Environmental Pollution 192 (2014) 204e211
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Wide-range particle characterization and elemental concentration in Beijing aerosol during the 2013 Spring Festival Hui Jing a, b, c, Yu-Feng Li a, *, Jiating Zhao a, Bai Li a, Jialong Sun b, Rui Chen d, Yuxi Gao a, Chunying Chen d, * a
CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Multidiscipline Initiative Center, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China Guizhou Academy of Environmental Science and Designing, Guiyang 550081, China c Guizhou Normal University, Guiyang 550001, China d CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, National Center for Nanoscience and Technology, Beijing 100190, China b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 21 April 2014 Received in revised form 3 June 2014 Accepted 6 June 2014 Available online 26 June 2014
The number and mass concentration, size distribution, and the concentration of 16 elements were studied in aerosol samples during the Spring Festival celebrations in 2013 in Beijing, China. Both the number and mass concentration increased sharply in a wide range from 10 nm to 10 mm during the firecrackers and fireworks activities. The prominent increase of the number concentration was in 50 nm e500 nm with a peak of 1.7 105/cm3 at 150 nm, which is 8 times higher than that after 1.5 h. The highest mass concentration was in 320e560 nm, which is 4 times higher than the control. K, Mg, Sr, Ba and Pb increased sharply during the firework activities in PM10. Although the aerosol emission from firework activities is a short-term air quality degradation event, there may be a substantial hazard arising from the chemical composition of the emitted particles. © 2014 Elsevier Ltd. All rights reserved.
Keywords: Firecrackers Fireworks Particle distribution Elemental concentration Spring Festival Beijing
1. Introduction The Spring Festival, falling on the Chinese lunar January 1st, is the most important festival celebrated in China and is when all family members get together, just like Christmas in the West. Burning firecrackers and fireworks is one of the most typical activities during the Spring Festival, which can release gaseous phase pollutants such as sulfur dioxide, nitrogen oxides, ozone and various sized particulate matters with trace metals and organic compounds. These emissions are associated with negative impacts on health and reduced visibility (Attri et al., 2001; Do et al., 2012; Godri et al., 2010; Joly et al., 2010; Li et al., 2009; Moreno et al., 2007; Nishanth et al., 2012; van Kamp et al., 2006; Vecchi et al., 2008; Wang et al., 2007). Several studies found increased releases of particulate matters after firecrackers and firework events. For example, Wehner et al., (2000) reported that the number of submicrometer (Dp > 100 nm) particles increased significantly during the Millennium fireworks
* Corresponding authors. E-mail addresses: [email protected] (Y.-F. Li), [email protected] (C. Chen). http://dx.doi.org/10.1016/j.envpol.2014.06.003 0269-7491/© 2014 Elsevier Ltd. All rights reserved.
€ nkko €nen et al., (2004) studied the particle in Leipzig, Germany. Mo number size distribution in the range from 3 to 800 nm during the Diwali festival in New Delhi, India in 2002 and very high concentrations (>105/cm3) of accumulation mode (100e800 nm) particles were detected. (Zhang et al., 2010) measured the number concentration and size distribution of particles during the Spring Festival celebrations in 2009 in Shanghai, China. It was found that the fireworks activities contributed to the number concentration of particles at 100e500 nm with an hourly average maximum of 2.8 104/cm3 during the peak hour on Spring Festival Eve, which is almost 3 times higher than the average number concentrations measured the day before. The Beijing municipal government has banned the manufacture, sale and setting off firecrackers and fireworks during the Spring Festival since 1993 considering the health, safety and environment concerns. However, due to the pressure from people who desire to follow the old tradition, the local government allowed the setting off firecrackers and fireworks in Spring Festival since 2006. An immediate study on the mass concentrations of PM2.5 and PM10 on Lantern Day in that year was performed and found that they were over six and four times as high as those in the normal day in Beijing,
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Table 1 Meteorological parameters during the 2013 Spring Festival.a Date
Temperature ( C)
Weather conditions Day
Night
Feb.2
Sunny
Light snow
Feb.3
Light snow
Feb.4
State of the wind Night (lowest)
Daytime
Night
2
6
Foggy
0
5
Intermittent winds 3 Winds N at 3e4
Sunny
Light snow
2
7
Intermittent winds 3 Intermittent winds 3 Winds N at 3e4
Feb.8
Sunny
Cloudy
2
9
winds
Feb.9
Cloudy
Cloudy
0
6
Feb.10
Cloudy
Overcast
1
6
Feb.11
Light snow
Light snow
1
6
Feb.12
Sunny
Sunny
2
7
Intermittent winds 3 Intermittent winds 3 Intermittent winds 3 Intermittent winds 3 Winds N at 3e4
a
Day (highest)
Intermittent 3 Intermittent 3 Intermittent 3 Intermittent 3 Intermittent 3 Intermittent 3
winds
winds winds winds winds
http://www.tianqihoubao.com/lishi/beijing/month/201302.html.
