J Radioanal Nucl Chem (2012) 291:95100 DOI 10.

1007/s10967-011-1307-4

Preliminary study on air pollution source identication in Xinzhen, Beijing, using NAA and PIXE
Caijin Xiao Guiying Zhang Donghui Huang Bangfa Ni Cunxiong Liu Yali Qin Hongchao Sun Pingsheng Wang Weizhi Tian

Received: 14 June 2011 / Published online: 26 June 2011 miai Kiado , Budapest, Hungary 2011 Akade

Abstract A total of 178 aerosol samples in two size fractions, PM10-2.5 (coarse) and PM2.5 (ne), were collected on nucleopore lms using a Gent stacked lter unit sampler at the Graduate School of China Nuclear Industrial Group during May 2007 to November of 2009. Black carbon was determined by a reectometer. A total of 16 elements, Mg, Al, S, Si, P, Cl, Ca, K, Ti, Mn, Fe, Ni, Cu, Zn, As and Pb, were determined by Particle Induced X-ray Emission. Mg, Al, Ca, K and Mn were also determined by Neutron Activation Analysis. Concentrations of all these elements were used to identify possible pollution sources and directions of the airborne particulate matter by means of softwares PMF and CPF. Some extraordinary events, such as sandstorms, rework and transboundary re smoke were pinpointed by a combination of time series of multielement, relevant meteorological data and softwares Wind rose, Hysplit, and Google earth. Keywords PIXE NAA APM Pollution sources Extraordinary events

Introduction The study on airborne particulate matter (APM), especially the distribution and multielement composition of PM2.5 (ne particles with diameter B2.5 lm) and PM10 (coarse particles with diameter B10 lm), is gaining worldwide attention because of its severe health effects [13], such as
C. Xiao G. Zhang D. Huang B. Ni (&) C. Liu Y. Qin H. Sun P. Wang W. Tian Department of Nuclear Physics, China Institute of Atomic Energy, P.O. Box 275-50, Beijing 102413, China e-mail: bfni@ciae.ac.cn

respiratory and cardiovascular disease [4], as well as visibility effects and transboundary transportation. Nuclear analytical techniques (NAT), neutron activation analysis (NAA) and particle induced X-ray emission (PIXE) in particular, have played an important role in the determinations of multielement in APM samples. As examples of some recent publications, NAA was used by Jasan et al. [5], Athari et al. [6] and Giaveri et al. [7], and PIXE by et al. [8] in the studies on APM. Almeidaa et al. [9] Roumie and Santosoa et al. [10] used both NAA and PIXE. Two recent review articles by Fang et al. [11] and Smodis [12] summarized APM studies mainly using NAT. A 3-year study has been undertaken on the air pollution trend at the Graduate School of China Nuclear Industrial Group in Xinzhen District, Beijing. It is part of a Regional Cooperation Agreement (RCA) project participated by 13 Asian countries and sponsored by International Atomic Energy Agency (IAEA). In this work, a Gent stacked lter unit (SFU) sampler was used to collect PM2.5 and PM10 samples. Both PIXE and NAA were used to determine important pollution and indicator elements in all APM samples, taking the advantages of NAA in multielement capability (up to 40 elements [13]) and PIXE in determining some key elements (S, Pb, Si, etc.) which are unable to determine in sufcient accuracy by NAA. Black carbon (BC), as a major component and indicator of anthropogenic discharge to atmosphere [14, 15], was also measured on all PM 2.5 samples by a Smokestain Reectometer. Positive matrix factorization (PMF) and conditional probability function (CPF) were performed for preliminary investigations on the pollution sources and directions. Four potential pollution sources, soil and y ash, coal burning, plant burning, industry smelt and vehicle exhaust, were identied by EPA PMF 3.0. Some extraordinary events, such

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as sandstorms, rework and transboundary re smoke, were clearly pinpointed using relevant meteorological data and softwares Wind rose (http://www.weblakes.com/products/ wrplot/index.html), Hysplit (http://www.arl.noaa.gov/rea dy/HYSPLIT4.html), and Google earth (http://www.google. com/earth/index.html).

