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The reaction of alkenes with ozone has great effect on atmospheric oxidation, its transient species can produce OH radicals and contribute to the formation of secondary organic aerosols (SOA). In the present study, the reaction of tetramethylethene (TME) with ozone was investigated using self-assembled low temperature matrix isolation system. The TME and ozone were co-deposited on a salt plate at 15 K, and then slowly warmed up the plate. The first transient species primary ozonide (POZ) was detected, indicating that the reaction followed Criegee mechanism. Then POZ began to decompose at 180 K. However, secondary ozonide (SOZ) was not observed according to Criegee mechanism. Probably, Criegee Intermediate (CI) did not react with inert carbonyl of acetone, but with remaining TME formed tetra-methyl epoxide (EPO).

International audience; Severe volatile organic compound (VOC) pollution has become an urgent problem during the heating season in the North China Plain (NCP), as exposure to hazardous VOCs can lead to chronic or acute diseases. A campaign with online VOC measurements was conducted at a rural site in Wangdu, NCP during the 2018 heating season to characterize the compositions and associated sources of VOCs and to assess their potential health risks. The total concentration of VOCs with 94 identified species was 77.21 ± 54.39 ppb. Seven source factors were identified by non-negative matrix factorization, including coal combustion (36.1%), LPG usage (21.1%), solvent usage (13.9%), biomass burning and secondary formation (14.2%), background (7.0%), industrial emissions (4.5%), and vehicle emissions (3.3%). The point estimate approach and Monte Carlo simulation were used to estimate the carcinogenic and non-carcinogenic risks of harzadous VOCs. The results showed that the cumulative health risk of VOCs was above the safety level. Acrolein, 1.2-dichloroethane, 1,2-dichloropropane, chloroform, 1,3-butadiene, and benzene were identified as the key hazardous VOCs in Wangdu. Benzene had the highest average carcinogenic risk. Solvent usage and secondary formation were the dominant sources of adverse health effects. During the Spring Festival, most sources were sharply reduced; and VOC concentration declined by 49%. However, coal and biomass consumptions remained relatively large, probably due to heating demand. This study provides important references for the control strategies of VOCs during the heating season in heavily polluted rural areas in the NCP.

International audience

The receptor model is an effectively and widely used tool for analyzing the source of PM2.5, and its development and improvement have always been focused and challenged. In this study, approaches of source analysis is applied and compared. The PM2.5 samples were collected in spring of 2015 at a remote background site of Weizhou, South China and were analyzed for water-soluble ions, trace metals, and sugars. The 28 measurement species were introduced into the positive matrix factorization (PMF) and a non-negative matrix factorization (NMF) model for inter-comparison of PM2.5 prediction. Results showed that the NMF model is a more robust tool to identify source types and source apportionment in the case of a small sample size (n = 31). In NMF, four source variants were obtained as dust (15.6%), biomass combustion (11.8%), secondary formation (17.6%), and coal combustion (54.9%), corresponding to four main source areas. These were Southeast Asia, South China Sea, Taiwan Strait, as well as Pearl River Delta, respectively. The areas were distinguished based on hybrid receptor models, potential source contribution function (PSCF) and concentration weighted trajectory (CWT), by introducing the daily loadings of each source factor from NMF method. These model results were highly consistent with categorized chemical characteristics of PM2.5, suggesting that NMF linking with hybrid receptor models provides valuable implications for exploring source types and source areas of PM2.5. Meanwhile, biomass combustion and coal combustion comparably contributed to the high PM2.5 concentrations indicating control strategy in South China in spring.

