Assessing photochemical ozone formation in the Pearl River Delta with a photochemical trajectory model

A photochemical trajectory model (PTM), coupled with the Master Chemical Mechanism (MCM) describing the degradation of 139 volatile organic compounds (VOCs) in the troposphere, was developed and used for the first time to simulate the formation of photochemical pollutants at Wangqingsha (WQS), Guangzhou during photochemical pollution episodes between 12 and 17 November, 2007. The simulated diurnal variations and mixing ratios of ozone were in good agreement with observed data (R2=0.80, P<0.05), indicating that the photochemical trajectory model - an integration of boundary layer trajectories, precursor emissions and chemical processing - provides a reasonable description of ozone formation in the Pearl River Delta (PRD) region. Calculated photochemical ozone creation potential (POCP) indices for the region indicated that alkanes and oxygenated organic compounds had relatively low reactivity, while alkenes and aromatics presented high reactivity, as seen in other airsheds in Europe. Analysis of the emission inventory found that the sum of 60 of the 139 VOC species accounted for 92% of the total POCP-weighted emission. The 60 VOC species include C2-C6 alkenes, C6-C8 aromatics, biogenic VOCs, and so on. The results indicated that regional scale ozone formation in the PRD region can be mainly attributed to a relatively small number of VOC species, namely isoprene, ethene, m-xylene, and toluene, etc. A further investigation of the relative contribution of the main emission source categories to ozone formation suggested that mobile sources were the largest contributor to regional O3 formation (40%), followed by biogenic sources (29%), VOC product-related sources (23%), industry (6%), biomass burning (1%), and power plants (1%). The findings obtained in this study would advance our knowledge of air quality in the PRD region, and provide useful information to local government on effective control of photochemical smog in the region. © 2010 Elsevier Ltd

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

Characterization of volatile organic compounds at a roadside environment in Hong Kong: An investigation of influences after air pollution control strategies

Vehicular emission is one of the important anthropogenic pollution sources for volatile organic compounds (VOCs). Four characterization campaigns were conducted at a representative urban roadside environment in Hong Kong between May 2011 and February 2012. Carbon monoxide (CO) and VOCs including methane (CH4), non-methane hydrocarbons (NMHCs), halocarbons, and alkyl nitrates were quantified. Both mixing ratios and compositions of the target VOCs show ignorable seasonal variations. Except CO, liquefied petroleum gas (LPG) tracers of propane, i-butane and n-butane are the three most abundant VOCs, which increased significantly as compared with the data measured at the same location in 2003. Meanwhile, the mixing ratios of diesel- and gasoline tracers such as ethyne, alkenes, aromatics, halogenated, and nitrated hydrocarbons decreased by at least of 37%. The application of advanced multivariate receptor modeling technique of positive matrix factorization (PMF) evidenced that the LPG fuel consumption is the largest pollution source, accounting for 60 ± 5% of the total quantified VOCs at the roadside location. The sum of ozone formation potential (OFP) for the target VOCs was 300.9 μg-O3 m-3, which was 47% lower than the value of 567.3 μg-O3 m-3 measured in 2003. The utilization of LPG as fuel in public transport (i.e., taxis and mini-buses) contributed 51% of the sum of OFP, significantly higher than the contributions from gasoline- (16%) and diesel-fueled (12%) engine emissions. Our results demonstrated the effectiveness of the switch from diesel to LPG-fueled engine for taxis and mini-buses implemented by the Hong Kong Special Administrative Region (HKSAR) Government between the recent ten years, in additional to the execution of substitution to LPG-fueled engine and restrictions of the vehicular emissions in compliance with the updated European emission standards

Ambient carbon monoxide and the risk of hospitalization due to chronic obstructive pulmonary disease

