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Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area
JES-01512; No of Pages 9 J O U RN A L OF E N V I RO N ME N TA L S CI EN CE S X X (2 0 1 8 ) XX X–XXX
Available online at www.sciencedirect.com
ScienceDirect www.elsevier.com/locate/jes
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Kai Zhang1,⁎, Fahe Chai1 , Zilong Zheng 1,2 , Qing Yang1,2 , Xuecai Zhong3 , Khanneh Wadinga Fomba4 , Guangzhu Zhou2
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Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area
1. State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China 2. College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China 3. Zhuzhou Environment Monitoring Center, Zhuzhou 412000, China 4. Leibniz-Institute for Tropospheric Research (TROPOS), Leipzig 04318, Germany
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Article history:
In order to understand the size distribution and the main kind of heavy metals in particulate
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Received 25 September 2017
matter on the lead and zinc smelting affected area, particulate matter (PM) and the source
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Revised 20 April 2018
samples were collected in Zhuzhou, Hunan Province from December 2011 to January 2012 and
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Accepted 20 April 2018
the results were discussed and interpreted. Atmospheric particles were collected with different
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Available online xxxx
sizes by a cascade impactor. The concentrations of heavy metals in atmospheric particles of
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Keywords:
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Heavy metals
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Lead and zinc smelting
Size distribution
concentration of PM, chromium (Cr), arsenic (As), cadmium (Cd) and lead (Pb) in PM was 177.3 ± 33.2 μg/m3, 37.3 ± 8.8 ng/m3, 17.3 ± 8.1 ng/m3, 4.8 ± 3.1 ng/m3 and 141.6 ± 49.1 ng/m3,
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respectively. The size distribution of PM displayed a bimodal distribution; the maximum PM
Pollution characteristics
size distribution was at 1.1–2.1 μm, followed by 9–10 μm. The size distribution of As, Cd and Pb in PM was similar to the distribution of the PM mass, with peaks observed at the range of 1.1–2.1 μm and 9–10 μm ranges while for Cr, only a single-mode at 4.7–5.8 μm was observed. PM (64.7%), As (72.5%), Cd (72.2%) and Pb (75.8%) were associated with the fine mode below 2.1 μm,
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coupled plasma mass spectrometry (ICP-MS). The results indicated that the average
Atmospheric particulate matter
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different sizes, collected from the air and from factories, were measured using an inductively
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respectively, while Cr (46.6%) was associated with the coarse mode. The size distribution characteristics, enrichment factor, correlation coefficient values, source information and the analysis of source samples showed that As, Cd and Pb in PM were the typical heavy metal in lead and zinc smelting affected areas, which originated mainly from lead and zinc smelting Q4
sources. © 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.
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Introduction
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Most heavy metals in the atmosphere are found in almost all aerosol size fractions, and their concentration and size
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Published by Elsevier B.V.
distribution are controlled by natural (crustal minerals, forest fires and oceans) and anthropogenic emissions (such as fossil fuel combustion and industrial processes) into the atmosphere as reported by many investigators (Shao et al., 2013; Duan and
⁎ Corresponding author. E-mail: [email protected]. (Kai Zhang).
https://doi.org/10.1016/j.jes.2018.04.018 1001-0742 © 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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1. Experimental methods
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1.1. Experimental methods of environment sampling
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1.1.1. Study area and sampling site
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Guangdong and Guangxi. These five Pb and zinc mining and processing bases account for more than 85% of total Pb output, and 95% of total Zn output in China, respectively. Hunan Province is famous as the “hometown of non-ferrous metal smelting”. The emissions from non-ferrous smelting in Hunan have been one of the main sources of heavy metals in the environment (Wei et al., 2009; Duan and Tan, 2013; Xie et al., 2016). Non-ferrous smelting activity has caused serious heavy metal pollution in surrounding districts, which has caused significant health and ecological risks (Lyu et al., 2017). Previous studies have not been able to provide a clear illustration of heavy metal variation in areas where intensive non-ferrous smelting activities have occurred, nor have been able to interpret the possible contamination-source relationship. Knowledge on the size of the atmospheric particles and their relationship to heavy metals is vital for understanding the characteristics of atmospheric heavy metals of the lead and zinc smelting affected regions. Chang-Zhu-Tan city clusters is a new urban agglomeration in central China, which is the first two-type social demonstration city group, i.e., environment-friendly and resourcesaving. Zhuzhou, the second largest city in Hunan province, is an important part of Chang-Zhu-Tan city clusters. It is one of the industrial regions in South China where non-ferrous smelting activities have developed rapidly since the 1950s (Ye et al., 2015), but many non-ferrous factories have closed in recent years due to the high demands required for environmental protection. Therefore the heavy metal pollution was very serious around the environment (Long et al., 2012). Wang and Stuanes (2003) studied the heavy metal pollution in air– water–soil–plant system of Zhuzhou city. Few studies on source identification and size distribution of heavy metals in atmospheric particles have been carried out in Zhuzhou. To understand the typical components of heavy metals in the atmosphere, we collected and analyzed the samplings in the atmospheric environment and from two non-ferrous smelting factories (lead and zinc smelting factories). The data obtained are important to understand the level of pollution and the type of heavy metals affected by the lead and zinc smelting factory. These results can be used to provide scientific evidence for setting up an air pollution control strategy. The first batch of elements identified in the “12th Five Year Plan on Heavy Metal's Comprehensive Prevention and Control” approved by the State Council were lead (Pb), mercury (Hg), chromium (Cr), cadmium (Cd) and arsenic (As). Mercury usually exists in a gaseous form in the atmosphere so that the concentration of mercury in PM is low. Although As is not a heavy metal (metalloid element), considering its negative health impacts it was regarded as a heavy metal and discussed as part of the study. Based on above, this study focused on the these four heavy metals.
