Liuju Zhong

Speciated VOC emission inventory and spatial patterns of ozone formation potential in the Pearl River Delta, China.

The Pearl River Delta region (PRD) of China has long suffered from severe ground-level ozone pollution. Knowledge of the sources of volatile organic compounds (VOCs) is essential for ozone chemistry. In this work, a speciated VOC emission inventory was established on the basis of updated emissions and local VOC source profiles. The top 10 species, in terms of ozone formation potentials (OFPs), consisted of isoprene, mp-xylene, toluene, ethylene, propene, o-xylene, 1,2,4-trimethylbenzene, 2-methyl-2-butene, 1-butene, and alpha-pinene. These species contributed only 35.9% to VOCs emissions but accounted for 64.1% of the OFP in the region. The spatial patterns of the VOC source inventory agreed well with city-based source apportionment results, especially for vehicle emissions and industry plus VOC product-related emissions. Mapping of the OFPs and measured ozone concentrations indicated that the formation of higher ozone in the south and southeast of the PRD region differed from that in the Conghua area, a remote area in the north of the PRD. We recommend that the priorities for the control of VOC sources include motorcycles, gasoline vehicles, and solvent use because of their larger OFP contributions.

Ground-level ozone in the Pearl River Delta and the roles of VOC and NOx in its production

In many regions of China, very rapid economic growth has been accompanied by air pollution caused by vehicle emissions. In one of these regions, the Pearl River Delta, the variations of ground-level ozone and its precursors were investigated. Overall, the ambient concentrations of NO(2) increased quickly between 1995 and 1996, but then slightly decreased due to stringent nitrogen oxide (NO(x)) emission controls. Nonetheless, ambient NO(2) levels in the Pearl River Delta remained high. The regional average concentrations of volatile organic compounds (VOCs) were 290 ppbC in summer and 190 ppbC in autumn. Local emissions and long-distance transportation of pollutants play important roles in the regional distribution of VOCs. Ambient O(3) production is significant in urban areas and also downwind of cities. The relative incremental reactivities (RIRs), determined by an observation-based model, showed that ground-level ozone formation in the Guangzhou urban area is generally limited by the concentrations of VOCs, but there are also measurable impacts of NO(x).

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.

Speciated OVOC and VOC emission inventories and their implications for reactivity-based ozone control strategy in the Pearl River Delta region, China

The increasing ground-ozone (O3) levels, accompanied by decreasing SO2, NO2, PM10 and PM2.5 concentrations benefited from air pollution control measures implemented in recent years, initiated a serious challenge to control Volatile Organic Compound (VOC) emissions in the Pearl River Delta (PRD) region, China. Speciated VOC emission inventory is fundamental for estimating Ozone Formation Potentials (OFPs) to identify key reactive VOC species and sources in order to formulate efficient O3 control strategies. With the use of the latest bulk VOC emission inventory and local source profiles, this study developed the PRD regional speciated Oxygenated Volatile Organic Compound (OVOC) and VOC emission inventories to identify the key emission-based and OFP-based VOC sources and species. Results showed that: (1) Methyl alcohol, acetone and ethyl acetate were the major constituents in the OVOC emissions from industrial solvents, household solvents, architectural paints and biogenic sources; (2) from the emission-based perspective, aromatics, alkanes, OVOCs and alkenes made up 39.2%, 28.2%, 15.9% and 10.9% of anthropogenic VOCs; (3) from the OFP-based perspective, aromatics and alkenes become predominant with contributions of 59.4% and 25.8% respectively; (4) ethene, m/p-xylene, toluene, 1,2,4-trimethyl benzene and other 24 high OFP-contributing species were the key reactive species that contributed to 52% of anthropogenic emissions and up to 80% of OFPs; and (5) industrial solvents, industrial process, gasoline vehicles and motorcycles were major emission sources of these key reactive species. Policy implications for O3 control strategy were discussed. The OFP cap was proposed to regulate VOC control policies in the PRD region due to its flexibility in reducing the overall OFP of VOC emission sources in practice.

Source apportionment of PM2.5 at urban and suburban areas of the Pearl River Delta region, south China - With emphasis on ship emissions

Daily PM2.5 samples were collected at an urban site in Guangzhou in 2014 and at a suburban site in Zhuhai in 2014-2015. Samples were subject to chemical analysis for various chemical components including organic carbon (OC), element carbon (EC), major water-soluble inorganic ions, and trace elements. The annual average PM2.5 mass concentration was 48±22μgm-3and 45±25μgm-3 in Guangzhou and Zhuhai, respectively, with the highest seasonal average concentration in winter and the lowest in summer at both sites. Regional transport of pollutants accompanied with different air mass origins arriving at the two sites and pollution sources in between the two cities caused larger seasonal variations in Zhuhai (>a factor of 3.5) than in Guangzhou (<a factor of 2.0). Positive matrix factorization (PMF) analysis identified six and five major source factors for PM2.5 in Guangzhou and Zhuhai, respectively. Ship emissions, a source factor previously ignored in making emission control policies in the Pearl River Delta region of south China, were among the top contributors to PM2.5 at both sites, accounting for >17% of PM2.5 mass concentrations.

