Zibing Yuan

Source apportionment of ambient volatile organic compounds in Hong Kong.

Volatile organic compounds (VOCs) were measured at four stations with different environments in Hong Kong (HK) during two sampling campaigns. Positive matrix factorization was applied to characterize major VOC sources in HK. Nine sources were identified, and the spatial and seasonal variations of their contributions were derived. The most significant local VOC sources are vehicle and marine vessel exhausts or liquefied petroleum gas (LPG) at different stations. Vehicle- and marine vessel-related sources accounted for 2.9-12.7ppbv in 2002-2003 and increased to 4.3-15.2ppbv in 2006-2007. Different from the emission inventory, solvent-related sources only contributed 11- 19% at both sampling campaigns. Therefore, emission control from transport sector should be prioritized to alleviate ambient local VOC levels. Additionally, the contribution of aged VOC, which roughly represents contributions from regional and super-regional transport, also showed moderate increase during the four years, indicating cooperation with environmental authorities in the Pearl River Delta and beyond should be strengthened. All the anthropogenic sources contribute most to Yuen Long and least to Tap Mun. However, Tap Mun exhibited different trends in comparison with the other three stations, especially for sources of vehicle and marine vessel exhausts, LPG and paint solvents. When the local source contributions were incorporated with wind data to derive the directional dependences of sources, we may conclude that the rapid development of Yantian Container Terminal, the associated emissions from marine vessels around the Terminal and the on-site activities were likely responsible for the distinct VOC features at Tap Mun. The current impact from the Terminal is mainly concentrated in the northeastern corner of HK; however, it has the potential threat to other locations if the Terminal continues to expand in such a rapid speed in the coming years. More stringent VOC control measures on activities related to the operation of the Terminal is therefore highly recommended.

Source analysis of volatile organic compounds by positive matrix factorization in urban and rural environments in Beijing

[1] This paper applies advance receptor model positive matrix factorization (PMF) source analysis to 1-h resolution VOC data collected at Yufa (rural site) and Peking University, or PKU (urban site), in Beijing. A range of major VOC sources was identified, including vehicle emissions, liquefied petroleum gas, coal combustion, and biogenic emissions. Vehicle activities contributed approximately 62% of VOC loading and 55% of ozone forming potential at the PKU site, compared to 38% of VOC loading and 42% of ozone forming potential at Yufa. These results indicate that the control of vehicle emissions is essential to alleviating VOC pollution, particularly in urban Beijing. We found that VOC emission strengths are relatively consistent throughout the day in the rural area; variation of mixing height therefore is a controlling factor for ground-level VOC concentration. In the urban area, both vehicle activity and variation of mixing height strongly impact VOC levels. Local sources within Beijing appeared to contribute most of the VOCs recorded at both urban and rural areas. However, as some of the VOC species are quite reactive, VOC emitted from distant sources would have been depleted during transportation, concurrent with the formation of secondary pollutants such as ozone and sulfate. Such depletion would mean that this source apportionment analysis would tend to overestimate the ozone forming capacity of local VOC sources compared to emissions from distant sources. Nevertheless, this study illustrates that high-resolution VOC measurements, especially those with a sampling frequency on the scale of less than 1 day, combined with PMF, can make a strong contribution to our understanding of pollutant emissions and transport characteristics and is a useful tool with which to formulate effective pollution control strategies.

VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China

Abstract Ambient air measurements of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) were conducted and characterised during a two-year grid study in the Pearl River Delta (PRD) region of southern China. The present grid study pioneered the systematic investigation of the nature and characteristics of complex VOC and OVOC sources at a regional scale. The largest contributing VOCs, accounting over 80% of the total VOCs mixing ratio, were toluene, ethane, ethyne, propane, ethene, butane, benzene, pentane, ethylbenzene, and xylenes. Sub-regional VOC spatial characteristics were identified, namely: i) relatively fresh pollutants, consistent with elevated vehicular and industrial activities, around the PRD estuary; and ii) a concentration gradient with higher mixing ratios of VOCs in the west as compared with the eastern part of PRD. Based on alkyl nitrate aging determination, a high hydroxyl radical (OH) concentration favoured fast hydrocarbon reactions and formation of locally produced ozone. The photochemical reactivity analysis showed aromatic hydrocarbons and alkenes together consisted of around 80% of the ozone formation potential (OFP) among the key VOCs. We also found that the OFP from OVOCs should not be neglected since their OFP contribution was more than one-third of that from VOCs alone. These findings support the choice of current air pollution control policy which focuses on vehicular sources but warrants further controls. Industrial emissions and VOCs emitted by solvents should be the next targets for ground-level ozone abatement.

