X.P. Lyu

Ambient volatile organic compounds and their effect on ozone production in Wuhan, central China

Ambient volatile organic compounds (VOCs) were continuously measured from February 2013 to October 2014 at an urban site in Wuhan. The characteristics and sources of VOCs and their effect on ozone (O3) formation were studied for the first time. The total VOC levels in Wuhan were relatively low, and of all VOCs, ethane (5.2 ± 0.2 ppbv) was the species with the highest levels. Six sources, i.e., vehicular exhausts, coal burning, liquefied petroleum gas (LPG) usage, the petrochemical industry, solvent usage in dry cleaning/degreasing, and solvent usage in coating/paints were identified, and their contributions to the total VOCs were 27.8 ± 0.9%, 21.8 ± 0.8%, 19.8 ± 0.9%, 14.4 ± 0.9%, 8.5 ± 0.5%, and 7.7 ± 0.4%, respectively. Model simulation of a photochemical box model incorporating the Master Chemical Mechanism (PBM-MCM) indicated that the contribution to O3 formation of the above sources was 23.4 ± 1.3%, 22.2 ± 1.2%, 23.1 ± 1.7%, 11.8 ± 0.9%, 5.2 ± 0.4%, and 14.2 ± 1.1%, respectively. LPG and solvent usage in coating/paints were the sources that showed higher contributions to O3 formation, compared to their contributions to VOCs. The relative incremental reactivity (RIR) analysis revealed that the O3 formation in Wuhan was generally VOC-limited, and ethene and toluene were the primary species contributing to O3 production, accounting for 34.3% and 31.5% of the total RIR-weighted concentration, respectively. In addition, the contribution of CO to the O3 formation was remarkable. The C4 alkanes and alkenes from the LPG usage also significantly contributed to the O3 formation. The results can assist local governments in formulating and implementing control strategies for photochemical pollution.

Tropospheric volatile organic compounds in China

Photochemical smog, characterized by high concentrations of ozone (O3) and fine particles (PM2.5) in the atmosphere, has become one of the top environmental concerns in China. Volatile organic compounds (VOCs), one of the key precursors of O3 and secondary organic aerosol (SOA) (an important component of PM2.5), have a critical influence on atmospheric chemistry and subsequently affect regional and global climate. Thus, VOCs have been extensively studied in many cities and regions in China, especially in the North China Plain, the Yangtze River Delta and the Pearl River Delta regions where photochemical smog pollution has become increasingly worse over recent decades. This paper reviews the main studies conducted in China on the characteristics and sources of VOCs, their relationship with O3 and SOA, and their removal technology. This paper also provides an integrated literature review on the formulation and implementation of effective control strategies of VOCs and photochemical smog, as well as suggestions for future directions of VOCs study in China.

Spatiotemporal variation of ozone precursors and ozone formation in Hong Kong: Grid field measurement and modelling study

Grid field measurements of volatile organic compounds (VOCs) covering the entire territory of Hong Kong were simultaneously carried out twice daily on 27 September 2013 and 24 September 2014, respectively, to advance our understanding on the spatiotemporal variations of VOCs and ozone (O3) formation, the factors controlling O3 formation and the efficacy of a control measure in Hong Kong. From before to after the control measure on liquefied petroleum gas (LPG) fueled vehicles, the VOCs originated from LPG vehicle exhaust deceased from 41.3±1.2μg/m(3) (49.7±1.5%) to 32.8±1.4μg/m(3) (38.8±1.7%) (p<0.05). In contrast, the contribution to VOCs made by gasoline and diesel vehicle exhaust and solvent usage increased (p<0.05). VOCs and nitric oxide (NO) in LPG source experienced the highest reductions at the roadside sites, while the variations were not significant at the urban and new town sites (p>0.05). For O3 production, LPG vehicle exhaust generally made a negative contribution (-0.17±0.06 ppbv) at the roadside sites, however it turned to a slightly positive contribution (0.004±0.038 ppbv) after the control measure. At the urban sites, although the reductions of VOCs and NO were minor (p>0.05), O3 produced by LPG vehicle significantly reduced from 4.19±1.92 ppbv to 0.95±0.38 ppbv (p<0.05). Meanwhile, O3 produced by LPG at the new town sites remained stable. The analysis of O3-precursor relationships revealed that alkenes and aromatics were the main species limiting roadside O3 formation, while aromatics were the most predominant controlling factor at urban and new town sites. In contrast, isoprene and sometimes NOx limited the O3 formation in rural environment.

Causes of ozone pollution in summer in Wuhan, Central China.