respectively (Wang et al., 2007). PM2.5, also called fine particles, is the particulate matter with an aerodynamic diameter of less than 2.5 mm, which can penetrate the respiratory system. PM10, also called inhalable particles, is the particulate matter with an aerodynamic diameter of less than 10 mm. The Lantern Day falls on the Chinese lunar January15th, when fireworks are also set off for celebration. However, to the best of our knowledge, no study on the wide-range particle characterization has yet been performed in ambient air during the Beijing Spring Festival, when much more intense firecrackers and fireworks are set off than on Lantern Day. Firecrackers and fireworks contain various inorganic and organic chemicals, such as charcoal, sulfur, potassium, lead, aluminum, iron and barium nitrate (Steinhauser et al., 2008). Besides the physical characterization of aerosol particles they emitted, the chemical analysis on the trace elements including K, Mg, Sr, Ba and Pb in them revealed significant increase during the firework events in London (Godri et al., 2010), Valencia (Moreno et al., 2007), al (Joly et al., 2010) and Tainan Milan (Vecchi et al., 2008), Montre (Do et al., 2012). Eighteen ions, 20 elements, and black carbon were measured in PM2.5 and PM10 in Beijing on Lantern Day (Wang et al., 2007). Primary components of Ba, K, Sr, Cl, Pb, Mg and secondary 2 2 2 2 components of C5H6O2 4 , C3H2O4 , C2O4 , C4H4O4 , SO4 , NO3 were over five times higher in Lantern Day than in the normal days. Although Li et al., (2009) studied the solvent extractable organic compounds in PM2.5 during 2007 Spring Festival in Beijing, the trace element levels were not studied (Li et al., 2009). In this study, we analyzed the particle number concentration (DP > 10 nm), size distribution (14.6 nm < DP < 10 mm), mass concentration (10 nm < DP < 10 mm) and elemental concentrations in particulate matters during the 2013 Spring Festival's firecrackers and fireworks celebrations in Beijing, China. These measurements were compared to that of before and after firework events, which is served to understand the physical and chemical characteristics of firework particles and their impact to local air quality. 2. Methods 2.1. Sampling site Atmospheric particulate samples were collected on the top of the laboratory building which is about 6 m above ground level at the Institute of High Energy Physics in Beijing (39 54' N, 11615' E), with a horizontal distance of approximately 200 m from one of the firework display areas. Besides, it should be noted that a large
amount of firework displays, firecrackers and sparkles were set off in the whole city throughout the Spring Festival week (9e16 February, 2013), with the main spectacular episode started soon after dinner (around 18:00) on the Spring Festival Eve (9 February, 2013), ended with the high point after midnight (0:00e2:00) on 10 February, 2013. The sampling site is about 2 km from west fourthring road and 4 km from west fifth-ring road, which are the two highways with heavy traffic. There are roughly 300 m from the nearest residential area. 2.2. Real-time sampling The real-time monitoring was carried out from February 8, 2013 to February 12, 2013 (the meteorological parameters were shown in Table 1). Scanning mobility particle sizer (SMPS 3936), optical particle sizer (OPS 3330) and the portable condensation particle counter (CPC 3007) were used to monitor the wide-range particle number concentration and particle size distribution in this study. The SMPS 3936 is consisted of a water-based condensation particle counter (CPC 3788), an electrostatic classifier (EC 3080), and a differential mobility analyzers (DMA 3081). The detection particle size range is 14.6e661.2 nm and the detection concentration range is 1 to 108/cm3. The OPS 3330 can detect particles ranging from 0.3 mm to 10 mm, and the upper limit of number concentration can reach 3000/cm3. The CPC 3007 is used to determine total number concentrations of aerosol particles with size more than 10 nm in the air, and the upper limit of concentration is 105/cm3. SMPS 3936 measures the electrical mobility diameter, whereas OPS 3330 measures the light scattering equivalent diameter, and CPC 3007 measures the aerodynamic diameter. The SMPS 3936 and OPS 3330 collect the data every 2 min, while the CPC 3007 collects the data every 1 s. 2.3. Integrated sampling Micro-orifice uniform-deposit impactor (MOUDI 125B, NanoMoudi-II, MSP Corporation, USA) was used to collect sizefractionated aerosol particle samples from 0.01 mm to 10 mm. The particulate matter is effectively separated into 13 ranges, with nominal cut-point diameter as 10,000, 5600, 3200, 1800, 1000, 560, 320, 180, 100, 56, 32, 18 and 10 nm. We collected the particles before (from 9:00 am February 2nd to 12:00 am February 4th 2013) and during the Spring Festival week (from 9:00 am February 9th to 12:00 am February 11th in 2013) for 50 h, respectively. The
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polycarbonate filter membranes (F47 mm, 0.8 mm, Millipore, USA) were used for the sample collection. Before and after sampling, the filter membranes were put into the temperature & humidity chamber (25 ± 1 C, 45 ± 1%) to balance for 24 h, and then were weighted. The differential method was used to calculate the mass of particles on the filter membranes. 2.4. Elemental analysis Half of the membranes were digested for 4 h at 150 C in highpressure Teflon digestion vessel with 9 mL concentrated HNO3 (BVⅢ grade, Beijing Chemicals) and 3 mL concentrated HF (GR grade, Beijing Chemicals). The solutions were then evaporated using hot plate until only 1 mL was left. Then the digested solutions were diluted to 3 mL with deionized water (resistivity 18.2 MU cm) and centrifuged at 8000 rpm. The supernatants were used for metal analysis including Mg, Ti, V, Co, Cu, Zn, Se, Rb, Sr, Cd, Cs, Ba, Pb by inductively coupled plasma e mass spectrometry (ICP-MS, X7, Thermo Electron, USA) and Na, K, Ca by inductively coupled plasma - optical emission spectrometer (ICP-OES, Optima 8000, PerkinElmer, USA). Each sample was measured three times. The calibration was made using Quality Control Standard 21 (Spex Certiprep, Lot No.: 25-79AS) and reference materials including Rb (12D719), Cs (GSB 04e1724-2004), Ba (GSB 04e1717-2004), Na (GSB 04e1738-2004), K (GSB 04e1733-2004) and Ca (GSB 04e1720-2004) purchased from National Center of Analysis and Testing for Nonferrous Metals and Electronic Materials. Recoveries were analyzed using a soil reference material (GBW-07405 (GSS-5), Chinese Academy of Geophysical and Geochemical Exploration). The recovery of those elements was in the range of 90%e110%. Blank filter values were subtracted from sample determinations. 3. Results and discussion 3.1. Total particle number concentration The total particle number concentration (particles with aerodynamic diameter larger than 10 nm) measured by CPC 3007 before (from 12:00 am February 8th to 05:00 am February 9th, 2013) and on Spring Festival Eve (from 12:00 am February 9th to 05:00 am February 10th, 2013) is shown in Fig. 1. From Fig. 1, it can be seen that the total number concentration began to rise sharply after 00:00 to 00:21 with the peak value of 7.7 104/cm3, which is consistent to the start of intensively setting off of firecrackers and
Fig. 1. Total particle number concentration before and on Spring Festival Eve (Feb.9th, 2013).
fireworks from 00:00 February 10th. Subsequently, the value began to decline, and dropped to 2.9 104/cm3 at 01:00, and went down to the minimum value of 1.1 104/cm3 at 02:00, which is only 1/7 of the peak value. These results indicated that large amount of particles were produced from firecrackers and fireworks activities, which were quickly released to the air and impaired the air quality seriously. On the other side, the particle number could decrease to the background level in only 1.5 h 3.2. Particle number concentration distribution We have used the SMPS 3936 (detection range from 14.6 nm to 661.2 nm) and OPS 3330 (detection range from 0.3 mm to 10 mm) to measure the particle number concentration distribution. Fig. 2 showed the particle size distributions covering 14.6e661.2 nm from 00:00 to 06:00 on February 8th, 10th and 12th, 2013, respectively as determined by SMPS 3936. The number concentration on February 8th decreased with particle size increased, and the highest was at 14.6 nm (the smallest size detectable by SMPS 3936); Particle concentration was relatively low at 14.6 nm on February 10th, and the peak number concentration occurred at 150 nm. Interestingly, trend of particle size distribution on February 12th presented bimodal pattern, whose peaks were roughly at 14.6 nm and 100 nm. On the other hand, the number concentration changes irregularly over time on February 8th and 12th, while on February 10th, it showed significant time variation: the number concentration of each mode particles determined by SMPS 3936 found the peak value at 00:21 at 150 nm. The highest particle number concentration reached 1.7 105/cm3. Subsequently, it began to decrease to stable level at 02:00 until 06:00. These results were consistent with the data as detected by CPC 3007. The particle size distributions determined by OPS 3330 covering 0.3e10 mm at 00:00e06:00 on February 8th, 10th and 12th are shown in Fig. 3. Before, during and after the Spring Festival, there was no obvious difference in the particle size distribution in the range from 300 nm to 10 mm: Larger particles had fewer number concentrations. In addition, the number concentration of particles at 300 nm reached the peak at 00:21 on February 10th, which was similar to the results of CPC 3007 and SPMS 3936. Particles in the size range from 10 nm to 10 mm can be divided into six size groups: Nucleation mode (10 nm < Dp < 20 nm), small Aitken mode (20 nm < Dp < 50 nm), large Aitken mode (50 nm < Dp < 100 nm), small accumulation mode (100 nm < Dp < 500 nm), large accumulation mode (0.5mm < Dp < 1 mm) and coarse mode (1mm < Dp < 10 mm) (Zhang et al., 2010). Smaller particles have a higher surface area-to-mass ratio and deposition efficiency in the alveoli and ultrafine particles can be more toxic than coarse particles of the same mass (Donaldson et al., 1998; € rster et al., 1992). Hughes et al., 1998; Oberdo In this study, the nucleation and Aitken mode particles are dominant before and after the Spring Festival. The most likely reason is a mixture influence of traffic emissions and meteorological conditions (Ferin et al., 1990). However, the number concentration of nucleation and small Aitken mode particles is relatively low on after fireworks display, which can be explained via the concept of the coagulation sink (Agus et al., 2008; Kulmala et al., €nkko € nen et al., 2004; Zhang et al., 2010). Some studies 2001; Mo show that small accumulation mode particles are main dominance in firework celebration, and would be due to primary emissions from the firework activity (Agus et al., 2008; Dutschke et al., 2011; € nkko € nen et al., 2004; Zhang et al., 2010). Dutschke et al., (2011) Mo reported that fireworks were likely to release particles with diameters in the range of 30e450 nm and the maximum value was between 80 and 175 nm in 2011. Our result is similar to Dutschke's. There is a small impact in nucleation, small Aitken, large
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Fig. 2. The particle size distribution (14.6e661.2 nm) at 00:00e6:00 on (a) February 8th, 2013; (b) February 10th, 2013; (c) February 12th, 2013.