Sulfate Formation Enhanced by a Cocktail of High NOx, SO2, Particulate Matter, and Droplet pH during Haze-Fog Events in Megacities in China: An Observation-Based Modeling Investigation

In recent years in a few Chinese megacities, fog events lasting one to a few days have been frequently associated with high levels of aerosol loading characterized by high sulfate (as high as 30 μg m(-3)), therefore termed as haze-fog events. The concomitant pollution characteristics include high gas-phase mixing ratios of SO2 (up to 71 ppbv) and NO2 (up to 69 ppbv), high aqueous phase pH (5-6), and smaller fog droplets (as low as 2 μm), resulting from intense emissions from fossil fuel combustion and construction activities supplying abundant Ca(2+). In this work, we use an observation-based model for secondary inorganic aerosols (OBM-SIA) to simulate sulfate formation pathways under conditions of haze-fog events encountered in Chinese megacities. The OBM analysis has identified, at a typical haze-fogwater pH of 5.6, the most important pathway to be oxidation of S(IV) by dissolved NO2, followed by the heterogeneous reaction of SO2 on the aerosol surface. The aqueous phase oxidation of S(IV) by H2O2 is a very minor formation pathway as a result of the high NOx conditions suppressing H2O2 formation. The model results indicate that the unique cocktail of high fogwater pH, high concentrations of NO2, SO2, and PM, and small fog droplets are capable of greatly enhancing sulfate formation. Such haze-fog conditions could lead to rapid sulfate production at night and subsequently high PM2.5 in the morning when the fog evaporates. Sulfate formation is simulated to be highly sensitive to fogwater pH, PM, and precursor gases NO2 and SO2. Such insights on major contributing factors imply that reduction of road dust and NOx emissions could lessen PM2.5 loadings in Chinese megacities during fog events.

A comparison of HYSPLIT backward trajectories generated from two GDAS datasets.

The Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model is widely used to generate backward trajectories in given starting locations. However, differences exist between trajectories generated from the model with different input datasets. In this study, backward trajectories in Hong Kong in the entire year of 2011 are derived by HYSPLIT model. Two sets of Global Data Assimilation System (GDAS) output data associated with different horizontal and vertical resolutions (GDAS1 and GDAS0P5) are used as drivers in an attempt to quantify the differences between the results and discover the underlying reasons responsible for discrepancy. The results reveal that the significant differences between back trajectories generated from the two GDAS datasets can be mainly attributed to different vertical velocity calculation methods due to the absence of vertical velocity in GDAS0P5 dataset. The HYSPLIT trajectories are also sensitive to the horizontal and vertical resolutions of the input meteorological data, but to lesser extents. Results of cluster analysis indicate that when the air mass is from the north, northeast, or west with a long-to-medium range, the HYSPLIT backward trajectories are sensitive to the vertical advection calculation method and data resolution, whereas when the air mass is from the south or southwest with a long range, the trajectories are more likely to remain unchanged with the shifting of vertical velocity or data resolution. By comparing the vertical velocities with the observations and the performance in retrieving PM contributions from different directions, we conclude that GDAS1 dataset is more plausible in backward trajectory analysis in the Pearl River Delta.

Insights into factors affecting nitrate in PM2.5 in a polluted high NOx environment through hourly observations and size distribution measurements

Nitrate, a major PM2.5 component in polluted environments, could be greatly elevated during pollution episodes. In this study, nitrate and other inorganic ions on PM2.5 were measured half hourly at a residential location in Hong Kong in December 2009. Hourly nitrate concentrations in PM2.5 varied from 0.8 to 40.5 µg m−3. In an episode during which hourly visibility was down to 3.7 ± 1.0 km and NO2 was 80.7 ± 14.4 ppb, PM2.5 NO3− reached 27.8 ± 8.0 µg m−3, ~6 times the level during the normal hours. Nitrate was fully balanced by NH4+, indicating abundant presence of NH3. Size-segregated measurements showed 84% of nitrate was in the fine mode during the episode and also suggested that less acidic fine particles and less abundant sea-salt particles were the contributing factors to the dominant presence in the fine mode. An observation-based model for secondary inorganic aerosols was applied to investigate the relative importance of homogeneous and heterogeneous reactions to production of NO3− potential (sum of HNO3 (g) and aerosol nitrate). The modeling analysis shows that both formation pathways were significantly more active during the episode. Gas phase production of HNO3 through reaction of NO2 + OH dominated during the initial rapid buildup of nitrate around noon time, but the heterogeneous N2O5 hydrolysis pathway made a sizable contribution in the subsequent few hours due to sustained high-NO2 concentrations combined with reduced photolysis loss of N2O5. This case study illustrates the important role of NH3 and NO2 in elevating PM2.5 in a high-NOx environment through the formation of nitrate.

A refined 2010-based VOC emission inventory and its improvement on modeling regional ozone in the Pearl River Delta Region, China.