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Tan, 2013; Pan and Wang, 2015). Particulate matters (PMs) are a mixture of primary and secondary aerosols and usually have bimodal mass distribution, which appears in both fine particulates (aerodynamic diameter less than 2.5 μm in) and coarse particulates (aerodynamic diameter between 2.5 and 10 μm), separately (Karanasiou et al., 2007). In general, fine particles carry higher concentrations of toxic metals than coarse particles (Fang and Huang, 2011). As particle size decreases, the specific surface (the surface area per unit volume (or mass)) increases, which makes harmful heavy metals to be easier absorbed by PM (Kaupp and McLachlan, 2000). Heavy metals associated with inhalable particulates have also been shown to increase numerous diseases such as lung or cardiopulmonary injuries (Hu et al., 2012; Pandey et al., 2013; Xie et al., 2016). Fine particles are able to penetrate into the lung, and consequently impair human health. Thus, much attention has been focused on the relationship between the heavy metal content and size of PM (Wilson et al., 2002; Liu et al., 2015; Masiol et al., 2015; Rogula-Kozlowska et al., 2013). Mohanral et al. (2004) indicated that about 70%–90% of heavy metals are contained by PM10, and the smaller the particles size, the higher the concentration of heavy metals. Brook et al. (1997) showed that heavy metals in PM2.5 were potentially harmful to the human body. Cyrys et al. (2003) and Duan and Tan (2013) hold that the content of heavy metals was higher in fine PM than that in coarse PM; poisonous and harmful heavy metals, such as Pb, Cd, Ni, Mn, V, Zn etc., were mainly adsorbed by fine particles. Heavy metals are released into the atmosphere by the combustion of fossil fuels, vehicle emission, high temperature industrial activities, metal mining and smelting, waste incineration and other human activities. Heavy metals in the atmosphere are frequently associated with specific pollutant sources, and these are often used as tracers to identify the source of atmospheric particles (Duan and Tan, 2013; Chen et al., 2013). Many studies have been undertaken to reveal PM and its associated heavy metal concentrations in the atmosphere surrounding industrial areas (Chen, 2007; Lim et al., 2010). Toscano et al. (2011) revealed that the coarse particles were thought to be formed by low temperature combustion, crustal erosion and road dust resuspension, while fine particles were believed to be principally emitted from anthropogenic sources including combustion, high-temperature industrial activities and automotive traffic. Wei et al. (2009) found that metal mining and smelting activities were the major sources of heavy metals entering the environment. Waste gas pollutants from nonferrous metal smelting are one of the main sources of heavy metal pollution in atmospheric particles (Davis et al., 1995). From recent report, the most severe polluted areas locate in northern China (Zhang and Cao, 2015). But the concentrations of Pb, Cr and Cd in PM in southern cities were 12.3%, 7.3% and 171%, higher respectively than those in northern cities, while the concentration of As in PM in northern cities was higher 65.5% than those in southerner cities according to the data obtained in 44 major cities in China during the last 10 years (Tan and Duan, 2013). Non-ferrous metal mining and smelting plants are one of the main sources of atmospheric heavy metals and are widely distributed in China (Wei et al., 2009). Lead and zinc smelting belong to non-ferrous smelting. There are five lead and zinc production bases: the northeast, the northwest, Yunnan and Sichuan, the Hunan, and the
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The weather of Zhuzhou is influenced by the prevalence of a 175 subtropical humid monsoon climate. Northwesterly winds are 176
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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1.1.2. Air sample collection, pretreatment and instrumental analysis A total of 81 samples were collected using an Anderson eightstage cascade impactor (Model 20–800, Tisch Environmental Inc., Cleves, OH, U.S.A), which provides a high-resolution size distribution of atmospheric particles. The atmospheric particles were separated into the following size ranges based on particle aerodynamic diameter (dae): < 0.4 (backup filter), 0.4–0.7, 0.7–1.1, 1.1–2.1, 2.1–3.3, 3.3–4.7, 4.7–5.8, 5.8–9.0 and 9.0–10 μm. The system provides a high resolution size distribution of atmospheric particles. The cascade impactor was operated at a constant flow rate of 28.3 L/min. An iron carapace was placed over the inlet of the impactor to provide protection from rain and to prevent the ingress of coarse resuspended materials. Quartz filters (QMA, Φ81 mm; Whatman, Florham Park, NJ, USA) were used on all stages (Oh et al., 2011), and were baked at 450°C in a furnace before use. The sampling filter was placed at a constant temperature (25 ± 0.5°C) and humidity (35% ± 2% RH) in a glass chamber for equilibration 48–72 hr before and after sampling, and was thereafter weighed (accurate to 0.01 mg) using an electronic microbalance (Type CPA225D, Sartorius, Göttingen, Germany). In order to get rid of the high background values effect of the quartz filters and make sure quality control of the samples, blank samples were
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collected synchronously before the end of the sampling process. PM mass concentrations were determined by gravimetric analysis before and after PM sampling. Each sampling filter was folded (the loaded particles inside) and individually wrapped in aluminum foil bags to avoid material loss. All samples were stored in a refrigerator at − 20°C prior to analysis. All observed results were blank corrected. Half of each filter was cut and digested by a mixture of acids in a microwave digestion system (MARS 5; CEM Corp., Matthews, NC, USA) as follows: the loaded filters were dissolved with 8.1 mL of HNO3 (65%)/H2O2(30%)/HF(40%) (6/2/ 0.1 V/V/V, Suprapur grade, Merck, Germany) in a closed vessel at 180°C for 8 hr; and extracts were filtered through 0.45 μm Polytetrafluoroethylene (PTFE) filters. The net digested solution was diluted to a volume of 25 mL using ultrapure water (MilliQ, 18.2 MΩ cm, Millipore, United States of America) for further metal analysis. To avoid matrix effects, a series of blanks (procedural blanks and field blanks) were prepared using the same digestion method. The reagents for standard solutions used in this study were AR grade. The concentrations of Pb, Cr, Cd, As and Ti were analyzed by an inductively coupled plasma mass spectrometry (ICP-MS) (Agilent 7500, Agilent Technologies, Santa Clara, CA, USA). Calibration was carried out in accordance with the reference external standards (Environmental Calibration Standard, Part 5183–4688; Agilent Technologies) and the instrument was optimized daily as per the manufacturer's manual. The multielement standard stock solution containing 10 or 1000 mg/L of Pb, Cd, Cr, As and Ti in nitric acid was diluted in 2% HNO3 to obtain five calibration standards (1, 10, 25, 50 and 100 μg/L) plus a blank that covered the expected range for the samples. The detection limit of the 5 elements was: Pb (0.0002 μg/L), Cd (0.00008 μg/L), Cr (0.001 μg/L), As (0.0004 μg/L) and Ti (0.00008 μg/L). The recoveries of the 5 elements were in the range of 90%– 110%. The precision was 1–3% RSD (relative standard deviation). More information associated with the instruments and data processing can be found in previous reports (Zhang et al., 2014; Pan and Wang, 2015).
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predominant in winter, and southeasterly or southerly winds are frequent in summer. The sampling site was on a roof of a teaching building at campus of the No. 8 High School of Zhuzhou, Hunan Province (113°06′48″E, 27°52′10″N) (Fig. 1), which is located near an industrial park downwind in winter, and the building is about 20 m above the ground. The distance between the sampling site and the industrial park is within 10 km. The samples were collected approximately every 47.5 hr (starting at 9:00 a.m. and ending at 8:30 a.m. on the third day). The sampling period was from 24 December 2011 to 11 January 2012.