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Fig. 3. The particle size distribution (0.3e10 mm) at 00:00e06:00 on (a) February 8th, 2013; (b) February 10th, 2013; (c) February 12th, 2013.
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different sampling time: we collected the air samples for 50 h, while others collected for 12 h. The longer sampling time leads to the decreased average mass concentration. 3.4. Elemental analysis
Fig. 4. Particle mass concentration distribution.
accumulation and coarse mode particles. But the increase of the concentration is apparent in large Aitken mode and small accumulation mode particles, especially when the Dp is about 150 nm. The reasons for these differences may be the discrepancy of the surrounding environment, height, weather and climate conditions etc. of the sampling points. 3.3. Particle mass concentration We chose the data detected from February 2nd to February 4th as control, whose weather conditions were similar to the Spring Festival (from February 9th to February 11th, see Table 1). As shown in Fig. 4, the trend of mass concentration distribution during the Spring Festival was similar to that on the control days, but the mass concentration of particles during the Spring Festival increased compared to the control in each particle size range, and the peak value was at 320e560 nm (40.26 mg/m3), which is 4 times higher than the control. In practice, the particles were generally divided into three size groups when considering mass concentration: PM0.01e0.1 (0.01mm < Dp < 0.1 mm), PM0.1e1.0 (0.1mm < Dp < 1.0 mm) and PM1e10 (1.0mm < Dp < 10 mm). In the present study, the mass concentrations of PM0.01e0.1, PM0.1-1.0 and PM1e10 were 3.79 mg/m3, 72.13 mg/m3, 27.43 mg/m3 during firework activities, which were 2.5, 2.4, 2.9 times higher than the control days, respectively. The mass concentration of PM10 (Dp < 10 mm) on the control days was 41.7 mg/m3, which was less than the mean concentration of PM10 (54 mg/m3) in one clean episode in the winter in Beijing (Hu et al., 2012). On the other hand, the mass concentration of PM10 (103.5 mg/m3) after setting off firecrackers was less than the maximum concentration of PM10 (466.2 mg/m3) detected by Wang et al., (2007) during the Lantern Day (Wang et al., 2007). This concentration was even lower than the maximum prescribed limit (150 mg/m3) of the Chinese national secondary air quality standard. Our data is relatively low compared to other studies and the most likely reason is due to the
The concentrations of various elements in PM10 during the Spring Festival and the control days were shown in Table 2. First of all, there are very sharp peaks for K, Mg, Sr, Ba and Pb during the Spring Festival. The concentration is in the order of K > Mg > Ba > Pb > Sr, which are almost 11, 6, 67, 6 and 25 times higher than those in the control days, respectively. On the other hand, the concentrations of Ti, V, Co, Zn, Rb and Cs see a moderate increase on the firework night, which are about 1.8e3.5 times higher than those in the control days, respectively. In addition, the concentrations of Na, Ca, Cu, Se and Cd are almost unchanged during the Spring Festival and control days. Therefore, K, Mg, Sr, Ba and Pb are the primary components, while Ti, V, Co, Zn, Rb and Cs are the secondary components during the firework event. The primary components found in this study agrees well with the studies by Wang et al. (Wang et al., 2007) and (Godri et al., 2010). In fact, Mg is widely used as a metallic component of firework fuel. Pb can be used to achieve a steady and reproducible burning rate. K, Sr, Ba can radiate purple, red and green colors, respectively (Conkling and Mocella, 2011). Other studies also found the elevation of Na (Wang et al., 2007), Ca (Do et al., 2012; Wang et al., 2007), Cu (Do et al., 2012; Harrison et al., 2000; Hughes € rster et al., 1992), Zn et al., 1998), Ti (Harrison et al., 2000; Oberdo (Do et al., 2012; Wang et al., 2007) during the firework events, but Na, Ca and Cu concentrations was not found changed in this study. The reasons for these differences may be as follows. Firstly, the sampling time is different: this study's sampling times is 50 h, while it is 12 h in Wang's (Wang et al., 2007). Secondly, the surrounding environment, height, weather and climate conditions of the sampling points are different. For instance, both the sampling date in this and Do's are February, but Taiwan belongs to tropical and subtropical climate while Beijing is a typical warm temperate semihumid continental monsoon climate. Therefore, the weather conditions vary widely. Finally, the production compositions of diverse firework manufacturers may be different. Fig. 5 shows the concentration distribution of Ba, K, Mg, Pb, Sr, Ti and Zn from 10 nm to 10 mm during the Spring Festival and the control days. The trend of the concentration distribution of Ba, K, Mg, Pb, Sr and Zn is similar to mass concentration distribution of particulate matters (see Fig. 4) during the Spring Festival. Thus, we think that Ba, K, Mg, Pb, Sr and Zn distribute evenly in various size particulate. Moreover, the concentration distribution of Ba, K, Pb, Sr, Zn were similar with those reported by Do et al. (Do et al., 2012) but they showed decreased Mg concentrations. The correlation of K and other elements (Mg, Sr, Ba, Pb, Zn, Ti) in different size range during the Spring Festival and the control days were tested. K showed notably stronger correlations (N ¼ 13) with Mg (r ¼ 0.96), Sr (r ¼ 0.98), Ba (r ¼ 0.96), Pb (r ¼ 0.86), Zn (r ¼ 0.99) in the Spring Festival than Mg (r2 ¼ 0.07), Sr (r ¼ 0.48), Ba (r2 ¼ 0.09), Pb (r ¼ 0.53), Zn (r ¼ 0.25) in the control days. The correlations with K and Ti are r2 ¼ 0.9 and r ¼ 0.6 respectively during the Spring
Table 2 The concentrations (ng/m3) of various elements in PM10 during the Spring Festival and the control days. Elemental concentration (ng/m3)
Control days Spring Festival Ratio (Spring Festival/Control)
K
Mg
Sr
Ba
Pb
Ti
V
Co
Zn
Rb
Cs
Cd
Ca
Se
Cu
Na
770 8855 11.5
205.9 1284 6.24
9.28 233 25.1
16.1 1079 67.0
47.8 287 6.00
40.3 140 3.48
3.02 5.94 1.97
2.35 4.27 1.82
69.4 128.5 1.85
2.92 7.57 2.59
0.24 0.50 2.08
0.65 0.81 1.24
1915 2011 1.05
1.28 1.86 1.45
117 158 1.35
3548 2312 0.65
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Fig. 5. The distribution of Ba, K, Mg, Pb, Sr, Zn and Ti from 10 nm to 10 mm in the Spring Festival and the control days.
