Double-Edged Role of VOCs Reduction in Nitrate Formation: Insights from Observations during the China International Import Expo 2018.

Aerosol nitrate (NO3-) constitutes a significant component of fine particles in China. Prioritizing the control of volatile organic compounds (VOCs) is a crucial step toward achieving clean air, yet its impact on NO3- pollution remains inadequately understood. Here, we examined the role of VOCs in NO3- formation by combining comprehensive field measurements conducted during the China International Import Expo (CIIE) in Shanghai (from 10 October to 22 November 2018) and multiphase chemical modeling. Despite a decline in primary pollutants during the CIIE, NO3- levels increased compared to pre-CIIE and post-CIIE─NO3- concentrations decreased in the daytime (by -10 and -26%) while increasing in the nighttime (by 8 and 30%). Analysis of the observations and backward trajectory indicates that the diurnal variation in NO3- was mainly attributed to local chemistry rather than meteorological conditions. Decreasing VOCs lowered the daytime NO3- production by reducing the hydroxyl radical level, whereas the greater VOCs reduction at night than that in the daytime increased the nitrate radical level, thereby promoting the nocturnal NO3- production. These results reveal the double-edged role of VOCs in NO3- formation, underscoring the need for transferring large VOC-emitting enterprises from the daytime to the nighttime, which should be considered in formulating corresponding policies.

Determination of Urban Formaldehyde Emission Ratios in the Shanghai Megacity.

We analyzed two data sets of atmospheric formaldehyde (FA) at an urban site in the Shanghai megacity during the summer of 2017 and the winter of 2017/18, with the primary objective of determining the emission ratio of formaldehyde versus carbon monoxide (CO). Through the photochemical age method and the minimum R squared (MRS) method, we derived the summer urban formaldehyde release ratios of 3.37 ppbv (ppmv of CO)-1 and 4.04 ppbv (ppmv of CO)-1, respectively. The error of both estimations is within ±20%, indicating the consistency of the results. We recognized the hourly minimum emission ratios determined from the MRS method to be indicative of actual formaldehyde emission ratios. Similarly, the emission ratio in winter is determined to be 2.10 ppbv (ppmv of CO)-1 utilizing the MRS method. The findings provide significant insights into the potential impact of motor vehicle exhaust on formaldehyde emissions in urban areas. This work demonstrates that the formaldehyde emission ratio determined by the MRS method can be used to represent the emissions of the freshest air mass. Formaldehyde photolysis contributed an average of 9% to the free radical primary reaction rate (P(ROx)) as a single chemical species during the daytime in summer, which was lower than the 11% recorded in winter. Formaldehyde emission reduction positively impacts local ozone production, so models describing ozone formation in Shanghai during summer need to reflect these emissions accurately. Evidence of the crucial catalytic role of formaldehyde in particulate matter formation has been confirmed by recent research. A potentially effective way to decrease the incidence of haze days in autumn and winter in the future is therefore to focus on reducing formaldehyde emissions.

Two-year online measurements of volatile organic compounds (VOCs) at four sites in a Chinese city: Significant impact of petrochemical industry.

Volatile organic compounds (VOCs) management has been recently given a high priority in China to mitigate ozone (O3) air pollution. However, there is a relatively poor understanding of VOCs due to their complexity and fewer observations. To better understand the pollution characteristics of VOCs and their impact on O3 pollution, two-year continuous measurements were conducted at four representative sites in Ji'nan, eastern China. These four sites cover urban, background, and industrial areas (within a petroleum refinery). Ambient VOCs showed higher concentrations at industrial site than at urban and background sites, owing to intensive emissions from petrochemical industry. The VOCs compositions present spatial heterogeneity with alkenes dominated in total reactivity at urban and background sites, while alkenes and aromatics together dominated at industrial site. The VOCs emission profile from petrochemical industry was calculated based on observational data, which revealed a huge impact on light alkanes (C2-C5), light alkenes (ethene), and aromatics (toluene and m/p-xylene). The positive matrix factorization (PMF) model analysis further refined the impact of different petrochemical industrial processes. Alkanes and alkenes dominated the emissions during refining process, while aromatics dominated during solvent usage process. Analysis by an observation-based model indicated stronger in-situ O3 production and higher sensitivity to nitrogen oxides at industrial site compared to urban and background sites. The reduction of VOCs emissions from petrochemical industry would significantly reduce the O3 concentrations. The analyses underline the significant impact of petrochemical industry on VOCs and O3 pollution, and provide important reference for the formulation of refined and effective control strategies.