In August 2016, continuous measurements of volatile organic compounds (VOCs) and trace gases were conducted at an urban site in Wuhan. Four high-ozone (O3) days and twenty-seven non-high-O3 days were identified according to the Chinas National Standard Level II (∼100 ppbv). The occurrence of high-O3 days was accompanied by tropical cyclones. Much higher concentrations of VOCs and carbon monoxide (CO) were observed on the high-O3 days (p < 0.01). Model simulations revealed that vehicle exhausts were the dominant sources of VOCs, contributing 45.4 ± 5.2% and 37.3 ± 2.9% during high-O3 and non-high-O3 days, respectively. Both vehicle exhausts and stationary combustion made significantly larger contributions to O3 production on high-O3 days (p < 0.01). Analysis using a chemical transport model found that local photochemical formation accounted for 74.7 ± 5.8% of the daytime O3, around twice the regional transport (32.2 ± 5.4%), while the nighttime O3 was mainly attributable to regional transport (59.1 ± 9.9%). The local O3 formation was generally limited by VOCs in urban Wuhan. To effectively control O3 pollution, the reduction ratio of VOCs to NOx concentrations should not be lower than 0.73, and the most efficient O3 abatement could be achieved by reducing VOCs from vehicle exhausts. This study contributes to the worldwide database of O3-VOC-NOx sensitivity research. Its findings will be helpful in formulating and implementing emission control strategies for dealing with O3 pollution in Wuhan.

Observation of SOA tracers at a mountainous site in Hong Kong: Chemical characteristics, origins and implication on particle growth

Secondary organic aerosol (SOA) is an important constituent of airborne fine particles. PM2.5 (particles with aerodynamic diameters≤2.5μm) samples were collected at a mountainous site in Hong Kong in autumn of 2010, and analyzed for SOA tracers. Results indicated that the concentrations of isoprene SOA tracers (54.7±22.7ng/m3) and aromatics SOA tracers (2.1±1.6ng/m3) were on relatively high levels in Hong Kong. Secondary organic carbon (SOC) derived from isoprene, monoterpenes, sesquiterpenes and aromatics was estimated with the SOA tracer based approach, which constituted 0.35±0.15μg/m3 (40.6±5.7%), 0.20±0.03μg/m3 (30.4±5.5%), 0.05±0.02μg/m3 (5.6±1.7%) and 0.26±0.20μg/m3 (21.3±8.2%) of the total estimated SOC. Biogenic SOC (0.60±0.18μg/m3) dominated over anthropogenic SOC (0.26±0.20μg/m3) at this site. In addition to the total estimated SOC (17.8±4.6% of organic carbon (OC) in PM2.5), primary organic carbon (POC) emitted from biomass burning also accounted for a considerable proportion of OC (11.6±3.2%). Insight into the OC origins found that regional transport significantly (p<0.05) elevated SOC from 0.37±0.17 to 1.04±0.39μg/m3. Besides, SOC load could also increase significantly if there was influence from local ship emission. Biomass burning related POC in regional air masses (0.81±0.24μg/m3) was also higher (p<0.05) than that in samples affected by local air (0.29±0.35μg/m3). Evidences indicated that SOA formation was closely related to new particle formation and the growth of nucleation mode particles, while biomass burning was responsible for some particle burst events in Hong Kong. This is the first SOA study in afforested areas of Hong Kong.

Modeling C1–C4 Alkyl Nitrate Photochemistry and Their Impacts on O3 Production in Urban and Suburban Environments of Hong Kong

Author(s): Lyu, XP; Guo, H; Wang, N; Simpson, IJ; Cheng, HR; Zeng, LW; Saunders, SM; Lam, SHM; Meinardi, S; Blake, DR | Abstract: ©2017. American Geophysical Union. All Rights Reserved. As intermediate products of photochemical reactions, alkyl nitrates (RONO2) regulate ozone (O3) formation. In this study, a photochemical box model incorporating master chemical mechanism well reproduced the observed RONO2 at an urban and a mountainous site, with index of agreement in the range of 0.66–0.73. The value 0.0003 was identified to be the most appropriate branching ratio for C1 RONO2, with the error less than 50%. Although levels of the parent hydrocarbons and nitric oxide (NO) were significantly higher at the urban site than the mountainous site, the production of C2–C3 RONO2 was comparable to or even lower than at the mountainous site, due to the lower concentrations of oxidative radicals in the urban environment. Based on the profiles of air pollutants at the mountainous site, the formation of C2–C4 RONO2 was limited by NOx (volatile organic compounds (VOCs)) when total volatile organic compounds (TVOCs)/NOx was higher (lower) than 10.0 ± 0.4 parts per billion by volume (ppbv)/ppbv. This dividing ratio decreased (p l 0.05) to 8.7 ± 0.4 ppbv/ppbv at the urban site, mainly due to the different air pollutant profiles at the two sites. For the formation of C1 RONO2, the NOx-limited regime extended the ratio of TVOCs/NOx to as low as 2.4 ± 0.2 and 3.1 ± 0.1 ppbv/ppbv at the mountainous and urban site, respectively. RONO2 formation led to a decrease of simulated O3, with reduction efficiencies (O3 reduction/RONO2 production) of 4–5 parts per trillion by volume (pptv)/pptv at the mountainous site and 3–4 pptv/pptv at the urban site. On the other hand, the variations of simulated O3 induced by RONO2 degradation depended upon the regimes controlling O3 formation and the relative abundances of TVOCs and NOx.