Accurate and gridded VOC emission inventories are important for improving regional air quality model performance. In this study, a four-level VOC emission source categorization system was proposed. A 2010-based gridded Pearl River Delta (PRD) regional VOC emission inventory was developed with more comprehensive source coverage, latest emission factors, and updated activity data. The total anthropogenic VOC emission was estimated to be about 117.4 × 10(4)t, in which on-road mobile source shared the largest contribution, followed by industrial solvent use and industrial processes sources. Among the industrial solvent use source, furniture manufacturing and shoemaking were major VOC emission contributors. The spatial surrogates of VOC emission were updated for major VOC sources such as industrial sectors and gas stations. Subsector-based temporal characteristics were investigated and their temporal variations were characterized. The impacts of updated VOC emission estimates and spatial surrogates were evaluated by modeling O₃ concentration in the PRD region in the July and October of 2010, respectively. The results indicated that both updated emission estimates and spatial allocations can effectively reduce model bias on O₃ simulation. Further efforts should be made on the refinement of source classification, comprehensive collection of activity data, and spatial-temporal surrogates in order to reduce uncertainty in emission inventory and improve model performance.

Ambient Ozone Control in a Photochemically Active Region: Short-Term Despiking or Long-Term Attainment?

China has made significant progress decreasing the ambient concentrations of most air pollutants, but ozone (O3) is an exception. O3 mixing ratios during pollution episodes are far higher than the national standard in the Pearl River Delta (PRD), thus greater evidence-based control efforts are needed for O3 attainment. By using a validated O3 modeling system and the latest regional emission inventory, this study illustrates that control strategies for short-term O3 despiking and long-term attainment in the PRD may be contradictory. VOC-focused controls are more efficient for O3 despiking in urban and industrial areas, but significant NOx emission reductions and a subsequent transition to a NOx-limited regime are required for O3 attainment. By tracking O3 changes along the entire path toward long-term attainment, this study recommends to put a greater focus on NOx emission controls region-wide. Parallel VOC reductions around the Nansha port are necessary in summertime and should be extended to the urban and industrial areas in fall with a flexibility to be strengthened on days forecasted to have elevated O3. Contingent VOC-focused controls on top of regular NOx-focused controls would lay the groundwork for striking a balance between short-term despiking and long-term attainment of O3 concentrations in the PRD.

Characterization of Secondary Aerosol and its Extinction Effects on Visibility over the Pearl River Delta Region, China

Aerosol samples collected from July 2007 to March 2008 were used to obtain major aerosol constituents in an urban location in the Pearl River Delta Region (PRD), China. The minimum organic carbon (OC)/elemental carbon (EC) ratio was used to calculate the primary and secondary organic carbon and the extinction effect of the secondary aerosol on visibility was estimated. As indicated in the analysis, the mass of secondary aerosol takes up 50% of the total mass of PM2.5; the OC/EC ratio is larger than 2 and there are significant characteristics of secondary aerosol generation; the levels of secondary OC are comparable with those of sulfate; and there is obvious enrichment of secondary aerosol on more polluted days. In a dry environment, the extinction weight is 59% for the secondary aerosol, while it is as high as 82% if the environment is highly humid (relative humidity [RH] = 95%). The hygroscopic growth of the aerosol can reduce visibility greatly; the secondary aerosol shares much larger quotas on more polluted days. For the Pearl River Delta (PRD), secondary aerosol and carbonaceous aerosol, especially secondary organic carbon (SOC), are a very acute problem; the study of the generating mechanism and sources for secondary aerosol is the key to the effort of controlling visibility in this region. The equation set forth in IMPROVE experiments can only be referenced but is not applicable to evaluate the extinction effect of individual aerosol components on visibility in the PRD region. Implications: The extinction effects on visibility by different constituents are studied in this work using compositional data derived from the measurements, with special efforts on examining the extinction of secondary aerosol and the enrichment and extinction contributions of the constituents with the variation of pollution level and relative humidity, so as to provide a scientific basis for the mitigation of atmospheric aerosol pollution and improving visibility in the PRD of China.

A New Combined Stepwise-Based High-Order Decoupled Direct and Reduced-Form Method To Improve Uncertainty Analysis in PM2.5 Simulations

The traditional reduced-form model (RFM) based on the high-order decoupled direct method (HDDM), is an efficient uncertainty analysis approach for air quality models, but it has large biases in uncertainty propagation due to the limitation of the HDDM in predicting nonlinear responses to large perturbations of model inputs. To overcome the limitation, a new stepwise-based RFM method that combines several sets of local sensitive coefficients under different conditions is proposed. Evaluations reveal that the new RFM improves the prediction of nonlinear responses. The new method is applied to quantify uncertainties in simulated PM2.5 concentrations in the Pearl River Delta (PRD) region of China as a case study. Results show that the average uncertainty range of hourly PM2.5 concentrations is -28% to 57%, which can cover approximately 70% of the observed PM2.5 concentrations, while the traditional RFM underestimates the upper bound of the uncertainty range by 1-6%. Using a variance-based method, the PM2.5 boundary conditions and primary PM2.5 emissions are found to be the two major uncertainty sources in PM2.5 simulations. The new RFM better quantifies the uncertainty range in model simulations and can be applied to improve applications that rely on uncertainty information.