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Changsha
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Zhuzhou city
Xiangtan Zhuzhou
Fig. 1 – Distribution of the sampling site.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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All samples were stored in a refrigerator at 0°C prior to analysis. A solid sample of 0.5000 g was weighed accurately and placed into a PTFE flask. Each sample was digested with 7 mL of HF (Suprapur grade, Merck, Germany) and 5 mL HNO3/HCl(1.25/ 3.75, V/V, Suprapur grade, Merck, Germany), and was capped, placed in a water bath, heated at 90°C for 8 hr, open the lid before cooling the digestion tank to room temperature; followed by digestion with boric acid and 40 mL ultra-pure water for 1 hr (90°C). Again, the lid was opened before the digestion tank was cooled to room temperature and the final digested solution in the PTFE flask was transferred to a volumetric flask and diluted to 1000 mL with ultrapure water. Extracts were filtered through 0.45 μm PTFE filters prior to analysis. This analysis method was based on the OHM (ontario-hydro method, US, EPA). To avoid matrix effects, a series of blanks were prepared using the same digestion method. The concentrations of Pb, Cr, Cd and As were determined by ICP-MS. The source samples analysis process was similar
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t1:1 t1:2 t1:3
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Table 1 – Atmospheric emission source sampling location and number of samples.
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Meteorological parameters (i.e., temperature, wind speed, wind direction, dew point, cloud cover, visibility and precipitation) were collected from the Institute of Meteorological Science of Hunan Province (Table 2, Fig. 2). During the sampling period, the weather conditions were without snow or rain, and the wind force was below 3–4°.
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1.4. Enrichment factors analysis
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Determination of the enrichment factor (EF) for elements in aerosols was been taken into consideration to evaluate anthropogenic versus crustal sources (Wang et al., 2005). The objective of this study was to elucidate the accumulation characteristics of heavy metals in fine mode and coarse mode particles, and to identify the sources of atmospheric heavy metals in Zhuzhou based on the calculated EF. The EF calculation methodology for heavy metals is as follows: EF ¼
ðXi =XR Þaerosol ðXi =XR Þcrust
System
t1:5 t1:6 t1:7 t1:8 t1:9 t1:10 t1:11 t1:12 t1:13 t1:14 t1:15 t1:16 t1:17 t1:18
Zinc smelting system
Sample site
Number
Acid ash Calcined Kiln slag Leaching slag Zinc oxide Lead concentrate Lead acid front ash Lead burning agglomerate Lead coke Dust collector of lead blast furnace Lead slag Lead coal powder Lead zinc oxide Lead water quenching slag
3 3 6 6 6 5 5 5 6 6 5 6 6 5
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Lead smelting system
295 296 297 298 299 300
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1.3. Meteorological data collection
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There are many factories in the industrial park which locates in an upwind direction of the environment sampling point such as non-ferrous smelting companies dominated by lead and zinc smelting, coal-fired power plants, chemical industry, etc. (Zeng et al., 2007); however, the lead and zinc smelting factories significantly outnumber the others. There is only one coal-fired power plant (620 MW) located in the industrial park. According to the air pollution source census data in 2011, the annual output of a lead smelting factory (where samples were collected) was 93,000 ton/year, and the annual output of a zinc smelting factory (where samples were collected) was 280,000 ton/year. To understand the emission of heavy metals from the lead-zinc smelting factories, 73 samples of different kinds and different points within the smelting systems of a lead smelting factory and a zinc smelting factory located in the industrial park were collected (Table 1). The source samples were collected during the air sampling period.
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1.2.1. Sampling site and period
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to that of the environmental samples. Detailed analysis 291 methods can be seen in Section 1.1.2. 292
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ð1Þ
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1.2. Source sampling methods
where, Xi is the targeting element i; XR is a reference element of crustal material; (Xi/XR)aerosol and (Xi/XR)crust refer to as the concentration ratio of element Xi to XR in the aerosol sample and in the crust, respectively. In this study, Ti was used as the reference element and the abundance of elements in the upper continental crust (UCC) was taken from a previous publication (Zhang et al., 2014). EF ≤ 10 indicates heavy metals mainly from natural sources such as earth crust; 10 < EF ≤ 100 indicates moderate anthropogenic enrichment; and EF > 100 is considered to be of anthropogenic origin (Koulousaris et al., 2009). The larger the value, the higher the degree of enrichment (Odabasi et al., 2002).
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2. Results and discussion
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2.1. Mass concentration of aerosol particles in different sizes
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According to Zhuzhou city's air quality daily, PM10 was the main pollutants in the ambient atmosphere (PM2.5 was monitored after 2016). The concentration of PM10 in spring (from March to May), summer (from June to August), autumn (from September to November) and winter (from December to February of the following year) in 2011 was 84.2 ± 30.1, 73.4 ± 28.0, 93.2 ± 53.1, 97.6 ± 43.0 μg/m3, respectively. During the sampling period, the concentration of PM10 was 138.4 ± 43.0 μg/m3, higher than the winter average, which indicated it was representative of the pollution process. The concentration of PM was 177.3 ± 33.2 μg/m3 in this experiment, which was similar to the PM10 concentration in the Chang-Zhu-Tan city clusters (162–191 μg/m3) (Zhang et al., 2014). The concentration level of atmospheric particles was
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Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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t2:1
Table 2 – Meteorological conditions during sampling periods.
t2:3 t2:2
t2:4
Date
Temperature (°C)
Dew point (°C)
Rain fall (mm)
Cloudy
Visibility (km)
t2:5 t2:6 t2:7 t2:8 t2:9 t2:10 t2:11 t2:12 t2:13
24 Dec 2011 9:00–26 Dec 8:30 26 Dec 2011 9:00–28 Dec 8:30 28 Dec 2011 9:00–30 Dec 8:30 30 Dec 2011 9:00–1 Jan 2012 8:30 1 Jan 2012 9:00–3 Jan 8:30 3 Jan 2012 9:00–5 Jan 8:30 5 Jan 2012 9:00–7 Jan 8:30 7 Jan 2012 9:00–9 Jan 8:30 9 Jan 2012 9:00–11 Jan 8:30 a
0–12.2 5.7–12.9 6.1–9.1 5–8.3 4–7.7 1.1–6.9 3.2–6.1 3.5–6.3 5.2–8.5
−9.3 to −2.8 −7–0.3 −0.6–4.4 2.5–4 2.2–5 −6.5–1.1 −2.8–0.5 −3.2 to −0.5 −1.8–0.6
0 0 0–0.01 0–3 0–3 0 0 0 0
0–7 6–8 8–8 7–8 8–8 7–8 8–8 7–8 8–8
6–14 8–15 3–7 0.6–5 0.9–6 1–14 8–12 5–10 3–7
t2:14
a
350 351 352 353 354 355 356 357 358 359 360 361 362 363 364
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Wind Frequency
NNW NW WNW W
Wind Speed (10-1 m/sec)
0.5
2.2. Concentration characteristics of heavy metals in atmospheric particles
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Four heavy metals (Cr, Cd, As and Pb) were measured in the composite mixture of particles. The average concentrations of Cr, As, Cd and Pb were 37.3 ± 8.8 ng/m3, 17.3 ± 8.1 ng/m3, 4.8 ± 3.1 ng/m3 and 141.6 ± 49.1 ng/m3, respectively. The concentrations of heavy metals in aerosols were segregated into two size fractions, and they were designated as fine mode and coarse mode, respectively. The results suggested that (with the exception of Cr (53.4%)) mass percentages of As, Cd and Pb were low in the coarse mode, with values varying from 24.2% for Pb to 27.8% for Cd (Table 3). For the contribution of each particle size fraction to the total metal concentration in aerosols (except for Cr) the fine mode contributed to a larger mass fraction (> 70%) for As, Cd and Pb. The ratios of coarse mode to fine mode for As, Cd and Pb were 0.4, 0.4 and 0.3, respectively, which was similar to the PM coarse to fine mode ratio of 0.5. The ratio of coarse to fine mode for Cr was 1.1.
