Aerosol liquid water in PM2.5 and its roles in secondary aerosol formation at a regional site of Yangtze River Delta.

Aerosol liquid water content (ALWC) plays an important role in secondary aerosol formation. In this study, a whole year field campaign was conducted at Shanxi in north Zhejiang Province during 2021. ALWC estimated by ISORROPIA-II was then investigated to explore its characteristics and relationship with secondary aerosols. ALWC exhibited a highest value in spring (66.38 µg/m3), followed by winter (45.08 µg/m3), summer (41.64 µg/m3), and autumn (35.01 µg/m3), respectively. It was supposed that the secondary inorganic aerosols (SIA) were facilitated under higher ALWC conditions (RH > 80%), while the secondary organic species tended to form under lower ALWC levels. Higher RH (> 80%) promoted the NO3- formation via gas-particle partitioning, while SO42- was generated at a relative lower RH (> 50%). The ALWC was more sensitive to NO3- (R = 0.94) than SO42- (R = 0.90). Thus, the self-amplifying processes between the ALWC and SIA enhanced the particle mass growth. The sensitivity of ALWC and OX (NO2 + O3) to secondary organic carbon (SOC) varied in different seasons at Shanxi, more sensitive to aqueous-phase reactions (daytime R = 0.84; nighttime R = 0.54) than photochemical oxidation (daytime R = 0.23; nighttime R = 0.41) in wintertime with a high level of OX (daytime: 130-140 µg/m3; nighttime: 100-140 µg/m3). The self-amplifying process of ALWC and SIA and the aqueous-phase formation of SOC will enhance aerosol formation, contributing to air pollution and reduction of visibility.

Aromatic formulas in ambient PM2.5 samples from Hong Kong determined using FT-ICR ultrahigh-resolution mass spectrometry.

Many aromatic compounds (e.g., polycyclic aromatic hydrocarbons (PAHs)) found in atmospheric aerosols are toxic and exist in both unsubstituted and substituted forms. Previous studies have mainly concentrated on investigating unsubstituted PAHs, leaving the substituted compounds largely uncharacterized. This study focuses on detection of both unsubstituted and substituted aromatics in ambient aerosol samples using ultrahigh-resolution mass spectrometry. Aerosol samples collected from roadside, urban, and suburban sites in Hong Kong were characterized by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled with atmospheric pressure photoionization (APPI) or electrospray ionization (ESI). In the APPI+ mode, 166 aromatic CH formulas (i.e., formulas containing C and H only and with a double bond equivalent (DBE) of 4 or higher) were determined through molecular formula calculations based on an accurate m/z determination. Among the determined aromatic CH formulas, 141 are possible alkylated monocyclic aromatic hydrocarbon (MAH) or PAH formulas, and account for ≥ 45% of the total intensity by aromatic CH+ formulas. Both APPI+ and ESI+ are effective in detecting nitroaromatics (i.e., CHO2N1 formulas and DBE ≥ 5). The two ionization modes provide complementary formula coverage, with formulas determined by APPI+ extending to higher DBE and those by ESI+ covering higher carbon numbers. Alkylated nitrobenzene compounds are the most abundant among nitroaromatics, and they, together with alkylated nitro-PAHs, account for > 80% of the total intensity of aromatic CHO2N+ formulas, indicating the importance of these compounds in real aerosol samples. Aromatic CHN+ and CHO+ formulas are also determined, confirming the atmospheric presence of some previously reported O- and N-containing aromatic compounds and revealing new possible formulas. The determination of aromatic organic formulas in this study provides useful guidance for future quantitative analysis of hazardous aromatic compounds. Future work is needed to determine the abundance and to study the toxicity of alkylated MAHs and PAHs outside the 16 US EPA priority PAH compounds. Graphical abstract.

Reactive Oxygen Species Production Mediated by Humic-like Substances in Atmospheric Aerosols: Enhancement Effects by Pyridine, Imidazole, and Their Derivatives.

Ambient particulate matter (PM) can cause adverse health effects via their ability to produce reactive oxygen species (ROS). Humic-like substances (HULIS), a complex mixture of amphiphilic organic compounds, have been demonstrated to contain the majority of redox activity in the water-extractable organic fraction of PM. Reduced organic nitrogen compounds, such as alkaloids resulting from biomass burning emissions, are among HULIS constituents. In this study, we examined the redox activities of pyridine, imidazole and their alkyl derivatives using a cell-free dithiothreitol (DTT) assay under simulated physiological conditions (37 °C, pH = 7.40). These compounds were found to have little redox activity on their own as measured by the DTT assay, but they enhanced ROS generation catalyzed by 1,4-naphthoquinone (as a model quinone compound) and HULIS isolated from multiple aerosol samples. The enhancement effect by the individual nitrogen-containing bases was determined to be proportional to their amount in the assay solutions. It is postulated that the underlying mechanism involves the unprotonated N atom acting as a H-bonding acceptor to facilitate hydrogen-atom transfer in the ROS generation cycle. The enhancement capability was found to increase with their basicity (i.e., pKa of their conjugated acids, BH(+)), consistent with the proposed mechanism for enhancement. Among the imidazole homologues, a linear relationship was observed between the enhancement factors (in log scale) of the unprotonated form of the imidazole compounds (B) and the pKa of their conjugated acids (BH(+)). This relationship predicts that the range of alkylimidazole homologues (C6-C13) observed in atmospheric HULIS would be 1.5-4.4 times more effective than imidazole in facilitating HULIS-mediated ROS generation. Our work reveals that the ability of atmospheric PM organics to catalyze generation of ROS in cells could be affected by coexisting redox inactive organic constituents and suggests further work deploying multiple assays be conducted to quantify redox capabilities and enhancement effects of the HULIS components.