Organosulfates from Pinene and Isoprene over the Pearl River Delta, South China: Seasonal Variation and Implication in Formation Mechanisms

Biogenic organosulfates (OSs) are important markers of secondary organic aerosol (SOA) formation involving cross reactions of biogenic precursors (terpenoids) with anthropogenic pollutants. Until now, there has been rare information about biogenic OSs in the air of highly polluted areas. In this study, fine particle (PM2.5) samples were separately collected in daytime and nighttime from summer to fall 2010 at a site in the central Pearl River Delta (PRD), South China. Pinene-derived nitrooxy-organosulfates (pNOSs) and isoprene-derived OSs (iOSs) were quantified using a liquid chromatograph (LC) coupled with a tandem mass spectrometer (MS/MS) operated in negative electrospray ionization (ESI) mode. The pNOSs with MW 295 exhibited higher levels in fall (151 ± 86.9 ng m(-3)) than summer (52.4 ± 34.0 ng m(-3)), probably owing to the elevated levels of NOx and sulfate in fall when air masses mainly passed through city clusters in the PRD and biomass burning was enhanced. In contrast to observations elsewhere where higher levels occurred at nighttime, pNOS levels in the PRD were higher during the daytime in both seasons, indicating that pNOS formation was likely driven by photochemistry over the PRD. This conclusion is supported by several lines of evidence: the specific pNOS which could be formed through both daytime photochemistry and nighttime NO3 chemistry exhibited no day-night variation in abundance relative to other pNOS isomers; the production of the hydroxynitrate that is the key precursor for this specific pNOS was found to be significant through photochemistry but negligible through NO3 chemistry based on the mechanisms in the Master Chemical Mechanism (MCM). For iOSs, 2-methyltetrol sulfate ester which could be formed from isoprene-derived epoxydiols (IEPOX) under low-NOx conditions showed low concentrations (below the detection limit to 2.09 ng m(-3)), largely due to the depression of IEPOX formation by the high NOx levels over the PRD.

Fast increasing of surface ozone concentrations in Pearl River Delta characterized by a regional air quality monitoring network during 2006–2011

Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone (O3), NO2 and total oxidant (O(x)) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3 concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3 increase is accompanied by a correspondingly fast NO(x) reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories--rural stations (non-urban) and suburban/urban stations. The O3 concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime (13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3 production is mainly volatile organic compounds (VOC)-controlled. However, the photochemical O3 production is sensitive to both NO(x) and VOC for O3 pollution episode. Accordingly, it is expected that a combined NO(x) and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.

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.

Road-Network-Based Spatial Allocation of On-Road Mobile Source Emissions in the Pearl River Delta Region, China, and Comparisons with Population-Based Approach

Abstract Gridded air pollutant emission inventories are prerequisites for using air quality models to assess air pollution control strategies and predict air quality. A precise gridded emission inventory will help improve the accuracy of air quality simulation. Mobile source emissions are one of the major contributors to volatile organic compound (VOC) and nitrogen oxide (NOx) pollutants, the precursors of ozone formation. However, because of the complexity of road networks and variations in traffic flows at different road types and locations, spatial allocation of emissions from mobile sources into grid cells is challenging. This paper proposes a new methodological framework, named as “the road-network-based approach,” for spatially allocating regional mobile source emission inventories. The new approach utilizes the Geographic Information System (GIS)-based road network information and road-types-based traffic flow data to provide spatial surrogates for allocating Pearl River Delta (PRD) regional mobile source emission inventories. The results show that the new approach provides reasonable spatial distributions of mobile source emissions, and the distributions are in good agreement with PRD regional on-road emission line sources. Comparisons between using the population-based and the new road-network-based approaches are made. The air quality modeling results indicate that the new approach can obviously improve model predictions with increasing accuracy in mobile source emission allocations. Means of choosing appropriate approaches for spatially allocating regional mobile source emissions are discussed.

Ambient CFCs and HCFC‐22 observed concurrently at 84 sites in the Pearl River Delta region during the 2008–2009 grid studies

Air samples were collected concurrently at 05:00 A.M. and 10:00 A.M. local Beijing time (geomagnetic time + 8) at 84 sites during two grid-study campaigns on 29 September 2008 and 1 March 2009 in the Pearl River Delta region, in order to offer snapshots of ambient CFCs and hydrochlorofluorocarbons (HCFCs) in different seasons and to indicate the presence of local emission sources. Compared to the subtropical northern hemisphere background levels, mean mixing ratios of CFC-11, CFC-12, CFC-113, CFC-114, and HCFC-22 were enhanced by 7%–11%, 8%–11%, 5%–6%, 8%–9%, and 71%–135%, respectively. When data from this tudy were pooled together with previous observations in the region, ambient CFC-11, CFC-12, and CFC-113 unambiguously showed declines in mixing ratios, while HCFC-22 showed an increase. Spatial variations revealed potential emission hot spots in the region, and levels of CFCs and HCFC-22 were higher in September than in March due to many more refrigeration and air-conditioning activities during summer. Source apportioning by positive matrix factorization revealed that new input of CFCs and HCFC-22 into the ambient air was largely attributed to emission from air-conditioning and refrigerating activities instead of industry activities. Average emissions in the region estimated by the CO-tracer method were 0.8 ± 0.2, 1.4 ± 0.6, 0.2 ± 0.1, 0.1 ± 0.02, and 4.4 ± 1.0 Gg/yr for CFC-11, CFC-12, CFC-113, CFC-114, and HCFC-22, respectively, and they accounted for 5.5%–25.5% of the total estimated CFC and HCFC-22 emissions in China.