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the atmosphere, making it difficult for particles to grow to 1.0 μm or larger (Hu et al., 2005). Compared with other's result, this experiment result with particle peak size range of 1.1– 2.1 μm indicated that the aerosol particles in the study area originate predominantly from anthropogenic sources, mainly industrial processes.
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comparable with that of Beijing (184.9–210.9 μg/m3) in winter (Duan et al., 2012). The concentration of fine mode (dae ≤ 2.1 μm) and coarse mode (dae ≥ 2.1 μm) was 114.8 μg/m3 (64.8%) and 62.5 μg/m3 (35.2%), respectively during the experiment period, and the average concentration ratio of coarse mode (dae ≥ 2.1 μm) to fine mode (dae ≤ 2.1 μm) was 0.5. The mean mass concentrations of atmospheric particles in different size ranges over the sampling period are presented in Fig. 3. The spectra of atmospheric particles in the range 0–10 μm showed a typical bimodal distribution, with one peak corresponding to the particle size range of 1.1–2.1 μm and the other to the range of 9–10 μm. Fan et al. (2011) studied the PM in Hangzhou, and found that the size distributions of PM showed bimodal distribution with peaks in the particles with size of <0.49 μm and 3–7.2 μm, respectively. Hu et al. (2005) showed that the mass size distribution of Beijing PM in winter and summer was also bimodal with the peak of fine particles mostly in the 0.32– 0.56 μm range, while the peak of the coarse particles appeared in the 3.2–5.6 μm range. Peak of fine particles at 0.7 μm was identified as a droplet mode, which grew out of the condensation mode by the addition of water and sulfate (John et al., 1990). For small particles, the time required for them to grow to larger than 1.0 μm is much greater than the time it takes to remove in
NNE
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Field blank samples.
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ENE
0.1 0
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WSW
ESE SW
SE SSW
c=14.86%
SSE S
Fig. 2 – Rose diagram of wind direction and wind speed in Zhuzhou.
Fig. 3 – Characteristics of atmospheric particles size distribution in winter.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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6
Element
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19.9 ± 9.6 4.8 ± 2.0 1.3 ± 1.1 34.3 ± 16.9
53.4 27.5 27.8 24.2
usually 0.7 μm or less in size (John et al., 1990). In this experiment, the temperature was low (T < 10°C), the light intensity was weak (Cloudy: 6–8) (Table 2), which was not conducive to the formation of secondary particles. During the sampling period, the northwest wind was predominant, and the sampling site is located in the industrial park downwind and the distance is not more than 10 km. The airborne samples were also collected and analyzed in summer at the same site in 2012. It was a good air quality episode during sampling period, and southerly winds were frequent. The sampling site located in the industrial park upwind. The size distribution of PM and heavy metals was irregular. Therefore, it is considered that the atmospheric particles collected at the sampling site are mainly derived from the primary emission of the industrial park. The correlation coefficients matrix is presented in Table 4. There were good correlations between PM and heavy metals
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The size distribution of the heavy metals was illustrated in Fig. 4. The normalized distribution of As, Cd and Pb showed a bimodal structure and were mainly concentrated in the range of fine mode (1.1–2.1 μm) and coarse mode (9–10 μm), similarly to the PM distribution. The normalized distribution of Cr shows a unimodal structure with higher concentration mainly in the range of coarse mode particles (4.7–5.8 μm). It is generally believed that heavy metals emitted from the source into the atmosphere do not have a chemical conversion process in the ambient atmosphere, but other components in the PM, such as water-soluble ions, undergo an atmospheric chemical process where the atmospheric particles are produced by primary and secondary mixture. The formation of secondary particles in atmosphere is usually occurring under high temperature and high intensity ultraviolet irradiation conditions (Andreas et al., 2003), and the secondary particles are
1.1 0.4 0.4 0.3
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396
46.6 72.5 72.2 75.8
T
395
17.4 ± 3.4 12.5 ± 6.6 3.5 ± 2.0 107.3 ± 33.5
Cr As Cd Pb
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Percentage (%)
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Concentration (ng/m )
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Percentage (%)
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Concentration (ng/m )
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course/fine
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3
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Coarse (≥2.1–3.3 μm)
3
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t3:5
Fine (≤ 1.1–2.1 μm)
R O
t3:4
Table 3 – Fine and coarse mode concentration of heavy metals.
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Fig. 4 – Characteristics of heavy metals size distribution in atmospheric particles in winter.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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Table 4 – Correlation matrix for Cr, As, Cd and Pb during sampling.
t4:3
t4:4
PM
t4:5 t4:6 t4:7 t4:8 t4:9
PM Cr As Cd Pb
t4:10
a
As
Cd
Pb
Industry
1 0.004 0.697 a 0.490 a 0.699 a
Pb
1 0.112 0.12 0.121
1 0.812 a 0.857 a
1 0.911 a
1
Elements from crustal sources are primarily associated with coarse mode while metals from anthropogenic sources accumulated in fine mode (Wang et al., 2005; Hu et al., 2005). The higher EF of As, Cd and Pb in fine mode (230–7398) than that in coarse mode (18–593) indicates that anthropogenic sources are a major source of As, Cd and Pb (Table 5). The smaller the particles size, the higher the degree of enrichment. The EF of Cd
431 432 433 434 435 436 437 438
442 443 444 445 446 447
t5:1 t5:2 t5:3
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430
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429
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428
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427
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Table 5 – Enrichment factors of heavy metals in different fraction particles in winter.