H. Jing et al. / Environmental Pollution 192 (2014) 204e211
Festival and the control days. Therefore, It can be further proved that K, Mg, Sr, Ba, Pb, Zn are largely from the same source, namely, firework, while Ti may not be directly from the firework. 4. Conclusions The total number concentration, mass concentrations, size distribution and elemental concentrations in aerosol particle were measured during the Spring Festival's firecrackers and fireworks events in 2013 in Beijing. This study shows that firework activities increase the number and mass concentrations of each particle size range from 10 nm to 10 mm. Total number concentration in the peak of firework celebrations is approximately 7 times higher than 1.5 h later. The mass concentration of PM10 is 103.5 mg/m3 during the Spring Festival, which is 2.5 times as high as that in control days. The increase of the number concentration is apparent in larger Aitken mode and small accumulation mode particles, especially at about 150 nm. The peak particle number concentration is 1.7 105/ cm3 at 00:21, which is 8 times more than that after 1.5 h in the same diameter. The highest average mass concentration is 40.26 mg/m3, which is 4 times as high as the control in the diameter range of 320e560 nm. The primary components as K, Mg, Sr, Ba and Pb increased sharply during the firework activities and are about 11, 6, 25, 67 and 6 times higher than those in the control days in PM10. Secondary component of Ti, V, Co, Zn, Rb and Cs increased moderately and are about 1.8e3.5 times higher than those in the normal days. The concentration distribution of Ba, K, Mg, Pb, Sr, Zn and mass concentration distribution of particulate is similar during the Spring Festival events with a peak in the range of 320e560 nm. Moreover, through correlations analysis, we think that Ba, K, Mg, Pb, Sr and Zn are largely from firework and evenly distributed in the various size particulate. This study demonstrates that the aerosol emission from firework activities is a short-term air quality degradation event. But primary emissions from firework celebrations significantly change the particle size distribution. And there may be a substantial hazard arising from the chemical composition of the particles. Finally, we suggest people wear a dust mask as far as possible during the firework activities and do not perform outdoor activities in the short term. Acknowledgments Y-F Li gratefully acknowledges the support of K. C. Wong Education Foundation and the Youth Innovation Association, Chinese Academy of Sciences. This work is supported by National Natural Science Foundation of China (11205168, 31070854 and 21277037) and the Ministry of Science and Technology of China (2011CB933401, 2012CB934003 and 2010CB934004). References Agus, E.L., Lingard, J.J., Tomlin, A.S., 2008. Suppression of nucleation mode particles by biomass burning in an urban environment: a case study. J. Environ. Monit. 10, 979e988.
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Attri, A.K., Kumar, U., Jain, V., 2001. Microclimate: formation of ozone by fireworks. Nature 411, 1015. Conkling, J.A., Mocella, C., 2011. Chemistry of Pyrotechnics: Basic Principles and Theory. CRC Press, New York. Do, T.-M., Wang, C.-F., Hsieh, Y.-K., Hsieh, H.-F., 2012. Metals present in ambient air before and after a firework festival in Yanshui, tainan, taiwan. Aerosol Air Qual. Res. 12, 981e993. Donaldson, K., Li, X., MacNee, W., 1998. Ultrafine (nanometre) particle mediated lung injury. J. Aerosol Sci. 29, 553e560. Dutschke, A., Lohrer, C., Kurth, L., Seeger, S., Barthel, M., Panne, U., 2011. Aerosol emissions from outdoor firework displays. Chem. Eng. Technol. 34, 2044e2050. €rster, G., Penney, D., Soderholm, S., Gelein, R., Piper, H., 1990. Ferin, J., Oberdo Increased pulmonary toxicity of ultrafine particles? I. Particle clearance, translocation, morphology. J. Aerosol Sci. 21, 381e384. Godri, K.J., Green, D.C., Fuller, G.W., Dall’Osto, M., Beddows, D.C., Kelly, F.J., Harrison, R.M., Mudway, I.S., 2010. Particulate oxidative burden associated with firework activity. Environ. Sci. Technol. 44, 8295e8301. Harrison, R.M., Shi, J.P., Xi, S., Khan, A., Mark, D., Kinnersley, R., Yin, J., 2000. Measurement of number, mass and size distribution of particles in the atmosphere. Philos. Trans. R. Soc. Lond. Ser. A 358, 2567e2580. Hu, M., Peng, J., Sun, K., Yue, D., Guo, S., Wiedensohler, A., Wu, Z., 2012. Estimation of size-resolved ambient particle density based on the measurement of aerosol number, mass, and chemical size distributions in the winter in Beijing. Environ. Sci. Technol. 46, 9941e9947. Hughes, L.S., Cass, G.R., Gone, J., Ames, M., Olmez, I., 1998. Physical and chemical characterization of atmospheric ultrafine particles in the Los Angeles area. Environ. Sci. Technol. 32, 1153e1161. Joly, A., Smargiassi, A., Kosatsky, T., Fournier, M., Dabek-Zlotorzynska, E., Celo, V., Mathieu, D., Servranckx, R., D'Amours, R., Malo, A., Brook, J., 2010. Characterisation of particulate exposure during fireworks displays. Atmos. Environ. 44, 4325e4329. €, M., Aalto, P., Miikkulainen, P., Kulmala, M., Maso, M., M€ akel€ a, J., Pirjola, L., V€ akeva €meri, K., O'Dowd, C., 2001. On the formation, growth and composition of Ha nucleation mode particles. Tellus B 53, 479e490. Li, X., Guo, X., Liu, X., Liu, C., Zhang, S., Wang, Y., 2009. Distribution and sources of solvent extractable organic compounds in PM2.5 during 2007 Chinese Spring Festival in Beijing. J. Environ. Sci. 21, 142e149. €nkko € nen, P., Koponen, I., Lehtinen, K., Uma, R., Srinivasan, D., H€ Mo ameri, K., Kulmala, M., 2004. Death of nucleation and Aitken mode particles: observations at extreme atmospheric conditions and their theoretical explanation. J. Aerosol Sci. 35, 781e787. n, M., Pey, J., Rodriguez, S., Moreno, T., Querol, X., Alastuey, A., Cruz Minguillo , J., Felis, C., Gibbons, W., 2007. Recreational atmospheric pollution Vicente Miro episodes: inhalable metalliferous particles from firework displays. Atmos. Environ. 41, 913e922. Nishanth, T., Praseed, K., Rathnakaran, K., Satheesh Kumar, M., Ravi Krishna, R., Valsaraj, K., 2012. Atmospheric pollution in a semi-urban, coastal region in India following festival seasons. Atmos. Environ. 47, 295e306. €rster, G., Ferin, J., Gelein, R., Soderholm, S.C., Finkelstein, J., 1992. Role of the Oberdo alveolar macrophage in lung injury: studies with ultrafine particles. Environ. Health Perspect. 