Atmospheric Pollution Research

Characteristics of carbonaceous aerosols in Beijing based on two-year observation

--Manuscript Draft--

Manuscript Number: APR-D-14-00099

Full Title: Characteristics of carbonaceous aerosols in Beijing based on two-year observation

Article Type: Research Paper

Keywords: Organic carbon; Elemental carbon; Carbonaceous aerosol; Beijing

Abstract: Size-segregated aerosol samples were collected over two years (2009-2011) in
Beijing, China. Organic and elemental carbon (OC and EC) concentrations from these
samples were measured to investigate their size distribution patterns, temporal
variations, ratios in particulate matter (PM) and interrelation. The results showed that
both OC and EC concentrations exhibited a bimodal size distribution, with one peak at
the fine mode (0.43-0.65 µm) and the other at the coarse mode (4.7-5.8 µm). The
carbonaceous species were prone to enrich in the fine particles, with 22.5 ± 11.5 and
15.9 ± 5.6 µg m-3 of OC in the fine particles (PM2.1) and the coarse particles
(PM>2.1), and 2.7 ± 1.5 and 1.1 ± 0.7 µg m-3 of EC in PM2.1 and PM>2.1,
respectively. OC and EC accounted for 39.9% and 8.2% of PM mass in < 0.43 μm size
range, respectively. The highest concentrations of carbonaceous species appeared in
winter, which may be mainly attributed to increasing fuel combustion for domestic
heating. It was further supported by the finding that higher concentrations of
carbonaceous species appeared in the heating periods in comparison with the non-
heating periods.

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1 1 Characteristics of carbonaceous aerosols in Beijing based on two-year