Over the past few decades, northeast Asia has suffered from the extreme levels of PM2.5 (particulate matter with an aerodynamic diameter smaller than 2.5 μm). Despite extensive efforts and the scientific advances in understanding PM2.5 pollution, the fundamental mechanisms responsible for the occurrence of high PM2.5 concentrations have not been comprehensively understood. In this study, we investigated the physical and chemical drivers for the formation and transformation of atmospheric particles using a four-year dataset of nanoparticle number size distributions, PM2.5 chemical composition, gaseous precursors, and meteorological variables in northeast Asia outflows. The empirical orthogonal function (EOF) analyses of size-separated particle numbers extracted two modes representing a burst of nanoparticles (EOF1) and an increase in PM2.5 mass (EOF2) associated with persistent anticyclone and synoptic-scale stagnation, respectively. The vertical structure of the particles demonstrated that the synoptic conditions also affected the daily evolution of boundary layer, promoting either the formation of nanoparticles through deep mixing or conversion into accumulation-mode particles in shallow mixed layers. In the haze-development episode equivalent to EOF2 during the KORUS-AQ (KORea-US Air Quality) campaign, the PM2.5 mass reached 63 μg m−3 with the highest contribution from inorganic constituents, which was accompanied by a thick coating of refractory black carbon (rBC) that linearly increased with condensation-mode particles. This observational evidence suggests that the thick coating of rBC resulted from an active conversion of condensable gases into particle-phase on the BC surface, thereby increasing the mass of the accumulation-mode aerosol. Consequently, this result complies with the strategy to reduce black carbon as a way to effectively mitigate haze pollution as well as climate change in northeast Asia.

Commodity plastic is ubiquitous in daily life and commonly disposed of via unregulated burning, particularly in developing regions. We report here the much higher emission factors (13.1 ± 7.5 g/kg) and toxicities of inhalable aerosols emitted from the unregulated burning of plastic waste based on field measurements and cellular experiments, including oxidative stress and cytotoxic tests in A549 cells. Plastic foam burning emitted aerosols possesses the highest EFs (34.8 ± 4.5 g/kg) and toxicities, which are 4.2- to 13.4-fold and 1.1- to 2.7-fold higher than those emitted from the burning of other waste types. These quantified toxicities are mainly attributed to aerosols containing carbonaceous matter, especially persistent organic pollutants, including polycyclic aromatic hydrocarbons and dioxins, which originate from incomplete combustion processes. The aerosol emission amounts were estimated from the obtained experimental results. Approximately 70.2 million tons (29%) of plastic waste was burned without regulation worldwide in 2016, leading to 0.92 ± 0.53 million tons of toxic aerosols being released into the air, a majority of which occurred in developing regions. The results indicate improved combustion technology and control strategies are urgently needed in developing regions for discarded plastic -waste to mitigate toxic exposure risks and achieve sustainable development.

Particulate nitrite is a critical source of hydroxyl radicals; however, it lacks high-resolution methods due to its low abundance and stability to explore its formation mechanism. In this study, a modified versatile aerosol concentration enrichment system (VACES) coupled with ion chromatography (IC) was used to measure particulate NO2- hourly online and achieve a lowered detection limit of 10-3 μg m-3. VACES-IC was used to observe a high- and low-concentration events of PM1.0-NO2- in Shanghai, corresponding to the ambient-level concentrations of 0.34 and 0.05 μg m-3, respectively. The morning peak concentrations of NO2- even exceeded 3σ (standard deviation) in the high-concentration event due to the reduction of NO2 by aerosol SO32- based on kinetics and regression analysis. This implies that controlling SO2 emissions would be an effective strategy to decrease morning NO2- concentrations, correspondingly reducing the kinetic formation of SO42- by 20.8-34.8%. However, after sunrise, NO2- formation was primarily attributed to NO2 hydrolysis at pH 4.97-6.14. In the low-concentration event, NO2 hydrolysis also accounted for an overwhelming proportion (∼90%) of NO2- formation. This work estimates the contribution of different paths to particulate NO2- formation based on newly established high-resolution measurements.

Acute toxicity assay presents vital significance in modern environmental monitoring, including online detection and in-situ assay for emergency events. Although photobacteria related detection methods were established and verified in the past decades with combination of photomultiplier tube (PMT), the price and size of PMT sensor hampered application of rapid acute toxicity assay and detection system miniaturization, especially in the resource-limited occasions. Wide application of smartphones with great low-light performance cameras could be used in photobacteria-based toxicity assay instead of the PMT methods. Herein a box-type portable detection system had been successfully established, including a disc-chip for detection, detection device, and smartphones with a high-performance camera. The system performed well showing stable temperature and rotation control. Results captured by CMOS-based camera presented a linear relationship with PMT-based detection method. An image progress algorithm was also established and tested by series diluted zinc sulfate solution as a reference substance. The system also performed well for toxicity analysis for real Atmospheric particle matter sample. The system could be used in some environmental monitoring scenarios as an alternative solution.