Nitrous acid in the polluted coastal atmosphere of the South China Sea: Ship emissions, budgets, and impacts.

Nitrous acid (HONO) can significantly contribute to hydroxyl radicals (OH) and thus regulate atmospheric oxidation chemistry; however, ambient HONO sources are not well quantified and vary in different environments. In this study, we conducted comprehensive field observations at a coastal site in the South China Sea and performed chemical box modelling to demonstrate contrasting budgets and impacts of diurnal atmospheric HONO derived from the sea, coastline and continent. The ship emission ratio of HONO/nitrogen oxides (NOx) (1.21 ± 0.99%) was calculated from hundreds of night-time fresh plume measurements. Offshore marine air was frequently influenced by ship exhausts, and the sea acted as an HONO sink. Heterogeneous conversions of nitrogen dioxide (NO2) on underlying surfaces and photolysis of adsorbed nitric acid (HNO3(ads)) were the major HONO sources in coastal air, when heterogeneous NO2 conversions on the ground surface and the homogeneous NO + OH reaction dominated HONO formation in continental air. HONO photolysis was a significant source of reactive radicals (ROx = OH + HO2 + RO2) in these air masses. Atmospheric box model including only homogeneous HONO source of the NO + OH reactions significantly underpredicted the OH concentration and atmospheric oxidising capacity in coastal and continental air. This study provides new insights into the complex sources and significant impacts of HONO in the polluted coastal boundary layer.

[Ozone Formation and Key VOCs of a Continuous Summertime O3 Pollution Event in Ji'nan].

In the summer of 2019, field measurements of ozone (O3) and its precursors[volatile organic compounds (VOCs) and nitrogen oxides (NOx)] were carried out at an urban site in Ji'nan. We found that the daily maximum 8-hour averages φ(O3) were (103.0±14.5)×10-9. The average φ(NOx) and φ(VOCs), which are ozone precursors, were (16.7±11.3)×10-9and (22.4±9.4)×10-9, respectively. The ·OH reactivity of VOCs was determined (9.6±3.8) s-1. Ji'nan suffered from serious O3 pollution. An observation-constrained chemical box model was deployed to evaluate in situ photochemical O3 production, which indicated that chemical reactions made positive contributions to O3 production rates between 07:00 and 19:00 LT, with the average hourly O3 production rate of 35.6×10-9 h-1. To evaluate the effectiveness of various ozone precursor control strategies in reducing ozone pollution, we combined the observation-based model (OBM) with the relative incremental reactivity (RIR) method. The key indicators that affect the local ozone production rate were identified. Ji'nan was under VOC-limited conditions and the key VOC precursors were alkenes. The O3 formation mechanism changed from the VOC-limited regime in the morning to the transitional regime in the afternoon. Correspondingly, the simulated local O3 production rate was increased from 18.3×10-9 h-1 to 29.6×10-9 h-1. To further explore the role of anthropogenic emissions in ozone pollution, we used the positive matrix factorization (PMF) model to identify the major sources contributing to VOCs. The major sources in Ji'nan were vehicular exhaust and gasoline evaporation, accounting for more than 50% of the observed VOCs. Therefore, constraints on vehicular emissions is the most effective strategy to control O3 pollution in Ji'nan.