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6 3 Zhongjun Xu1*, Tianxue Wen2, Xingru Li3, Jinggang Wang1, Yuesi Wang1,2
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12 5 1.Department of Environmental Science and Engineering, Beijing University of
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6 Chemical Technology, Beijing 100029, China
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17 7 2. State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric
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20 8 Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing
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26 10 3. Department of Chemistry, Analytical and Testing Center, Capital Normal
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28 11 University, Beijing 100048, China
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37 14 *Correspondence to Zhongjun Xu
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39 15 Tel: 0086-10-64427356
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42 16 Fax no.: 0086-10-62082586
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 1 23 Abstract
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24 Size-segregated aerosol samples were collected over two years (2009-2011) in
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6 25 Beijing, China. Organic and elemental carbon (OC and EC) concentrations from these
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12 27 variations, ratios in particulate matter (PM) and interrelation. The results showed that
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28 both OC and EC concentrations exhibited a bimodal size distribution, with one peak
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17 29 at the fine mode (0.43-0.65 µm) and the other at the coarse mode (4.7-5.8 µm). The
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20 30 carbonaceous species were prone to enrich in the fine particles, with 22.5 ± 11.5 and
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23 31 15.9 ± 5.6 µg m-3 of OC in the fine particles (PM2.1) and the coarse particles (PM>2.1),
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26 32 and 2.7 ± 1.5 and 1.1 ± 0.7 µg m-3 of EC in PM2.1 and PM>2.1, respectively. OC and
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28 33 EC accounted for 39.9% and 8.2% of PM mass in < 0.43 μm size range, respectively.
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31 34 The highest concentrations of carbonaceous species appeared in winter, which may be
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34 35 mainly attributed to increasing fuel combustion for domestic heating. It was further
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37 36 supported by the finding that higher concentrations of carbonaceous species appeared
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39 37 in the heating periods in comparison with the non-heating periods.
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42 38 Keywords: Organic carbon; Elemental carbon; Carbonaceous aerosol; Beijing
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 1 45 1. Introduction
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46 In recent years, China suffered from serious air pollution since a large number of
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6 47 fossil fuels were consumed. For example, the coal consumption in China accounted
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9 48 for 50.2% (1873.3 Mtoe) of the global coal consumption in 2012 (BP p. l. c., 2013).
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12 49 Beijing, the capital of China, has more than 20 million inhabitants and 5.2 million
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50 motor vehicles after the industrialization and the urbanization over thirty years.
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17 51 Besides soot from coal combustion, traffic exhaust has been considered as a
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20 52 predominant contributor to particulate matter (PM) in Beijing, although the local
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23 53 government tried with various means to reduce atmospheric pollutants (Zhang, ET
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26 54 AL., 2009). Carbonaceous aerosol is a major component of PM, accounting for 20-50%
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28 55 of atmospheric aerosol in heavy polluted atmosphere in urban areas (Duan et al.,
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31 56 2005). Carbonaceous aerosol is usually classified into organic carbon (OC), a
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34 57 light-scattering faction, and elemental carbon (EC), a light-absorbing faction. OC is a
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37 58 mixture of thousands of organic compounds such as polycyclic aromatic
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39 59 hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and other hazardous
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42 60 components (Duan et al., 2005; Offenberg and Baker, 2000). OC directly emits from
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45 61 the primary polluters, e.g., coal combustion, traffic exhaust and biomass burning, also
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48 62 indirectly forms through gas-to-particle conversion processes of volatile organic
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50 63 compounds (Viidanoja et al., 2002; Niu et al., 2012). EC is also a mixture of
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53 64 graphite-like organic compounds and mainly originates from the incomplete burning
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56 65 of carbonaceous fuels such as fossil and biomass fuels. Carbonaceous aerosol plays an
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59 66 important role in adverse health effects, reduced visibility, climate modulation, and
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 1 67 chemical reaction in the atmosphere (Jacobson, 2001; Menon et al., 2002; Pöschl,
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68 2005; Mauderly and Chow, 2008). Therefore, information on the concentration and
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6 69 the distribution of carbonaceous aerosol in atmosphere is of great interest.
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9 70 Studies on aerosol OC and EC in Beijing have been reported by a large body of
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12 71 literature, which was involved in a change in OC and EC concentrations during one
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72 season (Zhang et al., 2009; Duan et al., 2005), or during several seasons (Yang et l.,
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17 73 2011; Zhao et al., 2013). Few works were focused on carbonaceous faction of
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20 74 size-segregated aerosols in Beijing, although many studies demonstrated size