97, 193. Steinhauser, G., Sterba, J.H., Foster, M., Grass, F., Bichler, M., 2008. Heavy metals from pyrotechnics in New Years Eve snow. Atmos. Environ. 42, 8616e8622. van Kamp, I., van der Velden, P.G., Stellato, R.K., Roorda, J., van Loon, J., Kleber, R.J., Gersons, B.B., Lebret, E., 2006. Physical and mental health shortly after a disaster: first results from the Enschede firework disaster study. Eur. J. Public Health 16, 252e258. Vecchi, R., Bernardoni, V., Cricchio, D., D'Alessandro, A., Fermo, P., Lucarelli, F., Nava, S., Piazzalunga, A., Valli, G., 2008. The impact of fireworks on airborne particles. Atmos. Environ. 42, 1121e1132. Wang, Y., Zhuang, G., Xu, C., An, Z., 2007. The air pollution caused by the burning of fireworks during the Lantern Festival in Beijing. Atmos. Environ. 41, 417e431. Wehner, B., Wiedensohler, A., Heintzenberg, J., 2000. Submicrometer aerosol size distributions and mass concentration of the millennium fireworks 2000 in Leipzig, Germany. J. Aerosol Sci. 31, 1489e1493. Zhang, M., Wang, X., Chen, J., Cheng, T., Wang, T., Yang, X., Gong, Y., Geng, F., Chen, C., 2010. Physical characterization of aerosol particles during the Chinese New Year's firework events. Atmos. Environ. 44, 5191e5198.
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Wide-range particle characterization and elemental concentration in Beijing aerosol during the 2013 Spring Festival Hui Jing a, b, c, Yu-Feng Li a, *, Jiating Zhao a, Bai Li a, Jialong Sun b, Rui Chen d, Yuxi Gao a, Chunying Chen d, * a
CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Multidiscipline Initiative Center, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China Guizhou Academy of Environmental Science and Designing, Guiyang 550081, China c Guizhou Normal University, Guiyang 550001, China d CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, National Center for Nanoscience and Technology, Beijing 100190, China b
a r t i c l e i n f o
a b s t r a c t
Article history: Received 21 April 2014 Received in revised form 3 June 2014 Accepted 6 June 2014 Available online 26 June 2014
The number and mass concentration, size distribution, and the concentration of 16 elements were studied in aerosol samples during the Spring Festival celebrations in 2013 in Beijing, China. Both the number and mass concentration increased sharply in a wide range from 10 nm to 10 mm during the firecrackers and fireworks activities. The prominent increase of the number concentration was in 50 nm e500 nm with a peak of 1.7 105/cm3 at 150 nm, which is 8 times higher than that after 1.5 h. The highest mass concentration was in 320e560 nm, which is 4 times higher than the control. K, Mg, Sr, Ba and Pb increased sharply during the firework activities in PM10. Although the aerosol emission from firework activities is a short-term air quality degradation event, there may be a substantial hazard arising from the chemical composition of the emitted particles. © 2014 Elsevier Ltd. All rights reserved.
Keywords: Firecrackers Fireworks Particle distribution Elemental concentration Spring Festival Beijing
1. Introduction The Spring Festival, falling on the Chinese lunar January 1st, is the most important festival celebrated in China and is when all family members get together, just like Christmas in the West. Burning firecrackers and fireworks is one of the most typical activities during the Spring Festival, which can release gaseous phase pollutants such as sulfur dioxide, nitrogen oxides, ozone and various sized particulate matters with trace metals and organic compounds. These emissions are associated with negative impacts on health and reduced visibility (Attri et al., 2001; Do et al., 2012; Godri et al., 2010; Joly et al., 2010; Li et al., 2009; Moreno et al., 2007; Nishanth et al., 2012; van Kamp et al., 2006; Vecchi et al., 2008; Wang et al., 2007). Several studies found increased releases of particulate matters after firecrackers and firework events. For example, Wehner et al., (2000) reported that the number of submicrometer (Dp > 100 nm) particles increased significantly during the Millennium fireworks
* Corresponding authors. E-mail addresses: [email protected] (Y.-F. Li), [email protected] (C. Chen). http://dx.doi.org/10.1016/j.envpol.2014.06.003 0269-7491/© 2014 Elsevier Ltd. All rights reserved.
€ nkko €nen et al., (2004) studied the particle in Leipzig, Germany. Mo number size distribution in the range from 3 to 800 nm during the Diwali festival in New Delhi, India in 2002 and very high concentrations (>105/cm3) of accumulation mode (100e800 nm) particles were detected. (Zhang et al., 2010) measured the number concentration and size distribution of particles during the Spring Festival celebrations in 2009 in Shanghai, China. It was found that the fireworks activities contributed to the number concentration of particles at 100e500 nm with an hourly average maximum of 2.8 104/cm3 during the peak hour on Spring Festival Eve, which is almost 3 times higher than the average number concentrations measured the day before. The Beijing municipal government has banned the manufacture, sale and setting off firecrackers and fireworks during the Spring Festival since 1993 considering the health, safety and environment concerns. However, due to the pressure from people who desire to follow the old tradition, the local government allowed the setting off firecrackers and fireworks in Spring Festival since 2006. An immediate study on the mass concentrations of PM2.5 and PM10 on Lantern Day in that year was performed and found that they were over six and four times as high as those in the normal day in Beijing,
H. Jing et al. / Environmental Pollution 192 (2014) 204e211
205
Table 1 Meteorological parameters during the 2013 Spring Festival.a Date
Temperature ( C)
Weather conditions Day
Night
Feb.2
Sunny
Light snow
Feb.3
Light snow
Feb.4
State of the wind Night (lowest)
Daytime
Night
2
6
Foggy
0
5
Intermittent winds 3 Winds N at 3e4
Sunny
Light snow
2
7
Intermittent winds 3 Intermittent winds 3 Winds N at 3e4
Feb.8
Sunny
Cloudy
2
9
winds
Feb.9
Cloudy
Cloudy
0
6
Feb.10
Cloudy
Overcast
1
6
Feb.11
Light snow
Light snow
1
6
Feb.12
Sunny
Sunny
2
7
Intermittent winds 3 Intermittent winds 3 Intermittent winds 3 Intermittent winds 3 Winds N at 3e4
a
Day (highest)
Intermittent 3 Intermittent 3 Intermittent 3 Intermittent 3 Intermittent 3 Intermittent 3
winds
winds winds winds winds
http://www.tianqihoubao.com/lishi/beijing/month/201302.html.
