Xinfeng Wang

Polluted dust promotes new particle formation and growth

Understanding new particle formation and their subsequent growth in the troposphere has a critical impact on our ability to predict atmospheric composition and global climate change. High pre-existing particle loadings have been thought to suppress the formation of new atmospheric aerosol particles due to high condensation and coagulation sinks. Here, based on field measurements at a mountain site in South China, we report, for the first time, in situ observational evidence on new particle formation and growth in remote ambient atmosphere during heavy dust episodes mixed with anthropogenic pollution. Both the formation and growth rates of particles in the diameter range 15–50 nm were enhanced during the dust episodes, indicating the influence of photo-induced, dust surface-mediated reactions and resulting condensable vapor production. This study provides unique in situ observations of heterogeneous photochemical processes inducing new particle formation and growth in the real atmosphere, and suggests an unexpected impact of mineral dust on climate and atmospheric chemistry.

Radiative absorption enhancement from coatings on black carbon aerosols.

The radiative absorption enhancement of ambient black carbon (BC), by light-refractive coatings of atmospheric aerosols, constitutes a large uncertainty in estimates of climate forcing. The direct measurements of radiative absorption enhancement require the experimentally-removing the coating materials in ambient BC-containing aerosols, which remains a challenge. Here, the absorption enhancement of the BC core by non-absorbing aerosol coatings was quantified using a two-step removal of both inorganic and organic matter coatings of ambient aerosols. The mass absorption cross-section (MAC) of decoated/pure atmospheric BC aerosols of 4.4±0.8m(2)g(-1) was enhanced to 9.6±1.8m(2)g(-1) at 678-nm wavelength for ambiently-coated BC aerosols at a rural Northern China site. The enhancement of MAC (EMAC) rises from 1.4±0.3 in fresh combustion emissions to ~3 for aged ambient China aerosols. The three-week high-intensity campaign observed an average EMAC of 2.25±0.55, and sulfates were primary drivers of the enhanced BC absorption.

Impacts of firecracker burning on aerosol chemical characteristics and human health risk levels during the Chinese New Year Celebration in Jinan, China

Measurements for size distribution and chemical components (including water-soluble ions, OC/EC and trace elements) of particles were taken in Jinan, China, during the 2008 Chinese New Year (CNY) to assess the impacts of firecracker burning on aerosol chemical characteristics and human health risk levels. On the eve of the CNY, the widespread burning of firecrackers had a clear contribution to the number concentration of small accumulation mode particles (100-500 nm) and PM2.5 mass concentration, with a maximum PM2.5 concentration of 464.02 μg/m(3). The firecracker activities altered the number size distribution of particles, but had no influence on the mass size distribution of major water-soluble ions. The concentrations of aerosol and most ions peaked in the rush hour of firecracker burning, whereas the peaks of NO3(-) and NH4(+) presented on the day following the burning of firecrackers. K(+), SO4(2-) and Cl(-) composed approximately 62% of the PM2.5 mass, and they existed as KCl and K2SO4 during the firecracker period. However, during the non-firecracker period, organic matter (OM), SO4(2-), NO3(-) and NH4(+) were the major chemical components of the PM2.5, and major ions were primarily observed as (NH4)2SO4 and NH4NO3. Estimates of non-carcinogenic risk levels to human health showed that the elemental risk levels during the firecracker period were substantially higher than those observed during the non-firecracker period. The total elemental risk levels in Jinan for the three groups (aged 2-6 years, 6-12 years and ≥70 years) were higher than 2 during the firecracker period, indicating that increased pollutant levels emitted from the burning of firecrackers over short periods of time may cause non-carcinogenic human health risks.

A conceptual framework for mixing structures in individual aerosol particles

This study investigated the particle size- and age-dependent mixing structure of individual particles in clean and polluted air. Aerosols were classified into eight components: sea salt, mineral dust, fly ash, metal, soot, sulfates, nitrates, and organic matter (OM). Based on our aerosol classification, a particle that consists of two or more aerosol components can be defined as an internally mixed particle. Otherwise, it is considered to be an externally mixed particle. Within the internally-mixed particle class, we identified four heterogeneous mixing structures: core-shell, dumbbell, OM-coating, and dispersed-OM, as well as one homogeneous-like mixing structure. Homogeneous-like mixing mainly occurred in fine particles (<1 µm), while the frequency of heterogeneously mixed particles increased with particle size. Our study demonstrated that particle mixing structures depend on particle size and location, and evolve with time. OM-coating and core-shell structures are important indicators for particle aging in air as long as they are distant from specific emission sources. Long-range transported particles tended to have core-shell and OM-coating structures. We found that secondary aerosol components (e.g., sulfates, nitrates, and organics) determined particle mixing structures, because their phases change following particle hydration and dehydration under different relative humidities. Once externally mixed particles are transformed into internally mixed particles, they cannot revert to their former state, except when semi-volatile aerosol components are involved. Categorizing mixing structures of individual particles is essential for studying their optical and hygroscopic properties and for tracing the development of their physical or chemical properties over time.

