertime.

Brown carbon (BrC) can affect atmospheric radiation due to its strong absorption ability from the near ultraviolet to the visible range, thereby influencing global climate. However, given the complexity of BrC's chemical composition, its optical properties are still poorly understood, especially in mountainous areas. In this study, the black carbon (BC) tracer method is used to explore the light-absorbing properties of primary and secondary BrC at Mount Hua, China during the 2018 summer period. The primary BrC absorption contributes to 10-15% of the total BrC absorption at a wavelength of 370 nm. From the positive matrix factorization analysis, traffic emissions are found to be a major source of primary BrC absorption (44%), followed by industry and biomass-burning emissions (29%). The secondary BrC accounts for 87% of the total BrC absorption at a wavelength of 370 nm, indicating that BrC is dominated by secondary formation. The observation of a higher secondary BrC absorption diurnal pattern at Mount Hua can be affected by secondary BrC in the residual layer after sunrise and the formation of light-absorbing chromophores by photochemical oxidation in the afternoon. The estimated average mass absorption efficiencies of primary and secondary BrC (MAE_pri and MAE_sec, respectively) are 0.4 m2/g and 2.1 m2/g at wavelengths of 370 nm, respectively, indicating a stronger light-absorbing ability for secondary BrC than for primary BrC. There is no significant difference in MAE_pri within a daily variation, but the daytime MAE_sec value is higher than that during the night. Our study shows that secondary BrC is important to light absorption in mountainous areas.

Chemical characteristics and sources of nitrogen-containing organic compounds at a regional site in the North China Plain during the transition period of autumn and winter.

Organic nitrogen constitutes a significant fraction of the nitrogen budget in particulate matter (PM). However, the composition and sources of nitrogen-containing organic compounds (NOCs) in PM remain unclear currently in North China Plain (NCP), China. Rare local or regional studies on NOCs were conducted. In this study, ambient fine particles (PM2.5) were collected in Xianghe, a regional background site in NCP, from 26 October to 26 December 2017. The insights from this study include NOC molecule identification, concentration level, and NOC sources and origins. Specifically, we have identified and quantified >90 NOC species, with urea being the most abundant, accounting for 39.7 ± 4.7% of the total NOC followed by free amino acids (FAAs; 21.9 ± 1.5%), cyclic NOCs (15.3 ± 4.5%), amines (14.8 ± 1.5%), alkyl amides (5.8 ± 0.5%), isocyanates (1.7 ± 0.2%), and nitriles (1.1 ± 0.2%). The time series of FAAs was well correlated (r = 0.51-0.68, p < 0.01) with the organic marker of levoglucosan and was moderately correlated with Ox (r = 0.29-0.41, p < 0.01), suggesting biomass burning and secondary formation were important FAAs sources. We also show that amines can be oxidized and/or reacted by aqueous-phase processing to form secondary aerosols, which are further enhanced by the involvement of iron in the catalytic process. Using the receptor model of positive matrix factorization (PMF), six factors were identified including coal combustion, crustal sources, biomass burning, industry-related sources, traffic emissions, and secondary aerosols. Source apportionment of NOC shows biomass burning was the dominant factor, accounting for 31.8% of the total NOCs. This study provides a unique dataset of NOCs at this regional background site in the NCP, with the insights of NOC chemical composition and sources gained in this study being important for future NOC modeling as well as NOC health effects studies.

Impacts of primary emissions and secondary aerosol formation on air pollution in an urban area of China during the COVID-19 lockdown.

Restrictions on human activities were implemented in China to cope with the outbreak of the Coronavirus Disease 2019 (COVID-19), providing an opportunity to investigate the impacts of anthropogenic emissions on air quality. Intensive real-time measurements were made to compare primary emissions and secondary aerosol formation in Xi'an, China before and during the COVID-19 lockdown. Decreases in mass concentrations of particulate matter (PM) and its components were observed during the lockdown with reductions of 32-51%. The dominant contributor of PM was organic aerosol (OA), and results of a hybrid environmental receptor model indicated OA was composed of four primary OA (POA) factors (hydrocarbon-like OA (HOA), cooking OA (COA), biomass burning OA (BBOA), and coal combustion OA (CCOA)) and two oxygenated OA (OOA) factors (less-oxidized OOA (LO-OOA) and more-oxidized OOA (MO-OOA)). The mass concentrations of OA factors decreased from before to during the lockdown over a range of 17% to 58%, and they were affected by control measures and secondary processes. Correlations of secondary aerosols/ΔCO with Ox (NO2 + O3) and aerosol liquid water content indicated that photochemical oxidation had a greater effect on the formation of nitrate and two OOAs than sulfate; however, aqueous-phase reaction presented a more complex effect on secondary aerosols formation at different relative humidity condition. The formation efficiencies of secondary aerosols were enhanced during the lockdown as the increase of atmospheric oxidation capacity. Analyses of pollution episodes highlighted the importance of OA, especially the LO-OOA, for air pollution during the lockdown.

Chemical composition and sources of submicron aerosols in winter at a regional site in Beijing-Tianjin-Hebei region: Implications for the Joint Action Plan.

The Ministry of Environmental Protection released a Joint Action Plan for Control of Air Pollution (Hereafter, Joint Action Plan, JAP), to reduce PM2.5 concentrations in the Beijing-Tianjin-Hebei region (BTH) during the winter of 2017. To investigate the effectiveness of the controls, we deployed an aerosol chemical speciation monitor and collected filter samples at Xianghe, a representative site for the BTH, to characterize the aerosol composition during the implementation of the JAP. Those results were compared with earlier data obtained from a literature survey and reanalysis of studies in the BTH. During several pollution episodes in the control period, the major aerosol types changed relative to the earlier studies from sulfate, oxygenated organic aerosol, and coal combustion organic aerosol to nitrate and biomass burning organic aerosol. The dominant secondary inorganic aerosol species during the JAP changed from sulfate to nitrate, and the main source for primary organic aerosol switched from coal combustion to biomass burning. These changes can be explained by the fact that the JAP controls targeted coal combustion and SO2 but not biomass burning or NOx emissions. Our evaluation of the control measures provides a scientific basis for developing new policies in the future.

Wintertime Optical Properties of Primary and Secondary Brown Carbon at a Regional Site in the North China Plain.

The light-absorbing properties of atmospheric brown carbon (BrC) are poorly understood due to its complex chemical composition. Here, a black-carbon-tracer method was coupled with source apportionments of organic aerosol (OA) to explore the light-absorbing properties of primary and secondary BrC from the North China Plain (NCP). Primary emissions of BrC contributed more to OA light absorption than secondary processes, and biomass burning OA accounted for 60% of primary BrC absorption at λ = 370 nm, followed by coal combustion OA (35%) and hydrocarbon-like OA (5%). Secondary BrC absorption was high in the early morning and later decreased due to the bleaching of chromophores. Nighttime aqueous-phase chemistry promoted the formation of secondary light-absorbing compounds and the production of strongly absorbing particles. Source analysis showed that the NCP region was the most important source for primary and secondary BrC subtypes at the study site. The mean direct radiative forcing for BrC was 0.15 W m-2 (0.11 W m-2 and 0.04 W m-2 for the primary and secondary fractions, respectively). This study provides new information on the optical properties of primary and secondary BrC and highlights the importance of atmospheric oxidation on BrC absorption.