Experimental Sampling and sample handing The sampling site is located at the Graduate school of China Nuclear Industrial Group, Xinzhen, Fangshan (longitude 116.03 E, latitude 39.44 N, altitude 75 m), southwest of Beijing (representative of heavy trafc and residential district), 20 m above the ground level. A Gent SFU sampler [16] consisting of two nuclepore lters with 0.4 and 8 lm pore sizes was used for collecting PM10 and 2.5 APM at a general frequency of twice a week. Altogether 178 samples were obtained from May 2007 to November 2009. The humidity and temperature in balance room have been kept within 50 5%, rel. and 25 5 C, respectively, when samples were weighed before and after APM collection using a Mettler Toledo GmbH Microbalance, Switzerland (readability 1 lg). One blank lter for every 20 samples was analyzed to correct for lter blank. Black carbon (BC) determinations BC in PM2.5 air lter samples were estimated by measuring the light reection through the lters before and after exposure using an EEL 43D Smokestain Reectometer produced by England Diffusion Systems Ltd. The area density, ECR, in lg/cm2 and volume concentration, M, in lg/m3 air of BC on a lter were calculated by eqs. (1) and (2) [17].  ECR lg cm2 f100=2F eglnR0 =R 1 M ECR A=V
2

Twenty samples were stuck on a piece of target holder in sequence for one run. Each sample was bombarded for 3 min with a 2.5 MeV proton beam (beam current: 0.120 nA, beam spot size: 20 mm2) from a 2 9 1.7 MV tandem accelerator (GIC4117) in Institute of Low Energy Nuclear Physics, Beijing Normal University [18]. X-rays induced by incident proton beam were measured using a Si(Li) spectrometer system (Canberra 7383, USA) with the effective area of 80 mm2,and the thickness of 5 mm. The thickness of Be window is 25 lm and the distance between detector and Be window is 5 mm. The energy resolution of the system is 159 keV relative to the characteristic Ka X-ray of Mn (5.9 keV). X-ray spectra were recorded by an S-35 multichannel pulse height analyzer. Software GUPIXWIN was used for peak analysis. A total of 16 elements, Mg, Al, S, Si, P, Cl, Ca, K, Ti, Mn, Fe, Ni, Cu, Zn, As and Pb, were determined. Multielement determination by NAA A weighed Fe wire and a 25 mm Zr foil were used for comparator and neutron ux ratio monitors, respectively, in k0-NAA. NIST SRM 1632a (coal powder) and GBW 07312 (stream sediment) were concurrently analyzed with samples for quality control. Samples were packed in PE lm for irradiation. All samples were irradiated with a neutron ux of 5 9 1011 cm-2 s-1 at the miniature neutron source reactor (MNSR) in China Institute of Atomic Energy. All countings were performed on an automated HPGe spectrometer system (Canberra, Meriden, CT, USA, 35%, 2.1 keV). Software SPAN [19] was used for peak analysis and hybrid k0-relative software ADVNAA [20] for elemental concentration calculations. Mg, Al, Ca, K and Mn determined by INAA were used for statistic analysis. They are all in agreement with those by PIXE within uncertainty limits.

Results and discussion APM concentrations The annual averages of volume concentrations for PM2.5 and PM10 were found to be 50.6 and 189.0 lg/m3, respectively. The former is apparently larger than 15 lg/m3 prescribed in EPA standard of America (http://www. epa.gov/air/criteria.html). The latter is apparently larger than 100 lg/m3 prescribed in ambient air quality standard for the second criterion in GB3095-1996 [21]. Diurnal and monthly variations in the concentration of PM2.5, PM10-2.5 and PM10 shown in Figs. 1 and 2 indicate that the APM concentrations in the spring and

where e in m /g is mass absorption coefcient, F is a calibration factor (correction for absorption by non-BC components in a PM2.5 sample), R0 and R are light intensities before and after sample collection, respectively, A in cm2 is the area of APM collection on lter and V in m3 is total volume of air sampled. Calibration factor, e = 7 m2/g [17]. Multielement determination by PIXE Mylar standard lters produced by American Micromatter Company were analyzed for quality control in PIXE.

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Preliminary study on air pollution Fig. 1 Diurnal variations of PM2.5, PM10-2.5 and PM10
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autumn (windy seasons) were obviously higher than those in summer and winter. Correlations among PM2.5 concentration, visibility and BC concentration PM2.5 concentration is one of the major factors inuencing visibility. As shown in Fig. 3, PM2.5 concentration and visibility are negatively correlated. Visibility data were from http//www.wunderground.com. Figure 4 shows a strong positive correlation between BC and PM2.5 with a correlation coefcient of 0.83. The median content of BC in PM 2.5 samples was determined to be 5.09 lg/m3, which is lower than that in Bangladesh, Philippines and Sri Lanka and higher than that in India, Indonesia, Malaysia, Korea, Vietnam and Thailand [22]. Pollution sources analysis by PMF PMF analysis was performed on 17 elements in 89 ne APM samples (sampled from 200705 to 200911) using