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23 75 distribution characteristics of aerosol OC and EC worldwide (Gnauk et al., 2008;
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26 76 Saarikoski et al., 2008; Kam et al., 2012; Pio et al., 2013). Based on the reported
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28 77 findings, the mass concentration and size distribution of carbonaceous aerosol both
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31 78 exhibited a significant temporal variation. Therefore, the detailed information on the
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34 79 concentration and the distribution of carbonaceous aerosol in Beijing conduce to
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37 80 developing an effective measure for air pollution control. In this study, we carried out
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39 81 a two-year observation campaign to investigate the temporal variations of OC and EC
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42 82 in atmospheric PM in Beijing. Based on the measurement data in 2009-2011, we
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45 83 summarized the size distributions of EC and OC, the ratios of OC and EC, the
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48 84 relationship between OC and EC, and the mean concentrations of OC and EC in the
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50 85 heating period and the non-heating period.
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53 86 2. Material and methods
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56 87 2.1. Site description
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59 88 Carbonaceous aerosol measurement was conducted at the Institute of Atmospheric
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 1 89 Physics, Chinese Academy of Sciences in Haidian District, Beijing City, China (39º
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90 580´ N, 116º 220´ E). This site is located between the North Third Ring Road and the
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6 91 North Fourth Ring Road. The apparatus used in this study were installed on the roof
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9 92 of a two-story building. Meteorological data on temperature, relative humidity and
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12 93 wind speed were recorded concurrently (Fig. 1).
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17 95 2.2. Aerosol sampling
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20 96 Particle samples were collected using an Andersen sampler (Andersen Series
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23 97 20-800, USA) equipped with quartz fiber filters with 47 mm in diameter at a flow rate
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26 98 of 28.3 L min-1. Particle samples were segregated into 9 size stages by the
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28 99 sampler: >9.0, 9.0-5.8, 5.8-4.7, 4.7-3.3, 3.3-2.1, 2.1-1.1, 1.1-0.65, 0.65-0.43 and <0.43
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31 100 mm. All quartz fiber filters were pre-heated at 450 ºC for 4 h to remove all organic
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34 101 matters and have been conditioned in a constant humidity desiccator (temperature: 25
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37 102 ºC, relative humidity: 50%) for 24 h before weighing. After sampling, the filters were
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39 103 wrapped with aluminum foil and have been also conditioned in the same desiccator
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42 104 for 24 h. After weighing, the filters were stored in a freezer (-20 ºC) prior to
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45 105 carbonaceous faction analysis. The investigation was carried out from September
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48 106 2009 to August 2011 with a sampling frequency of one sample every 2-4 weeks.
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50 107 However, some samples were destroyed during the storage.
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53 108 2.3. Sample analysis
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56 109 The mass concentrations of size-segregated PM were obtained by subtracting the
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59 110 quartz fiber filters before sampling from the corresponding filters after sampling. The
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 1 111 mass of each filter was weighed by a microbalance with a resolution of 1 µg.
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112 OC and EC in aerosol samples were determined by a carbon analyzer (DRI Model
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6 113 2001A, Desert Research Institute, USA) using the thermal optical reflection method.
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9 114 Firstly, a punched piece (0.495 cm2) of a quartz fiber filter containing aerosol sample
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12 115 was heated stepwise up to 120 ºC, 250 ºC, 450 ºC and 550 ºC in a pure helium
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116 atmosphere for OC volatilization. Then the volatilized OC was converted into CO2 via
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17 117 a manganese dioxide (MnO2) catalyst. Subsequently, the residuum of aerosol sample
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20 118 was further heated stepwise up to 550 ºC, 700 ºC and 800 ºC in a 2%
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23 119 oxygen-contained helium atmosphere for EC oxidation to CO2. Finally, the produced
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26 120 CO2 was catalytically converted to CH4 by a MnO2 catalyst, and OC and EC were
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28 121 quantified by measuring the CH4 with a flame ionization detector (FID). The OC–EC
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31 122 split was corrected as the laser transmittance returned to the initial value. The analyzer
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34 123 was calibrated using a standard mixture of CH4 and CO2 before and after sample
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37 124 analysis. One sample was selected at random from every 10 samples to carry out a
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39 125 duplicate sample analysis. The errors in the measurement presented here were less
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42 126 than 10% for TC (OC+EC). Blank filters were also analyzed to check any possible
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45 127 background contamination. Normally, OC and EC concentrations in the blank filters
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48 128 were less than 1% of the sample filters.
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50 129 3. Results and discussion
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53 130 3.1. Temporal variations of OC and EC