Data from recent experimental and clinical studies have indicated that lower concentrations of inhaled carbon monoxide might have beneficial antiinflammatory effects. Inhaled carbon monoxide has the potential to be a therapeutic agent for chronic obstructive pulmonary diseases (COPD). However, population-based epidemiologic studies of environmentally relevant carbon monoxide exposure have generated mixed findings. We conducted a time-series study in Hong Kong to estimate the association of short-term exposure to ambient carbon monoxide with emergency hospitalizations for COPD. We collected daily emergency hospital admission data and air pollution data from January 2001 to December 2007. We used log-linear Poisson models to estimate the associations between daily hospital admissions for COPD and the average daily concentrations of carbon monoxide while controlling for the traffic-related copollutants nitrogen dioxide and particulate matter with an aerodynamic diameter less than 2.5 μm. Results showed that ambient carbon monoxide was negatively associated with the risk of hospitalizations for COPD. After adjustment for levels nitrogen dioxide or particulate matter with an aerodynamic diameter less than 2.5 μm, the negative associations of carbon monoxide with COPD hospitalizations became stronger. The risk estimates were similar for female and male subjects. In conclusion, short-term exposure to ambient carbon monoxide was associated with a decreased risk of hospitalization for COPD, which suggests that carbon monoxide exposure provides some acute protection of against exacerbation of COPD.postprin

Role of export industries on ozone pollution and its precursors in China

This study seeks to estimate how global supply chain relocates emissions of tropospheric ozone precursors and its impacts in shaping ozone formation. Here we show that goods produced in China for foreign markets lead to an increase of domestic non-methane volatile organic compounds (NMVOCs) emissions by 3.5 million tons in 2013; about 13% of the national total or, equivalent to half of emissions from European Union. Production for export increases concentration of NMVOCs (including some carcinogenic species) and peak ozone levels by 20–30% and 6–15% respectively, in the coastal areas. It contributes to an estimated 16,889 (3,839–30,663, 95% CI) premature deaths annually combining the effects of NMVOCs and ozone, but could be reduced by nearly 40% by closing the technology gap between China and EU. Export demand also alters the emission ratios between NMVOCs and nitrogen oxides and hence the ozone chemistry in the east and south coast

Species-specified VOC emissions derived from a gridded study in the Pearl River Delta, China

This study provides a top-down approach to establish an emission inventory of volatile organic compounds (VOC) based on ambient measurements, by combining the box model and positive matrix factorization (PMF) model. Species-specified VOC emissions, source contributions, and spatial distributions are determined based on regional-scale gridded measurements between September 2008 to December 2009 in the Pearl River Delta (PRD), China. The most prevalent anthropogenic species in the PRD was toluene estimated by the box model to be annual emissions of 167.8 ± 100.5 Gg, followed by m,p-xylene (68.0 ± 45.0 Gg), i-pentane (49.2 ± 40.0 Gg), ethene (47.6 ± 27.6 Gg), n-butane (47.5 ± 40.7 Gg), and benzene (46.8 ± 29.0 Gg). Alkanes such as propane, i-butane, and n-pentane were 2–8 times higher in box model than emission inventories (EI). Species with fewer emissions were highly variable between EI and box model results. Hotspots of VOC emissions were identified in southwestern PRD and port areas, which were not reflected by bottom-up EI. This suggests more research is needed for VOC emissions in the EI, especially for fuel evaporation, industrial operations and marine vessels. The species-specified top-down method can help improve the quality of these emission inventories

Characteristics of ammonia, acid gases, and PM_2.5 for three typical land-use types in the North China Plain

Air pollution is one of the most serious environmental problems in China due to its rapid economic development alongside a very large consumption of fossil fuel, particularly in the North China Plain (NCP). During the period 2011–2014, we integrated active and passive sampling methods to perform continuous measurements of NH3, HNO3, NO2, and PM2.5 at two urban, one suburban, and two rural sites in the NCP. The annual average concentrations of NH3, NO2, and HNO3 across the five sites were in the ranges 8.5–23.0, 22.2–50.5, and 5.5–9.7 μg m−3, respectively, showing no significant spatial differences for NH3 and HNO3 but significantly higher NO2 concentration at the urban sites. At each site, annual average concentrations of NH3 and NO2 showed increasing and decreasing trends, respectively, while there was no obvious trend in annual HNO3 concentrations. Daily PM2.5 concentrations ranged from 11.8 to 621.0 μg m−3 at the urban site, from 19.8 to 692.9 μg m−3 at the suburban site, and from 23.9 to 754.5 μg m−3 at the two rural sites, with more than 70 % of sampling days exceeding 75 μg m−3. Concentrations of water-soluble ions in PM2.5 ranked differently between the non-rural and rural sites. The three dominant ions were NH4 +, NO3 −, and SO4 2− and mainly existed as (NH4)2SO4, NH4HSO4, and NH4NO3, and their concentrations averaged 48.6 ± 44.9, 41.2 ± 40.8, and 49.6 ± 35.9 μg m−3 at the urban, suburban, and rural sites, respectively. Ion balance calculations indicated that PM2.5 was neutral at the non-rural sites but acidic at the rural sites. Seasonal variations of the gases and aerosols exhibited different patterns, depending on source emission strength and meteorological conditions. Our results suggest that a feasible pathway to control PM2.5 pollution in the NCP should target ammonia and acid gases together