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software EPA PMF3.0 [23] provided by American EPA. As shown in Fig. 5, four factors are identied. From the major elements in each factor, the following sources are

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Fig. 5 Loadings of elements in factors 14

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Preliminary study on air pollution Fig. 6 Location of sampling site

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deduced. In factor 1, elements with the highest scores include Mg, Al, Si, Ti, Ca, Fe and Mn, clearly indicating the soil and y ash origins. In factor 2, elements with the highest scores include BC, S, P, K and Cu, indicating a plant incineration origin. In factor 3, elements with the highest scores include BC, Cl, P, and Zn, indicating a coal burning origin. In factor 4, elements with the highest scores include BC, Mn, Cu, Zn, As and Pb, indicating a mixture of industry and motor vehicle exhaust origins. Directional distribution of pollutants by CPF The location of the sampling site is shown in Fig. 6. Province road 208 is in the southwest of sampling site.

Province road 317, the sixth ring road and Jingshi Highway are in the south of sampling site. Liangxiang, a residential and industrial zone, is in the southeast of sampling site. Downtown Beijing, the political, economic and cultural center of China, is in the northeast of sampling site. Directional distributions of some elements in PM 2.5 are shown in Fig. 7 based on software CPF and the information of wind speed and direction for each hour. The CPF values of element pairs Si-Ca, Cl-P and BC-K are higher in the northwest, northwest and south directions, respectively, than those in other directions, as shown in Fig. 7, clearly indicating that the three element pairs may originate from soil and y ash, coal burning and plant incineration, respectively. The CPF values of elements BC, Cu and Zn in

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the southwest direction is higher than those in other directions, indicating that the three elements may originate from the industrial zone in southwest of sampling site (where a large oil renery and some machine shops are located) and associated motor vehicles. The pollution sources identied by software CPF are in accordance with those by PMF. Some extraordinary events PM 2.5 values of Al and Si were 468 and 119 lg/m3, respectively, on 18 March, 2008, the day of sandstorm occurred in Beijing, much higher than the corresponding average 990 ng/m3 and 2.01 lg/m3 during sampling period. The backward trajectories of this sandstorm event using softwares Hysplit and Google earth indicate the sandstorm originates from Mongolia. The highest peaks of K and S on February 21, 2008, the day of Chinese lantern festival, are 5.7 and 6.9 times higher than those on February 7, clearly indicating that this event is attributed to rework display. The highest peak of BC on September 11, 2007 is 17.9 lg/m3, 57 times higher than the lowest peak on May 26, 2007. Fireworks are made of gunpowder, which contains KNO3, S, and charcoal. The simultaneous peaks of K and S in APM, combined with the wind direction, may reasonably attribute to the rework display in a nearby wedding celebration. BC in the second peak on February 21, 2008 is 12.5 lg/m3 (S and K are also peaked on the same day). The directions of the origin are north and northeast of sampling site analyzed by software Wind Rose. There was a celebration activity of rework display on that day just 500 m northeast of sampling site, that contributed to the BC (and S, K) peak. There was a re event in Russia on 15 July, 2007. Six days later, there was a soot wave in Beijing on 21 July, 2007, in which the concentration of BC is 8.45 lg/m3 (compared to monthly average of 5.69 lg/m3). Backward trajectories of these 6 days were analyzed using Hysplit model. The results indicate the soot event at Beijing on 21 July, 2007 may come from the re event of 15 July, 2007 in Russia.

The major pollution sources are preliminarily recognized to be soil and y ash, coal burning, plant burning, industry smelt and vehicle exhaust by EPA PMF 3.0. CPF was used to nd the major direction of each source. Wind rose, Hysplit, and Google earth were used to identify special events, such as sandstorms, rework and transboundary re smoke.
Acknowledgments This work has been nancially supported in part by IAEA RCA RAS/7/015. The support of the operational personnel in Institute of Low Energy Nuclear Physics, Beijing Normal University is sincerely acknowledged.

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Conclusions Taking the advantages of non-destruction, high-precision and multielement capability of PIXE and INAA, concentrations of multielement were obtained in both ne and coarse fractions of APM samples collected on nuclear pore lms during May 2007 to November of 2009. The annual averages of volume concentrations for PM2.5 and PM10 are still higher than international standards.

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