Characteristics and sources of ambient Volatile Organic Compounds (VOCs) at a regional background site, YRD region, China: Significant influence of solvent evaporation during hot months.

Continuous measurement of 98 volatile organic compounds (VOCs) was conducted during 2017-2019 at a regional background site (Shanxi) located at northeast of Zhejiang Province, YRD region, China. The average concentration of total VOCs (TVOCs) was 25.4 ± 18.4 ppbv, and an increasing trend (+12.2 %) was observed. Alkanes were the most abundant VOC group among all seasons, accounting for 43.5 % of TVOCs. Oxygenated VOCs (OVOCs), aromatics, halides and alkenes contributed 15.9 %, 15.7 %, 11.7 % and 10.3 % of TVOCs concentration, respectively. Biogenic VOCs (BVOCs) and OVOCs showed distinguished diurnal cycle from primary anthropogenic VOCs. Photochemical reactivity analysis based on ozone formation potential (OFP) and OH loss rate (LOH) indicated that aromatics and alkenes were the most significant contributor, respectively. Toluene, xylene (m/p- and o-), ethene and propene were the largest contributor of annual OFP, with the mean OFP being 33.8 ± 44.3 µg·m-3, 31.9 ± 32.1 µg·m-3, 9.29 ± 11.4 µg·m-3, 22.1 ± 21.3 µg·m-3 and 12.8 ± 19.5 µg·m-3, respectively. Seven sources were identified with positive matrix factorization (PMF): petrochemical industry (13.8 %), biogenic emission (1.0 %), solvent usage-toluene (16.9 %), vehicular exhaust (43.8 %), Integrated circuits industry (3.8 %), solvent usage-C8 aromatics (10.9 %), and gasoline evaporation (9.8 %). Vehicular exhaust was the most significant source (43.8 %) during the whole measurement period. Solvent usage, petrochemical industry, and gasoline evaporation showed high temperature dependency. The integrated contribution of solvent usage and industrial processes were higher than vehicular exhaust during hot months. These sources also have higher chemical reactivities and can contribute more on O3 formation. Our results are helpful on determining the control strategies aiming at alleviating O3 pollution.

Abundance of organosulfates derived from biogenic volatile organic compounds: Seasonal and spatial contrasts at four sites in China.

Atmospheric organosulfates (OSs) derived from biogenic volatile organic compounds (BVOCs) encode chemical interaction strength between anthroposphere and biosphere. We report BVOC-derived OSs in the summer of 2016 and the winter of 2017 at four locations in China (i.e., Hong Kong (HK), Guangzhou (GZ), Shanghai (SH), and Beijing (BJ)). The spatial coverage of three climatic zones from the south to the north in China is accompanied with a wide range of aerosol inorganic sulfate (4.9-13.8 µg/m3). We employed a combined targeted and untargeted approach using high-performance liquid chromatography-Orbitrap mass spectrometry to quantify/semi-quantify ~200 OSs and nitrooxy OSs derived from four types of precursors, namely C2-C3 oxygenated VOCs, isoprene, monoterpenes (MT), and sesquiterpenes (ST). The seasonal averages of the total quantified OSs across the four sites are in the range of 201-545 (summer) and 123-234 ng/m3 (winter), with the isoprene-derived OSs accounting for more than 80% (summer) and 57% (winter). The C2-3 OSs and isoprene-derived OSs share the same seasonality (summer >winter) and the same south-north spatial gradient as those of isoprene emissions. In contrast, the MT- and ST-derived OSs are of either comparable abundance or slightly higher abundance in winter at the four sites. The spatial contrasts for MT- and ST-derived OSs are not clearly discernable among GZ, SH, and BJ. HK is noted to have invariably lower abundances of all groups of OSs, in line with its aerosol inorganic sulfate being the lowest. These results indicate that BVOC emissions are the driving factor regulating the formation of C2-3 OSs and isoprene-derived OSs. Other factors, such as sulfate abundance, however, play a more important role in the formation of MT- and ST-derived OSs. This in turn suggests that the formation kinetics and/or pathways differ between these two sub-groups of BVOCs-derived OSs.

Chemical characterization, formation mechanisms and source apportionment of PM2.5 in north Zhejiang Province: The importance of secondary formation and vehicle emission.