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425
t5:4
Particle size
Cr
As
Cd
Pb
t5:5 t5:6 t5:7 t5:8 t5:9 t5:10 t5:11 t5:12 t5:13 t5:14 t5:15
<0.4 μm 0.4–0.7 μm 0.7–1.1 μm 1.1–2.1 μm 2.1–3.3 μm 3.3–4.7 μm 4.7–5.8 μm 5.8–9 μm 9–10 μm Fine (≤1.1–2.1 μm) Coarse (≥2.1–3.3 μm)
143 85 47 40 20 14 31 6 5 59 14
241 246 225 215 42 19 12 9 11 230 18
8158 8102 7237 7283 1284 573 302 394 475 7398 593
845 976 935 809 121 54 31 40 43 848 56
t5:16 t5:17
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
t6:6
Lead and zinc smelting 24,744.91 14,607.63 18,116.3 2750.93 industry Coal-fired power industry 1639.17 2779 48.75 662.46
t6:7
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
t6:9 t6:10
t6:8
was the largest in fine mode (>103) and coarse mode, especially in fine mode, which indicates that this element was contributed mostly by anthropogenic sources. The following were Pb and As in fine mode, whose EF exceeded 100. Both elements originated mainly from anthropogenic sources.
448
2.4. Source identification
453
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441
424
Cr
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2.3. Enrichment factors analysis
423
Cd
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440
422
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except for Cr. The correlation coefficients matrix showed that As, Cd, and Pb originated from similar sources and that industrial activities relating to fossil fuel combustion and lead and zinc smelting were the main sources of these metals. Duan et al. (2012) analyzed the size distribution of heavy metals in winter in Beijing and concluded that the concentrations of As, Cd and Pb were found mostly in fine mode and were mainly fossil fuel combustion related. Cr was found to be multi-modal and mainly from re-suspended soil, vehicle emissions and coal combustion. There wasn't non-ferrous metal smelting and however much coal was burned for heating in winter in Beijing, then As, Cd and Pb came mainly from fossil fuel. In this experiment, there were lead and zinc smelting factories near the sampling site, then the lead and zinc smelting factories were the important source for As, Cd and Pb in atmosphere. Wei et al. (2009) indicated that the same sources (smelting) and spreading processes, such as aerosols and atmospheric particles from smelting chimneys, demonstrated the same dispersion pattern as As, Cd and Pb.
t6:5
F
.Correlation is significant at the 0.01 level (2-tailed).
As
t6:1 t6:2 t6:3 t6:4
Total emissions
449 450 451 452
There are three coal-fired power plants in Chang-Zhu-Tan city clusters, which are Changsha coal-fired power plant (1200 MW, located in Changsha), Zhuzhou coal-fired power plant (620 MW, located in Zhuzhou), Xiangtan coal-fired power plant (1800 MW, located in Xiangtan). There are 41 lead and zinc smelting factories in Chang-Zhu-Tan city clusters, 5, 34 and 2 in Changsha, Zhuzhou and Xiangtan, respectively. Most of lead and zinc smelting factories are located in industrial park in Zhuzhou. For the whole of China, coal-fired power plants are considered to be important sources of Cd, Pb and Cr in atmospheric particles due to their large amount of coal (Tian et al., 2012). But for Zhuzhou city, the number of lead and zinc smelting factories is much more than that of coal-fired power plant, and the annual output of a lead smelting factory and a zinc smelting factory was more than ninety thousand tons per year. According to the survey of atmosphere heavy metal emissions from coal-fired power industry and from lead and zinc smelting industries in Chang-Zhu-Tan city clusters in 2011 (Table 6), Pb, As, Cd and Cr from the lead and zinc smelting industries were significantly higher than those from coal-fired power plants, indicating that coal-fired power is not the main source of atmospheric heavy metals in this region,
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Table 7 – The concentration of heavy metals in samples from the lead smelting factory (mg/g).
t7:1 t7:2
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Cr
Table 6 – Atmospheric heavy metal emissions from coalfired power industries and from lead and zinc smelting industries in Chang-Zhu-Tan city clusters in 2011 (kg).
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t4:1 t4:2
Lead smelting system
As
Cd
Cr
Pb
Lead concentrate Lead acid front ash Lead burning agglomerate Lead coke Dust collector of lead blast furnace Lead slag Lead coal powder Lead zinc oxide Lead water quenching slag
8.73 97.27 12.2 0.28 83.23 0.91 0.21 3.76 0.26
9.65 121.04 13.19 0.06 102.33 0.29 0 1.91 0.02
0.23 0.04 0.6 1.6 0.04 1.79 0.06 0.05 1.26
28.59 116.15 115 3.09 98.35 28.72 1.15 83.99 6.36
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476
t7:3
t7:4 t7:5 t7:6 t7:7 t7:8 t7:9 t7:10 t7:11 t7:12 t7:13 t7:14 t7:15
8
Cr
Pb
t8:5 t8:6 t8:7 t8:8 t8:9
Acid ash Calcined Kiln slag Leaching slag Zinc oxide
3.48 2.44 0.36 2.59 7.55
3.47 2.28 0 2.34 8.28
0.14 0.22 0.98 0.17 0.07
16.89 13.68 1.48 25.23 68.81
t8:10 t8:11
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
477
501 500
3. Conclusions
502
The size distribution of As, Cd, Pb and Cr in atmospheric particles and factory samples was discussed in this study. Based on the measurements and analyses the following summary and conclusions can be given.
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503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520
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(1) The size distribution of particulate matter was similar between As, Cd and Pb in PM, displaying a bimodal with peak at 1.1–2.1 and 9–10 μm, while the size distribution of Cr in PM was different with those on the lead and zinc smelting affected area. More than 70% of As, Cd and Pb in PM was observed in the fine mode (dae ≤ 2.1 μm) while only 46.6% of Cr in PM was in fine mode. (2) EF values for Cd were the highest, followed by As and Pb. The smaller the particle size, the higher the degree of enrichment. High EF levels of As, Cd and Pb indicated that they were the typical heavy metals in lead and zinc smelting affected area. (3) Most of the As, Cd and Pb from the lead and zinc smelting factories enter into the atmosphere through flue gas, and Cr mainly into the waste residue.