Investigating the sources of atmospheric nitrous acid (HONO) in the megacity of Beijing, China.

Nitrous acid (HONO) can powerfully influence atmospheric photochemistry by producing hydroxyl radical (OH), which is a crucial oxidant that controls the fate of atmospheric trace species. To deduce HONO formation mechanisms in polluted regions, two field observations were conducted in urban Beijing during the early summer of 2017 and the winter of 2018. These two seasons bore distinguishing pollution characteristics with a higher degree of ageing and heavier aerosol loading in the early summer and more abundant NOx (NOx = NO + NO2) in the winter. Elevated concentrations of HONO were observed during these two seasons, with the mean ± standard deviation (maximum) concentrations of 1.25 ± 0.94 (6.69) ppbv and 1.04 ± 1.27 (9.55) ppbv in early summer and winter, respectively. The observed daytime (08:00-17:00 h, local time) HONO production rate was several times higher in early summer than in winter (4.44 ± 1.93 ppbv h-1 vs. 0.88 ± 0.49 ppbv h-1). Budget analysis revealed distinct daytime HONO formation mechanisms during these two seasons. Photo-induced heterogeneous conversion of NO2 on the ground surface dominated in early summer, and homogeneous reaction of NO + OH was dominant in winter. Photolysis of HONO was the major source of primary OH in both seasons, and thus, played a key role in the regulation of atmospheric oxidising capacity. This study demonstrates the significant seasonal variations in HONO budget and underlines the predominant role of HONO in primary OH production in Beijing. Our findings will be helpful to gain an understanding of the chemical mechanisms underlying the formation of secondary pollution in metropolitan areas.

Formation of peroxyacetyl nitrate (PAN) and its impact on ozone production in the coastal atmosphere of Qingdao, North China.

Peroxyacetyl nitrate (PAN), acting as a relatively long-lived reservoir for both NOx and radicals, plays a crucial role in ozone (O3) formation in the troposphere. However, its quantitative impacts on radical concentrations and O3 production were rarely studied in the coastal atmosphere. In this study, ambient concentrations of PAN, O3, and related species were simultaneously measured from October 5 to November 10, 2018 (autumn), and July 14 to August 24, 2019 (summer) at a rural coastal site in Qingdao, North China. The formation mechanism of PAN and its impact on in-situ O3 production were explored with an observation-based chemical box model. Photochemical formation of PAN and O3 was controlled by both NOx and VOCs, and acetaldehyde and methylglyoxal were the main contributors to PAN formation. However, the sensitivities of PAN to precursors were larger than that of O3 in autumn while smaller in summer, which was mainly caused by the rapid decomposition of PAN at high temperatures. Zero-out sensitivity simulation showed that PAN could either promote or inhibit the in-situ O3 formation by affecting the radical chemistry. It tended to suppress O3 production by competing with precursors and terminating radical chain reactions under low-NOx and low-ROx circumstances but enhanced O3 production by supplying RO2 radicals under conditions with sufficient NOx. This study provides some new complementary insights into the formation mechanism of PAN and its impacts on O3 production, and has implications for the formulation of control policy to mitigate regional photochemical pollution in northern China.

[Source Apportionment of Ozone Pollution in Guangzhou: Case Study with the Application of Lagrangian Photochemical Trajectory Model].