PM2.5 affects air quality, therefore, chemical evolution, formation mechanism and source identification of PM2.5 are essential to help figure out mitigation measures. PM2.5 and its constituents were comprehensively characterized with highly time-resolved measurements from 2019 to 2020 in north Zhejiang Province (Shanxi, SX) for the first time, with an emphasis on the contribution of secondary formation and vehicle emission to PM2.5. Secondary inorganic ions (sulfate: 3.86 µg/m3, nitrate: 7.82 µg/m3 and ammonium: 4.59 µg/m3, SNA) were found to be the major components (54%) in PM2.5 (29.70 µg/m3). The highly consistence of nitrate, sulfate and secondary organic compounds (SOC) with Ox (NO2 + O3) or RH indicated the importance of photochemical oxidation and heterogeneous reaction in different scenarios. Higher atmospheric oxidative potential facilitated the SOC formation in spring. The PM2.5 mass was apportioned to eight sources resolved by positive matrix factorization (PMF): secondary nitrate (9.63 µg/m3), secondary sulfate (5.14 µg/m3), vehicle emission (7.26 µg/m3), coal combustion (2.39 µg/m3), biomass burning (1.38 µg/m3), soil dust (0.86 µg/m3), industry emission (0.50 µg/m3), and ship emission (0.32 µg/m3). Secondary nitrate (35%) and sulfate (19%) formation and vehicle emission (26%) were the main factors contributing to the PM2.5. Furthermore, the contribution of secondary nitrate formation increased with elevating PM2.5 concentration. Regional transport was synthetically studied by chemical and backward trajectory analysis, reflecting that secondary nitrate contributed severely to the air quality at SX, while vehicle emission contribution enhanced when atmosphere was stagnant. This study first provides long-term comprehensive chemical characterization and source apportionments of PM2.5 pollution in north Zhejiang, which may provide some guidance for the air pollution control.

Optical properties, source apportionment and redox activity of humic-like substances (HULIS) in airborne fine particulates in Hong Kong.

Humic-like substances (HULIS) account for a considerable fraction of water-soluble organic matter (WSOM) in ambient fine particulates (PM2.5) over the world. However, systemic studies regarding the chemical characteristics, sources and redox activity of HULIS are still limited. In this study, the mass concentration, optical properties, and reactive oxygen species (ROS)-generation potential of HULIS were investigated in PM2.5 samples collected in Hong Kong during 2011-2012, and they all showed higher levels on days under regional pollution than on days under long range transport (LRT) pollution and local emissions. Positive matrix factorization (PMF) analysis was conducted regarding the mass concentration and dithiothreitol (DTT) activity of HULIS. Four primary sources (i.e. marine vessels, industrial exhaust, biomass burning, and vehicle emissions), and two secondary sources (i.e. secondary organic aerosol formation and secondary sulfate) were identified. Most sources showed higher contributions to both the mass concentration and DTT activity of HULIS on regional days than on LRT and local days, except that marine vessels had a higher contribution on local days than the other two synoptic conditions. Secondary processes were the major contributor to HULIS (54.9%) throughout the year, followed by biomass burning (27.4%) and industrial exhaust (14.7%). As for the DTT activity of HULIS, biomass burning (62.9%) and secondary processes (25.4%) were found to be the top two contributors. Intrinsic ROS-generation potential of HULIS was also investigated by normalizing the DTT activity by HULIS mass in each source. HULIS from biomass burning were the most DTT-active, followed by marine vessels; while HULIS formed through secondary processes were the least DTT-active. For the optical properties of HULIS, multiple linear regression model was adopted to evaluate the contributions of various sources to the light absorbing ability of HULIS. Biomass burning was found to be the only source significantly associated with the light absorbing property of HULIS.

[Relationship between sewage treatment efficiency and bacterial community diversity in an A/O MBR].

An Anoxic/Oxic Membrane Bioreactor (A/O MBR) was used to treat sewage. Five different working conditions were run to determine the optimal process parameters. Bacterial community structures in both anoxic and oxic tanks were analyzed using denaturing gradient gel electrophoresis (DGGE). The relationship between effluent water quality and bacterial community diversity was established. The experimental results indicated that, under the optimal parameters of hydraulic retention time (HRT) 12 h, sludge retention time (SRT) 10 d, reflux ratio of nitrified effluent 300%, and reflux ratio of sludge 100%, the A/O MBR removed COD, NH4+ -N, and TN effectively and stably with the average removal rates of 96.4%, 99.1% and 75.8%, respectively. The bacterial communities varied markedly in both anoxic and oxic tanks during the sewage treatment experiment. Under a same working condition, the communities in both tanks were often similar with a similarity of more than 50%. The community diversity of the anoxic tank fluctuated depending on different working conditions, while the diversity of the oxic tank increased steadily along with the operation time. A positive correlation between the bacterial community diversity of the anoxic tank and the denitrification efficiency of the A/O MBR was established.