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REFERENCES
Andreas, L., Markku, K., Hans, P., 2003. Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles. Geophys. Res. Lett. 30 (30), 379–394. Bi, X.Y., Feng, X.B., Yang, Y.G., Qiu, G.L., Li, G.H., Li, F.L., et al., 2006. Environmental contamination of heavy metals from zinc smelting areas in Hezhang County, western Guizhou, China. Environ. Int. 32, 883–890. Brook, J.R., Dann, T.F., Bumett, R.T., 1997. The relationship among TSP, PM10, PM2.5 and inorganic constituents of atmospheric particulate matter at multiple Canadian locations. J. Air Waste Manage. Assoc. 47 (l), 2–19. Chen, H.W., 2007. Characteristics and risk assessment of trace metals in airborne particulates from a semiconductor industrial area of Northern Taiwan. Fresenius Environ. Bull. 16 (10), 1288–1294. Chen, B., Stein, A.F., Maldonado, P.G., Sanchez de la Campa, A.M., Gonzalez-Castanedo, Y., Castell, N., et al., 2013. Size distribution and concentrations of heavy metals in atmospheric aerosols originating from industrial emissions as predicted by the HYSPLIT model. Atmos. Environ. 71, 234–244. Cyrys, J., Stolzel, M., Heinrich, J., Kreyling, W.G., Menzel, N., Wittmaack, K., et al., 2003. Elemental composition and sources of fine and ultrafine ambient particles in Erfurt, Germany. Sci. Total Environ. 305 (1–3), 143. Davis, J.G., Weeks, G., Parker, M.B., 1995. Use of deep tillage and liming to reduce zinc toxicity in Peanuts grown on flue dust contaminated land. Soil Technol. 8 (2), 85–95. Duan, J.C., Tan, J.H., 2013. Atmospheric heavy metals and Arsenic in China: situation, sources and control policies. Atmos. Environ. 74, 93–101. Duan, J.C., Tan, J.H., Wang, S.L., Hao, J.M., Chai, F.H., 2012. Size distributions and sources of elements in particulate matter at curbside, urban and rural sites in Beijing. J. Environ. Sci. 24 (1), 87–94. Fan, X.B., Liu, W., Wang, G.H., Lin, J., Fu, Q.Y., Gao, S., et al., 2011. Size distributions of concentrations and chemical components in Hangzhou atmospheric particles. China Environ. Sci. 31 (1), 13–18. Fang, G.C., Huang, C.S., 2011. Atmospheric particulate and metallic elements (Zn, Ni, Cu, Cd and Pb) size distribution at three characteristic sampling sites. Environ. Forensic 12 (3), 191–199. Hu, M., Zhao, Y.L., He, L.Y., Huang, X.F., Tang, X.Y., Yao, X.H., et al., 2005. Mass size distribution of Beijing particulate matters and its inorganic water-soluble ions in winter and summer. Environ. Sci. 26 (4), 1–6. Hu, X., Zhang, Y., Ding, Z., Wang, T., Lian, H., Sun, Y., et al., 2012. Bioaccessibility and health risk of arsenic and heavy metals
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therefore, lead and zinc smelting emissions of heavy metals should be given sufficient attention. The content of the four heavy metals had many differences for every sample site, as shown in Tables 7 and 8. Pb was the highest heavy metal at every point, followed by As, Cd and Cr. In the lead and zinc smelting systems, the behaviors of As and Cd were similar, and the concentration of Cr was larger than any other heavy metal in the water quenching slag, slag and kiln slag after smelting. Previous research has shown that emissions from lead-zinc smelting factories are one of principal pollution sources of heavy metals in atmospheric particles (Bi et al., 2006). Exhaust emissions from industrial metallurgical processes may contain variable quantities of As, Cd, Ni and Pb (Wang et al., 2005). Wei et al. (2009) found smelting was the major source of heavy metal for soil contamination, especially for As, Pb and Cd. So it could be derived that Pb, As and Cd from the sample site downwind of the industrial park were connected with the emissions of the lead and zinc smelting systems. However, Cr from the raw ore mainly flows into ore slag and rarely into the atmosphere. Cr in atmospheric particles was not mainly from lead and zinc smelting. Those results were in accordance with other studies in mining and smelting areas (Wei et al., 2009).
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This work was supported by the National Natural Science Foundation of China (No. 41205093), the National Department Public Benefit Research Foundation (No. 201109005), the Fundamental Research Funds for Central Public Welfare Scientific Research Institutes of China (No. 2016YSKY-025) and National Research Program for Key Issues in Air Pollution Control (No. DQGG0304). We are gratefully indebted to the staff of the Zhuzhou Environmental Monitoring Centers for their help and support during these experiments.
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Table 8 – The concentration of heavy metal in samples from the zinc smelting factory (mg/g).
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Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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D
P
R O
O
F
Rogula-Kozlowska, W., Blaszczak, B., Szopa, S., Klejnowski, K., Sowka, I., Zwozdziak, A., et al., 2013. PM2.5 in the central part of Upper Silesia, Poland: concentrations, elemental composition, and mobility of components. Environ. Monit. Assess. 185: 581–601. https://doi.org/10.1007/s10661-012-2577-1. Shao, L.Y., Hu, Y., Wang, J., Hou, C., Yang, Y.Y., Wu, M.Y., 2013. Particle-induced oxidative damage of indoor PM10 from coal burning homes in the lung cancer area of Xuan Wei, China. Atmos. Environ. 77, 959–967. Tan, J.H., Duan, J.C., 2013. Heavy metals in aerosol in China: pollution, sources, and control strategies. Journal of Graduate University of Chinese. Acad. Sci. 30 (2), 145–155. Tian, H.Z., Cheng, K., Wang, Y., Zhao, D., Lu, L., Jia, W.X., et al., 2012. Temporal and spatial variation characteristics of atmospheric emissions of Cd, Cr, and Pb from coal in China. Atmospheric Environment. Atmos. Environ. 50, 157–163. Toscano, G., Moret, I., Gambaro, A., Barbante, C., Capodaglio, G., 2011. Distribution and seasonal variability of trace elements in atmospheric particulate in the Venice Lagoon. Chemosphere 85 (9), 1518–1524. Wang, H., Stuanes, A.O., 2003. Heavy metal pollution in air-watersoil-plant system of Zhuzhou city, Hunan province, China. Water Air Soil Pollut. 147 (1–4), 79–107. Wang, X., Sato, T., Xing, B., Tamamura, S., Tao, S., 2005. Source identification, size distribution and indicator screening of airborne trace metals in Kanazawa, Japan. J. Aerosol Sci. 36, 197–210. Wei, C.Y., Wang, C., Yang, L., 2009. Characterizing spatial distribution and sources of heavy metals in the soils from mining-smelting activities in Shuikoushan, Hunan Province, China. J. Environ. Sci. 21, 1230–1236. Wilson, M.R., Lightbody, J.H., Donaldson, K., Sales, J., Stone, V., 2002. Interactions between ultrafine particles and transition metals in vivo and in vitro. Toxicol. Appl. Pharmacol. 184 (3), 172–179. Xie, D.H., Yang, T.B., Liu, Z.Y., Wang, H., 2016. Epidemiology of birth defects based on a birth defect surveillance system from 2005 to 2014 in hunan province, China. PLoS One 11. https://doi.org/10.1371/journal.pone.0147280. Ye, X.J., Hu, D., Wang, H.H., Chen, L., Xie, H., Zhang, W., et al., 2015. Atmospheric mercury emissions from China's primary nonferrous metal (Zn, Pb and Cu) smelting during 1949–2010. Atmos. Environ. 103, 331–338. Zeng, C., Liu, P., Zhao, X., 2007. Mechanism of environmental contamination in old industrial base. J. Anhui Agric. Sci. 35 (28), 8974–8976. Zhang, Y.L., Cao, F., 2015. Fine particulate matter (PM2.5) in China at a city level. Sci. Rep. 5, 14884. Zhang, K., Chai, F.H., Zheng, Z.L., Yang, Q., Li, J.S., Wang, J., et al., 2014. Characteristics of atmospheric particles and heavy metals in winter in Chang-Zhu-Tan city clusters, China. J. Environ. Sci. 26 (1), 147–153.