A six-day ozone pollution episode in Guangzhou in early October 2018 was analyzed with the application of a Lagrangian photochemical trajectory model to trace the sources of ozone, quantify the contributions of different regions, and evaluate the effects of emission reduction measures targeted at different emission sectors and different precursors on ozone pollution. The results showed that during the ozone pollution episode, the maximum daily 8 h ozone exceeded 160 µg·m-3 and the highest value reached 271 µg·m-3. The average concentrations of nitrogen oxides and volatile organic compounds (VOCs) were (77.7±42.8) µg·m-3 and (71.9±56.2) µg·m-3, respectively. Aromatics and alkenes were the dominant reactive VOCs, with contributions of 38% and 30% to·OH reactivity and 51% and 16% to ozone formation potential, respectively. The ozone pollution in Guangzhou during this episode was affected by three types of air masses, with the primary source regions of Guangzhou, Guangdong Province, and regions outside Guangdong Province. For all three air mass types, ozone production in these source region was controlled by VOCs. Sensitivity tests showed that, in the primary source regions, reducing the emissions of VOCs is more effective than reducing NOx in terms of reducing ozone concentrations. Under the condition of full emission reduction, regulating traffic emissions could substantially reduce ozone levels by 14.6%-21.0% in Guangzhou, which was a more significant reduction than regulating controlled industry (8.4%-15.3%), power plant (0.9%-6.2%) and residential (2.3%-4.7%) emissions. However, the traffic emission reduction is not as effective (induced ozone reduction<10%) when the emissions reduction ratio is lower than 90%. In addition, biogenic emissions in the Pearl River Delta also substantially contributed to the ozone levels under certain circumstances, as indicated by the ozone reduction up to 19% when biogenic emissions were shut off.

Significance of carbonyl compounds to photochemical ozone formation in a coastal city (Shantou) in eastern China.

Carbonyl compounds are ubiquitous in the troposphere, yet their contributions to ambient ozone (O3) formation have rarely been quantified in China. To better understand their roles in O3 pollution, a field campaign was conducted at an urban site of Shantou, a coastal city in eastern China, during 7th-29th October 2019. Seven carbonyls were quantified (average ± standard deviation: 14.42 ± 3.05 ppbv), among which formaldehyde (4.12 ± 1.02 ppbv), acetaldehyde (1.57 ± 0.30 ppbv), acetone (7.55 ± 2.10 ppbv), and methyl ethyl ketone (0.94 ± 0.28 ppbv) were the most abundant species. Relative incremental reactivity (RIR) analysis indicated that O3 formation in Shantou was VOC-limited, specifically most sensitive to carbonyls, and formaldehyde showed the largest RIR values in terms of individual species. Budgets of O3 and ROx (OH, HO2, and RO2) radicals were elucidated with a chemical box model. Carbonyls played a vital role in both the primary formation and recycling of the ROx; more than 80% of the primary source of HO2 and RO2 came from photolysis of formaldehyde and other oxygenated VOCs. Zero-out sensitivity studies showed that the seven measured carbonyls accounted for 37% of the peak net O3 production rate, mainly by affecting the concentrations of HO2 and RO2. These results highlight the significance of carbonyls, especially formaldehyde, to photochemical O3 formation, and carbonyls should be paid more attention to mitigate the worsening O3 pollution in China.

Gas-Particle Partitioning of Carbonyl Compounds in the Ambient Atmosphere.

Despite their crucial roles in health and climate concerns, the gas-particle partitioning of carbonyl compounds is poorly characterized in the ambient atmosphere. In this study, we investigate their partitioning by simultaneously measuring six carbonyl compounds (formaldehyde, acetaldehyde, acetone, propionaldehyde, glyoxal, and methylglyoxal) in the gas and particle phase at an urban site in Beijing. The field-derived partitioning coefficients ( Kpf) are in the range of 10-5-10-3 m3 µg-1, and the corresponding effective Henry's law coefficients ( KHf) should be 107-109 M atm-1. The Pankow's absorptive partitioning theory and Henry's law both significantly underestimate concentrations of particle-phase carbonyl compounds (105-106 times and >103 times, respectively). The observed "salting-in" effects only partially explain the enhanced partitioning to particles, which is approximately 1 order of magnitude. The measured Kpf values are higher at low relative humidity, and the overall effective vapor pressure of these carbonyl species are lower than their hydrates, indicating that carbonyl oligomers potentially formed in highly concentrated particle phase. The reaction kinetics of oligomer formation should be included if applying Henry's law to low-to-moderate relative humidity, and the high partitioning coefficients observed need to be proved by further field and laboratory studies. These findings provide deeper insights into the formation of carbonyl secondary organic aerosols in the ambient atmosphere.