respectively (Wang et al., 2007). PM2.5, also called fine particles, is the particulate matter with an aerodynamic diameter of less than 2.5 mm, which can penetrate the respiratory system. PM10, also called inhalable particles, is the particulate matter with an aerodynamic diameter of less than 10 mm. The Lantern Day falls on the Chinese lunar January15th, when fireworks are also set off for celebration. However, to the best of our knowledge, no study on the wide-range particle characterization has yet been performed in ambient air during the Beijing Spring Festival, when much more intense firecrackers and fireworks are set off than on Lantern Day. Firecrackers and fireworks contain various inorganic and organic chemicals, such as charcoal, sulfur, potassium, lead, aluminum, iron and barium nitrate (Steinhauser et al., 2008). Besides the physical characterization of aerosol particles they emitted, the chemical analysis on the trace elements including K, Mg, Sr, Ba and Pb in them revealed significant increase during the firework events in London (Godri et al., 2010), Valencia (Moreno et al., 2007), al (Joly et al., 2010) and Tainan Milan (Vecchi et al., 2008), Montre (Do et al., 2012). Eighteen ions, 20 elements, and black carbon were measured in PM2.5 and PM10 in Beijing on Lantern Day (Wang et al., 2007). Primary components of Ba, K, Sr, Cl, Pb, Mg and secondary 2 2 2 2 components of C5H6O2 4 , C3H2O4 , C2O4 , C4H4O4 , SO4 , NO3 were over five times higher in Lantern Day than in the normal days. Although Li et al., (2009) studied the solvent extractable organic compounds in PM2.5 during 2007 Spring Festival in Beijing, the trace element levels were not studied (Li et al., 2009). In this study, we analyzed the particle number concentration (DP > 10 nm), size distribution (14.6 nm < DP < 10 mm), mass concentration (10 nm < DP < 10 mm) and elemental concentrations in particulate matters during the 2013 Spring Festival's firecrackers and fireworks celebrations in Beijing, China. These measurements were compared to that of before and after firework events, which is served to understand the physical and chemical characteristics of firework particles and their impact to local air quality. 2. Methods 2.1. Sampling site Atmospheric particulate samples were collected on the top of the laboratory building which is about 6 m above ground level at the Institute of High Energy Physics in Beijing (39 54' N, 11615' E), with a horizontal distance of approximately 200 m from one of the firework display areas. Besides, it should be noted that a large
amount of firework displays, firecrackers and sparkles were set off in the whole city throughout the Spring Festival week (9e16 February, 2013), with the main spectacular episode started soon after dinner (around 18:00) on the Spring Festival Eve (9 February, 2013), ended with the high point after midnight (0:00e2:00) on 10 February, 2013. The sampling site is about 2 km from west fourthring road and 4 km from west fifth-ring road, which are the two highways with heavy traffic. There are roughly 300 m from the nearest residential area. 2.2. Real-time sampling The real-time monitoring was carried out from February 8, 2013 to February 12, 2013 (the meteorological parameters were shown in Table 1). Scanning mobility particle sizer (SMPS 3936), optical particle sizer (OPS 3330) and the portable condensation particle counter (CPC 3007) were used to monitor the wide-range particle number concentration and particle size distribution in this study. The SMPS 3936 is consisted of a water-based condensation particle counter (CPC 3788), an electrostatic classifier (EC 3080), and a differential mobility analyzers (DMA 3081). The detection particle size range is 14.6e661.2 nm and the detection concentration range is 1 to 108/cm3. The OPS 3330 can detect particles ranging from 0.3 mm to 10 mm, and the upper limit of number concentration can reach 3000/cm3. The CPC 3007 is used to determine total number concentrations of aerosol particles with size more than 10 nm in the air, and the upper limit of concentration is 105/cm3. SMPS 3936 measures the electrical mobility diameter, whereas OPS 3330 measures the light scattering equivalent diameter, and CPC 3007 measures the aerodynamic diameter. The SMPS 3936 and OPS 3330 collect the data every 2 min, while the CPC 3007 collects the data every 1 s. 2.3. Integrated sampling Micro-orifice uniform-deposit impactor (MOUDI 125B, NanoMoudi-II, MSP Corporation, USA) was used to collect sizefractionated aerosol particle samples from 0.01 mm to 10 mm. The particulate matter is effectively separated into 13 ranges, with nominal cut-point diameter as 10,000, 5600, 3200, 1800, 1000, 560, 320, 180, 100, 56, 32, 18 and 10 nm. We collected the particles before (from 9:00 am February 2nd to 12:00 am February 4th 2013) and during the Spring Festival week (from 9:00 am February 9th to 12:00 am February 11th in 2013) for 50 h, respectively. The
206
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polycarbonate filter membranes (F47 mm, 0.8 mm, Millipore, USA) were used for the sample collection. Before and after sampling, the filter membranes were put into the temperature & humidity chamber (25 ± 1 C, 45 ± 1%) to balance for 24 h, and then were weighted. The differential method was used to calculate the mass of particles on the filter membranes. 2.4. Elemental analysis Half of the membranes were digested for 4 h at 150 C in highpressure Teflon digestion vessel with 9 mL concentrated HNO3 (BVⅢ grade, Beijing Chemicals) and 3 mL concentrated HF (GR grade, Beijing Chemicals). The solutions were then evaporated using hot plate until only 1 mL was left. Then the digested solutions were diluted to 3 mL with deionized water (resistivity 18.2 MU cm) and centrifuged at 8000 rpm. The supernatants were used for metal analysis including Mg, Ti, V, Co, Cu, Zn, Se, Rb, Sr, Cd, Cs, Ba, Pb by inductively coupled plasma e mass spectrometry (ICP-MS, X7, Thermo Electron, USA) and Na, K, Ca by inductively coupled plasma - optical emission spectrometer (ICP-OES, Optima 8000, PerkinElmer, USA). Each sample was measured three times. The calibration was made using Quality Control Standard 21 (Spex Certiprep, Lot No.: 25-79AS) and reference materials including Rb (12D719), Cs (GSB 04e1724-2004), Ba (GSB 04e1717-2004), Na (GSB 04e1738-2004), K (GSB 04e1733-2004) and Ca (GSB 04e1720-2004) purchased from National Center of Analysis and Testing for Nonferrous Metals and Electronic Materials. Recoveries were analyzed using a soil reference material (GBW-07405 (GSS-5), Chinese Academy of Geophysical and Geochemical Exploration). The recovery of those elements was in the range of 90%e110%. Blank filter values were subtracted from sample determinations. 3. Results and discussion 3.1. Total particle number concentration The total particle number concentration (particles with aerodynamic diameter larger than 10 nm) measured by CPC 3007 before (from 12:00 am February 8th to 05:00 am February 9th, 2013) and on Spring Festival Eve (from 12:00 am February 9th to 05:00 am February 10th, 2013) is shown in Fig. 1. From Fig. 1, it can be seen that the total number concentration began to rise sharply after 00:00 to 00:21 with the peak value of 7.7 104/cm3, which is consistent to the start of intensively setting off of firecrackers and
Fig. 1. Total particle number concentration before and on Spring Festival Eve (Feb.9th, 2013).