For PM2.5 filter samples collected daily at the Chinese Research Academy of Environmental Sciences (Beijing, China) from December of 2013 to February of 2014 (the winter period), chemical characteristics and sources were investigated with an emphasis on haze events in different alert levels. During the 3 months, the average PM2.5 concentration was 89 µg m−3, exceeding the Chinese national standard of 75 µg m−3 in 24  h. The maximum PM2.5 concentration was 307 µg m−3, which characterizes developed-type pollution (PM2.5 / PM10>0.5) in the World Health Organization criteria. PM2.5 was dominated by SO42−, NO3−, and pseudo-carbonaceous compounds with obvious differences in concentrations and proportions between non-haze and haze episodes. The non-negative matrix factorization (NMF) analysis provided reasonable PM2.5 source profiles, by which five sources were identified: soil dust, traffic emission, biomass combustion, industrial emission, and coal combustion accounting for 13, 22, 12, 28, and 25  % of the total, respectively. The dust impact increased with northwesterlies during non-haze periods and decreased under stagnant conditions during haze periods. A blue alert of heavy air pollution was characterized by the greatest contribution from industrial emissions (61  %). During the Chinese Lantern Festival, an orange alert was issued and biomass combustion was found to be the major source owing to firework explosions. Red-alert haze was almost equally contributed by local traffic and transported coal combustion emissions from the vicinity of Beijing (approximately 40  % each) that was distinguished by the highest levels of NO3− and SO42−, respectively. This study also reveals that the severity and source of haze are largely dependent on meteorological conditions.

From October till November in 2010 and during March of 2011, when Chinese outflow events were frequently encountered, the chemical composition of submicron particles (PM1.0) was determined hourly using a particle-into-liquid sampler at the Gosan Climate Observatory. Three distinctive pollution plume types were identified: haze aerosols impacted by biomass combustion, nanoparticle bursts associated with outflow from Beijing, and saline soil particles from salt deposits. The highest PM1.0 concentration was observed in a fall haze event, under near-stagnant high-pressure synoptic conditions that were characterized by the lowest visibility ( 104 cm–3 with highly elevated SO2 levels, even during the night. When air masses move rapidly from northeastern China to Gosan under strong wind conditions, the Ca2+ concentration, along with that of Cl– and Na+, is enhanced in PM1.0, which is attributed to the influence of saline transport from dry lakes. The results of this study reveal compositional details and information on both number and mass concentration for different PM1.0 plumes from anthropogenic and natural sources, all of which are associated with different kinds of Chinese outflow events.

Decabromodiphenyl ether (BDE209) has been widely used as a flame retardant in the past four decades, leading to human health consequences, especially neurological impairments. Our previous in vivo studies have suggested that developmental neurotoxicity in offspring may be the result of BDE209-induced placental type III iodothyronine deiodinase (Dio3) disturbance and consequent thyroid hormone (TH) instability. Dio3 is paternally imprinted gene, and its balanced expression is crucial in directing normal development and growth. In this study, we used placenta-derived cells to investigate how BDE209 affected Dio3 expression through interfering imprinting mechanisms in the delta-like homolog 1 (Dlk1)-Dio3 imprinted region. Gene chip analysis and RT-qPCR identified miR409-3p, miR410-5p, miR494-3p, miR668-3p and miR889-5p as potential candidates involved in Dio3 deregulation. The sodium bisulfite-clonal sequencing revealed the BDE209 affect methylation status of two differentially methylated regions (DMRs), intergenic-DMR (IG-DMR) and maternally expressed gene 3-DMR (MEG3-DMR). Our data indicate that placental Dio3 may be a potential molecular target for future study of BDE209 developmental toxicity. In particular, miRNAs, IG-DMR and MEG3-DMR in the Dlk1-Dio3 imprinted locus may be informative in directing studies in TH disturbance and developmental toxicity induced by in utero exposure to environmental persistent organic pollutants (POPs), and those candidate miRNAs may prove to be convenient and noninvasive biomarkers for future large-scale population studies.