E
T
C
E
R
O R
N C
688
(Cd, Co, Cr, Cu, Ni, Pb, Zn and Mn) in TSP and PM2.5 in Nanjing, China. Atmos. Environ. 57, 146–152. John, W., Wall, S.M., Ondo, J.L., Winklmavr, W., 1990. Models in the size distributions of atmospheric inorganic aerosol. Atmos. Environ. 24A, 2349–2359. Karanasiou, A.A., Sitaras, I.E., Siskos, P.A., Eleftheriadis, K., 2007. Size distribution and sources of trace metals and n-alkanes in the Athens urban aerosol during summer. Atmos. Environ. 41 (11), 2368–2381. Kaupp, H., McLachlan, M.S., 2000. Distribution of polychlorinated dibenzo-P-dioxins and dibenzifurans (PADD/Fs) within the full size range of atmospheric particles. Atmos. Environ. 34, 73–83. Koulousaris, M., Aloupi, M., Angelidis, M.O., 2009. Total metal concentration in atmospheric precipitation from the Northern Agean Sea. Water Air Soil Pollut. 201 (4), 389–403. Lim, J.M., Lee, J.H., Moon, J.H., Chung, Y.S., Kim, K.H., 2010. Airborne PM10 and metals from multifarious sources in an industrial complex area. Atmos. Res. 96 (1), 53–64. Liu, X.T., Zhai, Y.B., Zhu, Y., Liu, Y.N., Chen, H.M., Li, P., et al., 2015. Mass concentration and health risk assessment of heavy metals in size-segregated airborne particulate matter in Changsha. Sci. Total Environ. 517, 215–221. Long, Y.Z., Dai, T.G., Chi, G.X., Yang, L., 2012. Assessment of heavy metals in sediment cores from Xiangjiang River, Chang-Zhu-Tan region, Hunan Province, China. J. Cent. South Univ. 19:2634–2642. https://doi.org/10.1007/s11771-012-1321-x. Lyu, Y., Zhang, K., Chai, F.H., Cheng, T.T., Yang, Q., Zheng, Z.L., et al., 2017. Atmospheric size-resolved trace elements in a city affected by nonferrous metal smelting: indications of respiratory deposition and health risk. Environ. Pollut. 224, 559–571. Masiol, M., Squizzato, S., Ceccato, D., Pavoni, B., 2015. The size distribution of chemical elements of atmospheric aerosol at a semi-rural coastal site in Venice (Italy). The role of atmospheric circulation. Chemosphere 119, 400–406. Mohanral, R., Azeez, P.A., Priscilla, T., 2004. Heavy metal in airborne particulate matter of urban coimbatore. Arch. Environ. Contam. Toxicol. 47B, 162–167. Odabasi, M., Muezzinoglu, A., Bozlaker, A., 2002. Ambient concentrations and dry deposition fluxes of trace elements in Izmir, Turkey. Atmos. Environ. 36 (38), 5841–5851. Oh, M.S., Lee, T.J., Kim, D.S., 2011. Quantitative source apportionment of size-segregated particulate matter at urbanized local site in Korea. Aerosol Air Qual. Res. 11, 247–264. Pan, Y.P., Wang, Y.S., 2015. Atmospheric wet and dry deposition of trace elements at 10 sites in Northern China. Atmos. Chem. Phys. 15 (2), 951–972. Pandey, P., Patel, D.K., Khan, A.H., Barman, S.C., Murthy, R.C., Kisku, G.C., 2013. Temporal distribution of fine particulates (PM2.5, PM10), potentially toxic metals, PAHs and Metal-bound carcinogenic risk in the population of Lucknow City, India. J. Environ. Sci. Health A Tox. Hazard. Subst. Environ. Eng. 48 (7), 730–745.
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Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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Available online at www.sciencedirect.com
ScienceDirect www.elsevier.com/locate/jes
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Kai Zhang1,⁎, Fahe Chai1 , Zilong Zheng 1,2 , Qing Yang1,2 , Xuecai Zhong3 , Khanneh Wadinga Fomba4 , Guangzhu Zhou2
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Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area
1. State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China 2. College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China 3. Zhuzhou Environment Monitoring Center, Zhuzhou 412000, China 4. Leibniz-Institute for Tropospheric Research (TROPOS), Leipzig 04318, Germany
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Article history:
In order to understand the size distribution and the main kind of heavy metals in particulate
16 21
Received 25 September 2017
matter on the lead and zinc smelting affected area, particulate matter (PM) and the source
17 22
Revised 20 April 2018
samples were collected in Zhuzhou, Hunan Province from December 2011 to January 2012 and
18 23
Accepted 20 April 2018
the results were discussed and interpreted. Atmospheric particles were collected with different
19 24
Available online xxxx
sizes by a cascade impactor. The concentrations of heavy metals in atmospheric particles of
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Keywords:
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Heavy metals
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Lead and zinc smelting
Size distribution
concentration of PM, chromium (Cr), arsenic (As), cadmium (Cd) and lead (Pb) in PM was 177.3 ± 33.2 μg/m3, 37.3 ± 8.8 ng/m3, 17.3 ± 8.1 ng/m3, 4.8 ± 3.1 ng/m3 and 141.6 ± 49.1 ng/m3,
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respectively. The size distribution of PM displayed a bimodal distribution; the maximum PM
Pollution characteristics
size distribution was at 1.1–2.1 μm, followed by 9–10 μm. The size distribution of As, Cd and Pb in PM was similar to the distribution of the PM mass, with peaks observed at the range of 1.1–2.1 μm and 9–10 μm ranges while for Cr, only a single-mode at 4.7–5.8 μm was observed. PM (64.7%), As (72.5%), Cd (72.2%) and Pb (75.8%) were associated with the fine mode below 2.1 μm,
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coupled plasma mass spectrometry (ICP-MS). The results indicated that the average
Atmospheric particulate matter
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different sizes, collected from the air and from factories, were measured using an inductively
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respectively, while Cr (46.6%) was associated with the coarse mode. The size distribution characteristics, enrichment factor, correlation coefficient values, source information and the analysis of source samples showed that As, Cd and Pb in PM were the typical heavy metal in lead and zinc smelting affected areas, which originated mainly from lead and zinc smelting Q4
sources. © 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences.