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56 131 The temporal variations of OC and EC in the size-segregated aerosols in Beijing
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59 132 from August 2009 to August 2011 are shown in Fig. 2. OC and EC experienced
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 1 133 significant fluctuation during the two-year observation. Overall, OC concentrations in
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134 the fine particles (PM2.1) and the coarse particles (PM>2.1) were on average 22.5 ± 11.5
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6 135 µg m-3 and 15.9 ± 5.6 µg m-3 during the period, respectively. EC concentration in
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9 136 PM2.1 and PM>2.1 were on average 2.7 ± 1.5 µg m-3 and 1.1 ± 0.7 µg m-3 during the
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12 137 period, respectively. The results indicate that more carbonaceous species enriched in
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138 fine particles than in coarse particles. The seasonal average concentrations of OC and
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17 139 EC distributed in PM2.1 and PM>2.1 are illustrated in Fig. 3. During the two-year
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20 140 observation, OC concentrations in PM2.1 followed the order of winter > autumn >
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23 141 summer > spring while no significant difference of OC concentrations in PM>2.1
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26 142 among the four seasons. The highest EC concentrations in PM2.1 and PM>2.1were all in
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28 143 winter. The lowest EC concentration appeared in spring for PM2.1and in summer for
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31 144 PM>2.1during the first-year observation, and in autumn for PM2.1 and PM>2.1during the
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34 145 second-year observation. In addition, there were inter-annual differences in OC and
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37 146 EC concentrations between the two-year observation. The average OC concentration
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39 147 in PM tended to increase between both winters and to decrease slightly between the
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42 148 other seasons, respectively. The average EC concentration in PM showed a systematic
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45 149 increase between the two-year observation. In Beijing, coal consumption dropped by
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48 150 11.2 %, from 26.65 million tons in 2009 to 23.66 million tons in 2011, while the
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50 151 motor vehicle population rose by 23.9%, from 4.02 million in 2009 to 4.98 million in
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53 152 2011 (Beijing Municipal Bureau of Statistics, 2013). Correspondingly, petroleum
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56 153 (gasoline, kerosene and diesel oil) consumption increased by 11.1%, from 9.46
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59 154 million tons in 2009 to 10.51 million tons in 2011 (Beijing Municipal Bureau of
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 1 155 Statistics, 2013). EC emission is closely associated with carbonaceous fuel
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156 combustion. Thus, the increment of EC emission between the two-year observation
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6 157 might be mainly attributed to the vehicular exhaust. Cheng et al. (2013) found that the
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9 158 vehicular emission contributed to 27.0-50.5% of the total EC in PM2.5. Besides, the
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12 159 introduction of carbonaceous pollutants from increasing coal consumption in
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160 neighboring provinces might partly contribute to the increasing EC emission. For
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17 161 example, coal consumption in Hebei increased by 12.4%, from 235.15 million tons in
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20 162 2009 to 264.33 million tons in 2011 (Hebei Provincial Bureau of Statistics, 2013),
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23 163 while coal consumption in Tianjin increased by 27.7%, from 41.20 million tons in
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26 164 2009 to 52.62 million tons in 2011 (Tianjin Municipal Bureau of Statistics, 2013).
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28 165 Similarly, the increasing vehicular exhaust in Beijing and the increasing emission
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31 166 from coal consumption in neighboring provinces may result in a higher OC
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34 167 concentration in the winter of 2010 than in the winter of 2009.
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37 168 Fig. 2
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42 170 The OC and EC concentrations in fine particles peaking in winter in Beijing agreed
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45 171 with the observations in a series of publications (He et al., 2001; Yang et al., 2010;
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48 172 Yang et al., 2011 ). Generally, a mass of coal is used as the fuel for domestic heating
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50 173 in a cold season in North China including Beijing, which leads to a sharp increase in
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53 174 the coal-related carbonaceous emission in this region (Yang et al., 2011). A isotopic
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56 175 signature study found the significant differences of winter vs. summer in δ13C (~1–
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59 176 3 ‰) for OC and EC in seven northern Chinese cities, demonstrating that
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 1 177 carbonaceous PM2.5 in the northern cities of China is strongly impacted by coal
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178 combustion during winter (Cao et al., 2011). Besides, vehicular cold starts also
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6 179 significantly increase emissions of carbonaceous particles and precursors (Singer et al.,
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9 180 1999). On meteorological conditions, a stable atmosphere and low temperatures
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12 181 facilitate the accumulation of air pollutants and accelerate the condensation or
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182 adsorption of VOCs in winter (Yang et al., 2011; Zhao et al., 2013). Similar OC
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17 183 concentrations in PM>2.1 among the four seasons indicated that no obvious effects of