Measuring isotopic ratios in aerosol particles is a powerful tool for identifying major sources, particularly in separating fossil from non-fossil sources and investigating aerosol formation processes. We measured the radiocarbon, stable carbon, and stable nitrogen isotopic composition of PM2.5 in Beijing (BJ) and Changdao (CD) in the North China Plain (NCP) from May to mid-June 2016. The mean PM2.5 concentrations were 48.6 ± 28.2 μg m−3 and 71.2 ± 29.0 μg m−3 in BJ and CD, respectively, with a high contribution (∼66%) from secondary inorganic aerosol (SIA; NO3−, NH4+, and SO42−). The mean δ13C of total carbon (TC) and δ15N of total nitrogen (TN) values differed significantly between the two sites (p-value of

The North China Plain (NCP) is the most heavily polluted region in China and the explosive growth (EG) events of PM2.5 frequently occur in winter in this region. A campaign from 17 Nov. 2018 to 1 Mar. 2019 was conducted at a rural site in NCP. EG events of PM2.5 were defined as the dynamic increase in PM2.5 concentration by 100 μg/m3 within half day. The intensity of EG events were then graded by the time cost, i.e. 3, 6 and 9 h. EG events with a total number of 120 were identified during the study. Mean growth rates and corresponding standard deviations of PM2.5 of 3 h-, 6 h- and 9 h-EG events were 43.4 ± 6.9, 19.3 ± 1.8 and 12.5 ± 0.5 μg/m3/h, respectively. All of them except one 3 h-EG event occurred with windspeed lower than 2 m/s. Based on the evolution of hourly chemical composition of PM2.5, the EG events were investigated on their formation mechanism. The average mass fraction ratios of SNA (sulphate, SO42−; nitrate, NO3−; ammonium, NH4+) in PM2.5 were 26.3%/18.7%, 32.6%/18.0% and 33.6%/26.9% in 3 h-, 6 h- and 9 h-EG events in the daytime/nighttime, respectively. About two thirds of EG events occurred in the nighttime with a significant increase in the concentrations of organic matter (OM) and chloride (Cl−), which is attributable to nocturnal primary emissions such as coal combustion. In addition, CO-scaled growth rate was calculated as chemical growth rate, the results indicate that OM was the dominant components in EG events.

The measurement of volatile organic compounds (VOCs) was carried out using an online GC-FID/MS at a rural site in North China Plain from 1 Nov. 2017 to 21 Jan. 2018. Their concentrations, emission ratios and source apportionment are investigated. During the entire experiment period, the average mixing ratio of VOCs was 69.5 ± 51.9 ppb, among which alkanes contributed the most (37% on average). Eight sources were identified in the non-negative matrix factorization (NMF) model as short-chain alkanes (13.3%), biomass burning (4.6%), solvent (10.8%), industry (3.7%), coal combustion (41.1%), background (4.5%), vehicular emission (7.7%) and secondary formation (14.2%). In addition to the formation of OVOCs through photochemical reactions, the primary sources, such as coal combustion, biomass burning, vehicular emission, solvent and industry, can also contribute to OVOCs emissions. High OVOCs emission ratios thus were observed at Wangdu site. Primary emission was estimated to contribute 50%, 45%, 73%, 77%, 40%, and 29% on average to acrolein, acetone, methylvinylketone (MVK), methylethylketone (MEK), methacrolein and n-hexanal according to NMF analysis, respectively, which was well consistent with the contribution from photochemical age method. Secondary organic aerosol formation potential (SOAFP) was evaluated by SOA yield, which was significantly higher under low-NOx condition (13.4 μg m−3 ppm−1) than that under high-NOx condition (3.2 μg m−3 ppm−1). Moreover, the photochemical reactivity and sources of VOCs showed differences in seven observed pollution episodes. Among, the largest OH loss rate and SOAFP were found in severe pollution plumes, which were induced primarily by coal combustion. Therefore, mitigation strategies for severe pollution formation should focus on reducing coal combustion emitted VOCs that lead to SOA formation.