Evaluating PM2.5 ionic components and source apportionment in Jinan, China from 2004 to 2008 using trajectory statistical methods

The mass concentrations and major chemical components of PM(2.5) in Jinan, Shandong Province, China from Dec. 2004 to Oct. 2008 were analyzed using backward trajectory cluster analysis in conjunction with the potential source contribution function (PSCF) model. The aim of this work was to study the inter-annual variations of mass concentrations and major chemical components of PM(2.5), evaluate the air mass flow patterns and identify the potential local and regional source areas that contributed to secondary sulfate and nitrate in PM(2.5) in Jinan. The annual mean concentrations of PM(2.5), sulfate and nitrate in 2004-2008 were almost the highest in the world. The most significant air parcels contributing to the highest mean concentrations of mass and secondary ions in PM(2.5) originated from the industrialized areas of Shandong Province. Clusters with a lower ratio of NO(3)(-)/SO(4)(2-) in PM(2.5) originated from the Yellow Sea, while a higher ratio was observed in the clusters passing through Beijing and Tianjin. PSCF modeling indicated that the provinces of Shandong, Henan, Jiangsu, Anhui and the Yellow Sea were the major potential source regions for sulfate, in agreement with the cluster analysis results. Regional and long-range transport of NH(4)NO(3) played an important role in the nitrate concentration of Jinan. By comparing the distributions of secondary sulfate and nitrate over three years, enhanced emission control management before and during the 29(th) Olympic Games led to a discernible decrease in source contributions from Beijing and its environs in 2007-2008.

Aerosol ionic components at Mt. Heng in central southern China: Abundances, size distribution, and impacts of long-range transport

Water-soluble ions in PM(2.5) were continuously measured, along with the measurements of many other species and collection of size-resolved aerosol samples, at the summit of Mt. Heng in the spring of 2009, to understand the sources of aerosols in rural central southern China. The mean concentrations of SO(4)(2-), NH(4)(+) and NO(3)(-) in PM(2.5) were 8.02, 2.94 and 1.47 μg/m(3), indicating a moderate aerosol pollution level at Mt. Heng. Water-soluble ions composed approximately 40% of the PM(2.5) mass on average. PM(2.5) was weakly acidic with about 66% of the samples being acidic. SO(4)(2-), NO(3)(-) and NH(4)(+) exhibited similar diurnal patterns with a broad afternoon maximum. SO(4)(2-) and NH(4)(+) were mainly present in the fine aerosols with a peak in the droplet mode of 0.56-1 μm, suggesting the important role of cloud processing in the formation of aerosol sulfate. NO(3)(-) was largely distributed in the coarse particles with a predominant peak in the size-bin of 3.2-5.6 μm. Long-distance transport of processed air masses, dust aerosols, and cloud/fog processes were the major factors determining the variations of fine aerosol at Mt. Heng. The results at Mt. Heng were compared with those obtained from our previous study at Mt. Tai in north China. The comparison revealed large differences in the aerosol characteristics and processes between southern and northern China. Backward trajectories indicated extensive transport of anthropogenic pollution from the coastal regions of eastern/northern China and the Pearl River Delta (PRD) to Mt. Heng in spring, highlighting the need for regionally coordinated control measures for the secondary pollutants.

On the use of an explicit chemical mechanism to dissect peroxy acetyl nitrate formation

Peroxy acetyl nitrate (PAN) is a key component of photochemical smog and plays an important role in atmospheric chemistry. Though it has been known that PAN is produced via reactions of nitrogen oxides (NOx) with some volatile organic compounds (VOCs), it is difficult to quantify the contributions of individual precursor species. Here we use an explicit photochemical model--Master Chemical Mechanism (MCM) model--to dissect PAN formation and identify principal precursors, by analyzing measurements made in Beijing in summer 2008. PAN production was sensitive to both NOx and VOCs. Isoprene was the predominant VOC precursor at suburb with biogenic impact, whilst anthropogenic hydrocarbons dominated at downtown. PAN production was attributable to a relatively small class of compounds including NOx, xylenes, trimethylbenzenes, trans/cis-2-butenes, toluene, and propene. MCM can advance understanding of PAN photochemistry to a species level, and provide more relevant recommendations for mitigating photochemical pollution in large cities.