fireworks from 00:00 February 10th. Subsequently, the value began to decline, and dropped to 2.9 104/cm3 at 01:00, and went down to the minimum value of 1.1 104/cm3 at 02:00, which is only 1/7 of the peak value. These results indicated that large amount of particles were produced from firecrackers and fireworks activities, which were quickly released to the air and impaired the air quality seriously. On the other side, the particle number could decrease to the background level in only 1.5 h 3.2. Particle number concentration distribution We have used the SMPS 3936 (detection range from 14.6 nm to 661.2 nm) and OPS 3330 (detection range from 0.3 mm to 10 mm) to measure the particle number concentration distribution. Fig. 2 showed the particle size distributions covering 14.6e661.2 nm from 00:00 to 06:00 on February 8th, 10th and 12th, 2013, respectively as determined by SMPS 3936. The number concentration on February 8th decreased with particle size increased, and the highest was at 14.6 nm (the smallest size detectable by SMPS 3936); Particle concentration was relatively low at 14.6 nm on February 10th, and the peak number concentration occurred at 150 nm. Interestingly, trend of particle size distribution on February 12th presented bimodal pattern, whose peaks were roughly at 14.6 nm and 100 nm. On the other hand, the number concentration changes irregularly over time on February 8th and 12th, while on February 10th, it showed significant time variation: the number concentration of each mode particles determined by SMPS 3936 found the peak value at 00:21 at 150 nm. The highest particle number concentration reached 1.7 105/cm3. Subsequently, it began to decrease to stable level at 02:00 until 06:00. These results were consistent with the data as detected by CPC 3007. The particle size distributions determined by OPS 3330 covering 0.3e10 mm at 00:00e06:00 on February 8th, 10th and 12th are shown in Fig. 3. Before, during and after the Spring Festival, there was no obvious difference in the particle size distribution in the range from 300 nm to 10 mm: Larger particles had fewer number concentrations. In addition, the number concentration of particles at 300 nm reached the peak at 00:21 on February 10th, which was similar to the results of CPC 3007 and SPMS 3936. Particles in the size range from 10 nm to 10 mm can be divided into six size groups: Nucleation mode (10 nm < Dp < 20 nm), small Aitken mode (20 nm < Dp < 50 nm), large Aitken mode (50 nm < Dp < 100 nm), small accumulation mode (100 nm < Dp < 500 nm), large accumulation mode (0.5mm < Dp < 1 mm) and coarse mode (1mm < Dp < 10 mm) (Zhang et al., 2010). Smaller particles have a higher surface area-to-mass ratio and deposition efficiency in the alveoli and ultrafine particles can be more toxic than coarse particles of the same mass (Donaldson et al., 1998; € rster et al., 1992). Hughes et al., 1998; Oberdo In this study, the nucleation and Aitken mode particles are dominant before and after the Spring Festival. The most likely reason is a mixture influence of traffic emissions and meteorological conditions (Ferin et al., 1990). However, the number concentration of nucleation and small Aitken mode particles is relatively low on after fireworks display, which can be explained via the concept of the coagulation sink (Agus et al., 2008; Kulmala et al., €nkko € nen et al., 2004; Zhang et al., 2010). Some studies 2001; Mo show that small accumulation mode particles are main dominance in firework celebration, and would be due to primary emissions from the firework activity (Agus et al., 2008; Dutschke et al., 2011; € nkko € nen et al., 2004; Zhang et al., 2010). Dutschke et al., (2011) Mo reported that fireworks were likely to release particles with diameters in the range of 30e450 nm and the maximum value was between 80 and 175 nm in 2011. Our result is similar to Dutschke's. There is a small impact in nucleation, small Aitken, large
H. Jing et al. / Environmental Pollution 192 (2014) 204e211
Fig. 2. The particle size distribution (14.6e661.2 nm) at 00:00e6:00 on (a) February 8th, 2013; (b) February 10th, 2013; (c) February 12th, 2013.
207
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H. Jing et al. / Environmental Pollution 192 (2014) 204e211
Fig. 3. The particle size distribution (0.3e10 mm) at 00:00e06:00 on (a) February 8th, 2013; (b) February 10th, 2013; (c) February 12th, 2013.
H. Jing et al. / Environmental Pollution 192 (2014) 204e211
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different sampling time: we collected the air samples for 50 h, while others collected for 12 h. The longer sampling time leads to the decreased average mass concentration. 3.4. Elemental analysis
Fig. 4. Particle mass concentration distribution.