Characteristics of aerosol acidity in Hong kong

The ammonium-to-sulfate ratio ([NH4+]/[SO42-]) and the strong acidity have been generally used as parameters to describe the acidic nature of atmospheric aerosols. However, both parameters do not provide the in situ acidic characteristics of atmospheric aerosols, which are more relevant to the reactivity and the environmental impacts of the aerosols. In this study, the in situ free acid concentrations and the in situ pH of aerosols are investigated to understand the acidic characteristics of atmospheric aerosols in Hong Kong (HK). Over 182 datasets on 24 h Respirable Suspended Particles (RSP) samples collected in 2001 from seven air-quality-monitoring sites run by the Hong Kong Environmental Protection Department are analyzed. Simulations using the Aerosol Inorganic Model (AIM2) reveal that the in situ acidity, i.e., the free acid concentration ([H+](free)), is only a minor fraction (similar to23\%) of the estimated strong acidity in the fine particles because of the presence of bisulfate ions. The acidity characteristics of fine particles are a function of mainly RH and ammonium to sulfate ratio. The in situ free acid concentration, the normalized water content ([H2O](AIM2)/[SO42-]), and the dissociation of bisulfate to free acid in the aerosols decrease as the [NH4+]/[SO42-] ratio increases and the Relative Humidity (RH) decreases. The acidic fine mode particles have average molar [NH4+]/[SO42-] ratio of 1.42, strong acidity of 51 nmol m(-3), in situ acidity of 11 nmol m(-3), and in situ pH of 0.25 on average. Our findings suggest that even the more neutralized ([NH4+]/[SO42-] > 1.5) particles, such as those found when HK is under the influence of continental air masses from the Chinese mainland, can have high in situ acidity and low pH when the RH is low. This study calls for more investigation of the acidity of aerosols in HK, incorporating the concepts of in situ acidity and pH. (C) 2004 Elsevier Ltd. All rights reserved

Abundance and sources of ambient dioxins in Hong Kong: A review of dioxin measurements from 1997 to 2001

Ambient measurements of seventeen 2,3,7,8-polychlorinated dibenzo-p-dioxin/dibenzofuran congeners (2,3,7,8-PCDD/Fs) have been taken in a number of monitoring programs or ad-hoc studies in Hong Kong. The longest monitoring program started at two locations in the territory in July 1997. The other monitoring efforts are ad-hoc studies, varying from a few coordinated sampling events at multiple sites to a year-long monitoring project that targeted suspected local dioxin sources. In this paper, we examined these measurements to understand the ambient levels, temporal and spatial variation, and possible sources of the 2,3,7,8-PCDD/Fs in Hong Kong. The territory-wide annual average concentration of the dioxins was 0.052 pg I-TEQ/m(3) measured at the regular monitoring stations in the most recent annual cycle of 2000/2001. This level fell at the lower end of the range of dioxin concentrations measured at other urban locations around the world. The dioxin levels showed a clear seasonality in that elevated concentrations were observed in the winter and lower concentrations in the summer at all monitoring sites with one year or more regular measurements. The measurements indicated that the few known local dioxin sources, including a major chemical waste incinerator facility, landfill sites, and vehicular traffic, are not important contributors to ambient dioxins in Hong Kong. On days of high dioxin concentrations, the 2,3,7,8-PCDD/F congeners were observed to have almost identical compositions with a north-northwest to south-southeast spatial gradient in concentrations at different sampling locations in Hong Kong. This observation, along with other collaborative evidence, established a strong link between high dioxin concentration days in Hong Kong and regional transport of the polluted air masses from the north. (c) 2005 Elsevier Ltd. All rights reserved