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20 184 the coal combustion for domestic heating and meteorological conditions on OC in
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23 185 coarse particles. This implies that anthropogenic emissions and secondary organic
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26 186 carbon (SOC) mainly contribute to fine particles rather than coarse particles.
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28 187 3.2. Size distributions of OC and EC
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31 188 Fig. 4 shows the mean concentrations of the size-segregated OC and EC based on
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34 189 the two-year observed data. The size distributions of OC and EC were consistent,
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37 190 showing a bimodal pattern with one peak at the fine mode (0.43-0.65 µm) and the
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39 191 other at the coarse mode (4.7-5.8 µm). OC had a smaller presence at the fine peak and
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42 192 a larger presence in the coarse peak while EC had a comparable presence at both the
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45 193 peaks. The size distributions of OC and EC in this study were consistent with those
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48 194 measured in this site during the 2008 Olympics by Li et al. (Li et al., 2012). Generally,
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50 195 EC originates mainly from primary sources while OC originates from both primary
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53 196 and secondary sources. The OC/EC ratio in the fine mode (9.8) was significantly
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56 197 smaller than those in the coarse mode (12.2), indicating that EC in the fine mode is
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59 198 fresh soot particles while EC in the coarse mode is aged with extra OC coating (Yu et
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 1 199 al., 2010).
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200 Fig. 4
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6 201
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12 203 The Size-segregated ratios of OC/PM and EC/PM on the basis of mass are
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204 presented in Fig. 5. The ratios of OC/PM and EC/PM had a similar trend with particle
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17 205 size. The contributions of OC and EC to PM attained 39.9% and 8.2% in < 0.43 μm
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20 206 size range, and intensively dropped to 16.9% and 1.3% in 0.65-1.1 μm size range,
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23 207 respectively. Thereafter, Both the contributions slowly decreased to 8.4% and 0.5% in >
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26 208 9.0 μm size range, respectively. OC includes a variety of hazardous organic materials,
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28 209 e.g., alkanes, PAHs and PCBs (Duan et al., 2005; Offenberg and Baker, 2000; Kong et
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31 210 al., 2010; Mirante et al., 2013). Considering that OC highly contributed to the fine PM
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34 211 (< 1.1 μm) observed in this study, the hazardous organic materials associated with the
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37 212 fine PM are likely to be dispersed to a large area, and easily transport through the
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39 213 upper respiratory tract into the bronchiole and alveoli of the lungs where they pose a
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42 214 direct health risk (Chen et al., 1997). Severe air pollution episodes frequently hit
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45 215 Beijing in recent years, which has urged the local government to implement a series of
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48 216 measures to mitigate the emission of air pollutants, especially NOx and SO2.
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50 217 Considering that PM is reported to be the major air pollutant on about 90% of the
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53 218 days in Beijing (Chan and Yao, 2008) and a high percentage of carbonaceous
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56 219 components appear in PM, the primary and secondary sources of carbonaceous
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59 220 aerosols also need abating to improve air quality.
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 1 221 3.3. OC and EC in heating period and non-heating period
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6 223 Fig. 7
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9 224 The data on OC and EC in the heating period (from mid-November to the following
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12 225 mid-March) and the non-heating period are analyzed to reveal the characteristics of
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226 carbonaceous aerosols. Fig. 6 shows the mean concentrations of the size-segregated
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17 227 OC and EC in heating period and non-heating period, respectively. OC concentration
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20 228 in PM2.1 was significantly higher than the others while EC concentration in PM0.43
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23 229 was significantly higher than the others. OC and EC concentrations tended to decrease
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26 230 with an increase in particle size. In < 2.1 μm size range, OC concentration in the
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28 231 heating period was significantly higher than that in the non-heating period. In > 2.1
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31 232 μm size range, there was no significant difference between OC concentrations in the
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34 233 heating period and the non-heating period. EC concentration in the heating period was
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37 234 systematically higher than that in the non-heating period in all size ranges. Although
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39 235 coal combustion in Beijing deceased year by year, coal combustion for domestic
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42 236 heating lead to the highest monthly coal consumption in Beijing and the neighboring
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45 237 provinces during a heating period. Thus, the local emission and the external transport
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48 238 of carbonaceous aerosols from the neighboring provinces to Beijing result in the
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50 239 highest OC and EC concentrations during a heating period (Yang et al., 2011). Fig. 7