accumulation and coarse mode particles. But the increase of the concentration is apparent in large Aitken mode and small accumulation mode particles, especially when the Dp is about 150 nm. The reasons for these differences may be the discrepancy of the surrounding environment, height, weather and climate conditions etc. of the sampling points. 3.3. Particle mass concentration We chose the data detected from February 2nd to February 4th as control, whose weather conditions were similar to the Spring Festival (from February 9th to February 11th, see Table 1). As shown in Fig. 4, the trend of mass concentration distribution during the Spring Festival was similar to that on the control days, but the mass concentration of particles during the Spring Festival increased compared to the control in each particle size range, and the peak value was at 320e560 nm (40.26 mg/m3), which is 4 times higher than the control. In practice, the particles were generally divided into three size groups when considering mass concentration: PM0.01e0.1 (0.01mm < Dp < 0.1 mm), PM0.1e1.0 (0.1mm < Dp < 1.0 mm) and PM1e10 (1.0mm < Dp < 10 mm). In the present study, the mass concentrations of PM0.01e0.1, PM0.1-1.0 and PM1e10 were 3.79 mg/m3, 72.13 mg/m3, 27.43 mg/m3 during firework activities, which were 2.5, 2.4, 2.9 times higher than the control days, respectively. The mass concentration of PM10 (Dp < 10 mm) on the control days was 41.7 mg/m3, which was less than the mean concentration of PM10 (54 mg/m3) in one clean episode in the winter in Beijing (Hu et al., 2012). On the other hand, the mass concentration of PM10 (103.5 mg/m3) after setting off firecrackers was less than the maximum concentration of PM10 (466.2 mg/m3) detected by Wang et al., (2007) during the Lantern Day (Wang et al., 2007). This concentration was even lower than the maximum prescribed limit (150 mg/m3) of the Chinese national secondary air quality standard. Our data is relatively low compared to other studies and the most likely reason is due to the
The concentrations of various elements in PM10 during the Spring Festival and the control days were shown in Table 2. First of all, there are very sharp peaks for K, Mg, Sr, Ba and Pb during the Spring Festival. The concentration is in the order of K > Mg > Ba > Pb > Sr, which are almost 11, 6, 67, 6 and 25 times higher than those in the control days, respectively. On the other hand, the concentrations of Ti, V, Co, Zn, Rb and Cs see a moderate increase on the firework night, which are about 1.8e3.5 times higher than those in the control days, respectively. In addition, the concentrations of Na, Ca, Cu, Se and Cd are almost unchanged during the Spring Festival and control days. Therefore, K, Mg, Sr, Ba and Pb are the primary components, while Ti, V, Co, Zn, Rb and Cs are the secondary components during the firework event. The primary components found in this study agrees well with the studies by Wang et al. (Wang et al., 2007) and (Godri et al., 2010). In fact, Mg is widely used as a metallic component of firework fuel. Pb can be used to achieve a steady and reproducible burning rate. K, Sr, Ba can radiate purple, red and green colors, respectively (Conkling and Mocella, 2011). Other studies also found the elevation of Na (Wang et al., 2007), Ca (Do et al., 2012; Wang et al., 2007), Cu (Do et al., 2012; Harrison et al., 2000; Hughes € rster et al., 1992), Zn et al., 1998), Ti (Harrison et al., 2000; Oberdo (Do et al., 2012; Wang et al., 2007) during the firework events, but Na, Ca and Cu concentrations was not found changed in this study. The reasons for these differences may be as follows. Firstly, the sampling time is different: this study's sampling times is 50 h, while it is 12 h in Wang's (Wang et al., 2007). Secondly, the surrounding environment, height, weather and climate conditions of the sampling points are different. For instance, both the sampling date in this and Do's are February, but Taiwan belongs to tropical and subtropical climate while Beijing is a typical warm temperate semihumid continental monsoon climate. Therefore, the weather conditions vary widely. Finally, the production compositions of diverse firework manufacturers may be different. Fig. 5 shows the concentration distribution of Ba, K, Mg, Pb, Sr, Ti and Zn from 10 nm to 10 mm during the Spring Festival and the control days. The trend of the concentration distribution of Ba, K, Mg, Pb, Sr and Zn is similar to mass concentration distribution of particulate matters (see Fig. 4) during the Spring Festival. Thus, we think that Ba, K, Mg, Pb, Sr and Zn distribute evenly in various size particulate. Moreover, the concentration distribution of Ba, K, Pb, Sr, Zn were similar with those reported by Do et al. (Do et al., 2012) but they showed decreased Mg concentrations. The correlation of K and other elements (Mg, Sr, Ba, Pb, Zn, Ti) in different size range during the Spring Festival and the control days were tested. K showed notably stronger correlations (N ¼ 13) with Mg (r ¼ 0.96), Sr (r ¼ 0.98), Ba (r ¼ 0.96), Pb (r ¼ 0.86), Zn (r ¼ 0.99) in the Spring Festival than Mg (r2 ¼ 0.07), Sr (r ¼ 0.48), Ba (r2 ¼ 0.09), Pb (r ¼ 0.53), Zn (r ¼ 0.25) in the control days. The correlations with K and Ti are r2 ¼ 0.9 and r ¼ 0.6 respectively during the Spring
Table 2 The concentrations (ng/m3) of various elements in PM10 during the Spring Festival and the control days. Elemental concentration (ng/m3)
Control days Spring Festival Ratio (Spring Festival/Control)
K
Mg
Sr
Ba
Pb
Ti
V
Co
Zn
Rb
Cs
Cd
Ca
Se
Cu
Na
770 8855 11.5
205.9 1284 6.24
9.28 233 25.1
16.1 1079 67.0
47.8 287 6.00
40.3 140 3.48
3.02 5.94 1.97
2.35 4.27 1.82
69.4 128.5 1.85
2.92 7.57 2.59
0.24 0.50 2.08
0.65 0.81 1.24
1915 2011 1.05
1.28 1.86 1.45
117 158 1.35
3548 2312 0.65
210
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Fig. 5. The distribution of Ba, K, Mg, Pb, Sr, Zn and Ti from 10 nm to 10 mm in the Spring Festival and the control days.
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Festival and the control days. Therefore, It can be further proved that K, Mg, Sr, Ba, Pb, Zn are largely from the same source, namely, firework, while Ti may not be directly from the firework. 4. Conclusions The total number concentration, mass concentrations, size distribution and elemental concentrations in aerosol particle were measured during the Spring Festival's firecrackers and fireworks events in 2013 in Beijing. This study shows that firework activities increase the number and mass concentrations of each particle size range from 10 nm to 10 mm. Total number concentration in the peak of firework celebrations is approximately 7 times higher than 1.5 h later. The mass concentration of PM10 is 103.5 mg/m3 during the Spring Festival, which is 2.5 times as high as that in control days. The increase of the number concentration is apparent in larger Aitken mode and small accumulation mode particles, especially at about 150 nm. The peak particle number concentration is 1.7 105/ cm3 at 00:21, which is 8 times more than that after 1.5 h in the same diameter. The highest average mass concentration is 40.26 mg/m3, which is 4 times as high as the control in the diameter range of 320e560 nm. The primary components as K, Mg, Sr, Ba and Pb increased sharply during the firework activities and are about 11, 6, 25, 67 and 6 times higher than those in the control days in PM10. Secondary component of Ti, V, Co, Zn, Rb and Cs increased moderately and are about 1.8e3.5 times higher than those in the normal days. The concentration distribution of Ba, K, Mg, Pb, Sr, Zn and mass concentration distribution of particulate is similar during the Spring Festival events with a peak in the range of 320e560 nm. Moreover, through correlations analysis, we think that Ba, K, Mg, Pb, Sr and Zn are largely from firework and evenly distributed in the various size particulate. This study demonstrates that the aerosol emission from firework activities is a short-term air quality degradation event. But primary emissions from firework celebrations significantly change the particle size distribution. And there may be a substantial hazard arising from the chemical composition of the particles. Finally, we suggest people wear a dust mask as far as possible during the firework activities and do not perform outdoor activities in the short term. Acknowledgments Y-F Li gratefully acknowledges the support of K. C. Wong Education Foundation and the Youth Innovation Association, Chinese Academy of Sciences. This work is supported by National Natural Science Foundation of China (11205168, 31070854 and 21277037) and the Ministry of Science and Technology of China (2011CB933401, 2012CB934003 and 2010CB934004). References Agus, E.L., Lingard, J.J., Tomlin, A.S., 2008. Suppression of nucleation mode particles by biomass burning in an urban environment: a case study. J. Environ. Monit. 10, 979e988.
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