Characteristics of carbonaceous aerosols: Impact of biomass burning and secondary formation in summertime in a rural area of the North China Plain

To determine the characteristics of carbonaceous aerosols in rural areas of the North China Plain, field measurements were conducted at Yucheng (YC) in the summers of 2013 and 2014. The concentrations of carbonaceous aerosols at YC exhibited clear diurnal variation, with higher concentrations in the early morning and at night and lower concentrations during the afternoon hours. The mass-balance method designed for particulate matter smaller than 2.5μm (PM2.5) was used to calculate the organic matter (OM)/organic carbon (OC) ratio. The value obtained, 2.07±0.05, was suggested as a reference to estimate organics in PM2.5 in rural areas of the North China Plain. Biomass burning was identified to be a significant source of carbonaceous aerosols; approximately half of the samples obtained at YC were affected by biomass burning during summer 2013. Case studies revealed that biomass burning accounted for up to 52.6% of the OC and 51.1% of the elemental carbon in PM2.5 samples. The organic coatings observed on sulphur-rich and potassium-rich particles indicated the formation of secondary organic aerosols (SOA) from the oxidation of precursor volatile organic compounds (VOCs) during the aging of smoke released from biomass burning. Based on the evolution of the VOCs, the contribution of VOCs oxidation to SOA concentration was 3.21 and 1.07μgm(-3)ppm(-1) CO under conditions of low nitrogen oxide (NOx) and high NOx, respectively. Aromatics (e.g. benzene, toluene, xylene and ethylbenzene) made the greatest contribution to SOA concentration (88.4% in low-NOx conditions and 80.6% in high-NOx conditions). The results of the study offer novel insights into the effects of biomass burning on the carbonaceous aerosols and SOA formation in polluted rural areas.

Levels, indoor-outdoor relationships and exposure risks of airborne particle-associated perchlorate and chlorate in two urban areas in Eastern Asia.

Indoor and outdoor concentrations of PM2.5-associated perchlorate (ClO4(-)) and chlorate (ClO3(-)) were investigated in Jinan, China, and size-resolved perchlorate and chlorate were studied in Kumamoto, Japan. The average outdoor PM2.5-associated concentrations of perchlorate and chlorate were 4.18 ng m(-3) and 2.82 ng m(-3), respectively, in Jinan. Perchlorate and chlorate were mainly distributed in fine particles, and their approximate PM2.5-associated concentrations were 0.04 ng m(-3) and 4.14 ng m(-3), respectively, in Kumamoto. The ratios of ClO3(-)/ClO4(-) ranged from 18.72 to 360.22 in Kumamoto and from 0.03 to 7.45 in Jinan. The highest concentration of perchlorate (173.76 ng m(-3)) was observed on Spring Festival Eve. This finding and the significant correlation between perchlorate and fireworks-related components (Cl(-) and K(+)) indicated that the fireworks display was a significant source of perchlorate in Jinan. The indoor concentrations of perchlorate and chlorate in Jinan were 3.54 ng m(-3) (range, 0.14-125.14 ng m(-3)) and 0.94 ng m(-3) (range, 0.10-1.80 ng m(-3)), respectively. In the absence of an indoor source of perchlorate, the occurrence of indoor concentrations higher than those found outdoors was a common effect of individual fireworks displays near the sampling sites, coupled with meteorological influences and poor indoor diffusion conditions. The exposure risks of perchlorate and chlorate indoors indicated that the potential risk of perchlorate exposure to children during fireworks displays is deserving of concern.

Size distributions of aerosol sulfates and nitrates in Beijing during the 2008 Olympic Games: Impacts of pollution control measures and regional transport

For the 2008 Olympic Games, drastic control measures were implemented on industrial and urban emissions of sulfur dioxide (SO2), nitrogen oxides (NOx) and other pollutants to address the issues of poor air quality in Beijing. To investigate the effects of SO2 and NOx reductions on the particulate sulfate and nitrate concentrations as well as their size distributions, size-segregated aerosol samples were collected using micro-orifice uniform deposit impactors (MOUDIs) at urban and downwind rural sites in Beijing before and after full-scale controls. During the sampling period, the mass concentrations of fine particles (PM1.8) at the urban and rural sites were 94.0 and 85.9 μg m−3, respectively. More than 90% of the sulfates and ∼60% of nitrates formed as fine particles. Benefiting from the advantageous meteorological conditions and the source controls, sulfates were observed in rather low concentrations and primarily in condensation mode during the Olympics. The effects of the control measures were separately analyzed for the northerly and the southerly air-mass-dominated days to account for any bias. After the control measures were implemented, PM, sulfates, and nitrates were significantly reduced when the northerly air masses prevailed, with a higher percentage of reduction in larger particles. The droplet mode particles, which dominated the sulfates and nitrates before the controls were implemented, were remarkably reduced in mass concentration after the control measures were implemented. Nevertheless, when the polluted southerly air masses prevailed, the local source control measures in Beijing did not effectively reduce the ambient sulfate concentration due to the enormous regional contribution from the North China Plain.