The production of formaldehyde and hydroxyacetone in methacrolein photooxidation: New insights into mechanism and effects of water vapor.

Methacrolein (MACR) is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios (0 to 4.04) and relative humidities (<3% to 80%) using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde (HCHO) were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH3C(CH2)OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NOx level, while lower at high-NOx level. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NOx level is that water vapor promotes the production of methacrolein nitrate in the reaction of HOCH2C(CH3)(OO)CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89×10-18cm3/molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor.

Insight into Generation and Evolution of Sea-Salt Aerosols from Field Measurements in Diversified Marine and Coastal Atmospheres.

This report focuses on studying generation and/or evolution of sea-salt aerosols (SSA) on basis of measurements in the Northwest Pacific Ocean (NWPO), the marginal seas of China, at sea-beach sites and a semi-urban coastal site in 2012-2015. From measurements in the NWPO, we obtained the smallest generation function of the super-micron SSA mass ([MSSA]) by the local wind comparing to those previously reported. Vessel-caused wave-breaking was found to greatly enhance generation of SSA and increase [MSSA], which was subject to non-natural generation of SSA. However, naturally enhanced generation of SSA was indeed observed in the marginal seas and at the sea-beach site. The two enhancement mechanisms may explain the difference among this and previous studies. Size distributions of super-micron SSA exhibited two modes, i.e., 1-2 µm mode and ~5 µm mode. The 1-2 µm mode of SSA was enhanced more and comparable to the ~5 µm mode under the wind speed >7 m/s. However, the smaller mode SSA was largely reduced from open oceans to sea-beach sites with reducing wind speed. The two super-micron modes were comparable again at a semi-urban coastal site, suggesting that the smaller super-micron mode SSA may play more important roles in atmospheres.

[Concentration distribution of metal elements in atmospheric aerosol under different weather conditions in Qingdao Coastal Region].

To know the influence of different weather conditions on the concentration of metal elements in aerosols in the coastal region, total suspended particles (TSP) samples were collected from April to May 2012, and August 2012 to March 2013 in the Qingdao coastal region, and common trace metals were analyzed by using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). The results showed that Al, Ca, Fe, Na, K and Mg were the dominant metal elements in TSP, and the sum of the six elements accounted for 94.2% of the sum of all metals. TSP and metal elements had significant monthly variations, Fe, Al, K, Ca, Mg, Zn, Ba, Mn, Ti, Sr and Li had the highest concentration in November and January, while Be, Sc, Co, Ni and Cr showed the highest value in January. Na had the highest concentration in August, November and February, and the lowest in December. Pb had the highest concentration in January and February, and the lowest in August and December. Enrichment factors indicated that Be, Co, Al, Ca, Fe, K, Mg, Mn, Sr and Ti were mainly affected by natural sources; Li, Cr, Ni, Zn, Ba and Na were affected by natural sources and part of anthropogenic sources; Pb was mainly from anthropogenic sources. Different weather conditions had great impact on TSP and metal elements concentrations, all the measured metals had the highest concentrations in smog except Ti. Compared with the sunny day, the concentration of atmospheric particulate Ti decreased, while the other elements increased by 1 to 4 times in smog. Li, Be, Cr, Ni, Al, Fe, Mg and Mn had little variation in concentration in foggy day, and the concentration of Pb and Na increased considerably. The concentration of Co, Ca and Ti reduced obviously in fog. Except for Cr, Co and Ti, the other elements increased by 1 to 3 times in haze. Most of the elements had the minimal enrichment factors in sunny day, while the other had the maximal enrichment factor in foggy day. Enrichment factors of Ni, Zn, Ba, K, Na, Pb and Sr varied in the order of sunny day < haze day < smog day