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53 240 presents relationship between OC and EC . Except a significant correlation between
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56 241 OC and EC (R2 = 0.75, P < 0.01) in the fine mode during the heating periods, OC was
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59 242 poorly related to EC. This demonstrates that OC and EC in the fine mode during the
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 1 243 heating periods had one or more co-genetic sources, e.g. vehicle exhaust and coal
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244 combustion (Duan et al., 2005; Li et al, 2012). Except for combustions, various
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6 245 sources contributed to OC in coarse particles, resulting in a weak correlation between
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9 246 OC and EC. Usually, the average values of temperature and light intensity during a
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12 247 non-heating period are much higher compared to a heating period. Thus, a weak
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248 correlation between OC and EC in the fine mode during non-heating periods was due
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17 249 to a mass of SOC originating from high photochemical activity.
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20 250 4. Conclusions
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23 251 The measurement of size-segregated aerosol samples during the two years
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26 252 indicated that the concentrations of carbonaceous species in PM2.1 (ca. 22.5 µg m-3 of
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28 253 OC and 2.7 µg m-3 of EC) were higher than those in PM>2.1 (ca. 15.9 µg m-3 of OC
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31 254 and 1.1 µg m-3 of EC). Especially, OC and EC accounted for 39.9% and 8.2% of PM
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34 255 mass in < 0.43 μm size range, respectively. The seasonal variations of the
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37 256 carbonaceous speies demostrated that the highest concentrations of carbonaceous
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39 257 species appeared in winter in comparison with the other seasons. When one year is
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42 258 divided into a heating period and a non-heating period, higher concentrations of
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45 259 carbonaceous species appeared in both heating periods during the two years. This
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48 260 illustrated that increasing fuel combustion for domestic heating may lead to the more
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50 261 emissions of carbonaceous species in the heating periods, including winter. Based on
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53 262 the two-year observation, OC and EC concentrations both exhibited a bimodal size
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56 263 distribution, with one peak at the fine mode (0.43-0.65 µm) and the other at the coarse
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59 264 mode (4.7-5.8 µm).
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 1 265 Acknowledgements This work was supported by the CAS Strategic Priority
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266 Research Program (No. XDA05100100), National Natural Science Foundation of
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6 267 China (No. 41230642) and the CAS Strategic Priority Research Program (B) (No.
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9 268 XDB05020000). We thank Dr. B. Hu for providing the meteorological data.
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12 269 References
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 1 353 Characteristics of carbonaceous aerosol in the region of Beijing, Tianjin, and Hebei,
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354 China. Atmospheric Environment 71, 389–398.
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6 355 Figure captions
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9 356 Fig. 1. Temperature, relative humidity and wind speed in Beijing from August 2009 to
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12 357 August 2011.
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358 Fig. 2. OC and EC concentrations in the size-segregated aerosols in Beijing during the
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17 359 two-year observation. Particle size displaying in the legend is based on µm.
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20 360 Fig. 3. The seasonal average concentrations of OC and EC distributed in PM2.1 and
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23 361 PM>2.1. Plot a and b denote OC concentration in PM2.1 and PM>2.1, plot c and d denote
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26 362 EC concentration in PM2.1 and PM>2.1, respectively.
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28 363 Fig. 4. The size distributions of EC and OC based on the two-year observed data.
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31 364 Fig. 5. The Size-segregated proportions of EC and OC in PM on the basis of mass.
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34 365 Fig. 6. Size-segregated EC and OC concentrations during the heating period and the
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37 366 non-heating period.
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39 367 Fig. 7. OC related to EC in PM during the heating period and the non-heating period.
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42 368 Plot a and b denote PM2.1 and PM>2.1 in the heating periods, plot c and d denote PM2.1
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45 369 and PM>2.1 in the non-heating periods, respectively.
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Figures
Click here to download Figure: Figures.docx

Fig. 1. Temperature, relative humidity and wind speed in Beijing from August 2009 to

August 2011.
Fig. 2. OC and EC concentrations in the size-segregated aerosols in Beijing during the

two-year observation. Particle size displaying in the legend is based on µm.

Fig. 3. The seasonal average concentrations of OC and EC distributed in PM2.1 and

PM>2.1. Plot a and b denote OC concentration in PM2.1 and PM>2.1, plot c and d denote

EC concentration in PM2.1 and PM>2.1, respectively.

Fig. 4. The size distributions of EC and OC based on the two-year observed data.
Fig. 5. The Size-segregated proportions of EC and OC in PM on the basis of mass.
Fig. 6. Size-segregated EC and OC concentrations during the heating period and the

non-heating period.
Fig. 7. OC related to EC in PM during the heating period and the non-heating period.

Plot a and b denote PM2.1 and PM>2.1 in the heating periods, plot c and d denote PM2.1

and PM>2.1 in the non-heating periods, respectively.