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Introduction
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Most heavy metals in the atmosphere are found in almost all aerosol size fractions, and their concentration and size
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Published by Elsevier B.V.
distribution are controlled by natural (crustal minerals, forest fires and oceans) and anthropogenic emissions (such as fossil fuel combustion and industrial processes) into the atmosphere as reported by many investigators (Shao et al., 2013; Duan and
⁎ Corresponding author. E-mail: [email protected]. (Kai Zhang).
https://doi.org/10.1016/j.jes.2018.04.018 1001-0742 © 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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1. Experimental methods
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1.1. Experimental methods of environment sampling
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1.1.1. Study area and sampling site
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Guangdong and Guangxi. These five Pb and zinc mining and processing bases account for more than 85% of total Pb output, and 95% of total Zn output in China, respectively. Hunan Province is famous as the “hometown of non-ferrous metal smelting”. The emissions from non-ferrous smelting in Hunan have been one of the main sources of heavy metals in the environment (Wei et al., 2009; Duan and Tan, 2013; Xie et al., 2016). Non-ferrous smelting activity has caused serious heavy metal pollution in surrounding districts, which has caused significant health and ecological risks (Lyu et al., 2017). Previous studies have not been able to provide a clear illustration of heavy metal variation in areas where intensive non-ferrous smelting activities have occurred, nor have been able to interpret the possible contamination-source relationship. Knowledge on the size of the atmospheric particles and their relationship to heavy metals is vital for understanding the characteristics of atmospheric heavy metals of the lead and zinc smelting affected regions. Chang-Zhu-Tan city clusters is a new urban agglomeration in central China, which is the first two-type social demonstration city group, i.e., environment-friendly and resourcesaving. Zhuzhou, the second largest city in Hunan province, is an important part of Chang-Zhu-Tan city clusters. It is one of the industrial regions in South China where non-ferrous smelting activities have developed rapidly since the 1950s (Ye et al., 2015), but many non-ferrous factories have closed in recent years due to the high demands required for environmental protection. Therefore the heavy metal pollution was very serious around the environment (Long et al., 2012). Wang and Stuanes (2003) studied the heavy metal pollution in air– water–soil–plant system of Zhuzhou city. Few studies on source identification and size distribution of heavy metals in atmospheric particles have been carried out in Zhuzhou. To understand the typical components of heavy metals in the atmosphere, we collected and analyzed the samplings in the atmospheric environment and from two non-ferrous smelting factories (lead and zinc smelting factories). The data obtained are important to understand the level of pollution and the type of heavy metals affected by the lead and zinc smelting factory. These results can be used to provide scientific evidence for setting up an air pollution control strategy. The first batch of elements identified in the “12th Five Year Plan on Heavy Metal's Comprehensive Prevention and Control” approved by the State Council were lead (Pb), mercury (Hg), chromium (Cr), cadmium (Cd) and arsenic (As). Mercury usually exists in a gaseous form in the atmosphere so that the concentration of mercury in PM is low. Although As is not a heavy metal (metalloid element), considering its negative health impacts it was regarded as a heavy metal and discussed as part of the study. Based on above, this study focused on the these four heavy metals.
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C
62
Tan, 2013; Pan and Wang, 2015). Particulate matters (PMs) are a mixture of primary and secondary aerosols and usually have bimodal mass distribution, which appears in both fine particulates (aerodynamic diameter less than 2.5 μm in) and coarse particulates (aerodynamic diameter between 2.5 and 10 μm), separately (Karanasiou et al., 2007). In general, fine particles carry higher concentrations of toxic metals than coarse particles (Fang and Huang, 2011). As particle size decreases, the specific surface (the surface area per unit volume (or mass)) increases, which makes harmful heavy metals to be easier absorbed by PM (Kaupp and McLachlan, 2000). Heavy metals associated with inhalable particulates have also been shown to increase numerous diseases such as lung or cardiopulmonary injuries (Hu et al., 2012; Pandey et al., 2013; Xie et al., 2016). Fine particles are able to penetrate into the lung, and consequently impair human health. Thus, much attention has been focused on the relationship between the heavy metal content and size of PM (Wilson et al., 2002; Liu et al., 2015; Masiol et al., 2015; Rogula-Kozlowska et al., 2013). Mohanral et al. (2004) indicated that about 70%–90% of heavy metals are contained by PM10, and the smaller the particles size, the higher the concentration of heavy metals. Brook et al. (1997) showed that heavy metals in PM2.5 were potentially harmful to the human body. Cyrys et al. (2003) and Duan and Tan (2013) hold that the content of heavy metals was higher in fine PM than that in coarse PM; poisonous and harmful heavy metals, such as Pb, Cd, Ni, Mn, V, Zn etc., were mainly adsorbed by fine particles. Heavy metals are released into the atmosphere by the combustion of fossil fuels, vehicle emission, high temperature industrial activities, metal mining and smelting, waste incineration and other human activities. Heavy metals in the atmosphere are frequently associated with specific pollutant sources, and these are often used as tracers to identify the source of atmospheric particles (Duan and Tan, 2013; Chen et al., 2013). Many studies have been undertaken to reveal PM and its associated heavy metal concentrations in the atmosphere surrounding industrial areas (Chen, 2007; Lim et al., 2010). Toscano et al. (2011) revealed that the coarse particles were thought to be formed by low temperature combustion, crustal erosion and road dust resuspension, while fine particles were believed to be principally emitted from anthropogenic sources including combustion, high-temperature industrial activities and automotive traffic. Wei et al. (2009) found that metal mining and smelting activities were the major sources of heavy metals entering the environment. Waste gas pollutants from nonferrous metal smelting are one of the main sources of heavy metal pollution in atmospheric particles (Davis et al., 1995). From recent report, the most severe polluted areas locate in northern China (Zhang and Cao, 2015). But the concentrations of Pb, Cr and Cd in PM in southern cities were 12.3%, 7.3% and 171%, higher respectively than those in northern cities, while the concentration of As in PM in northern cities was higher 65.5% than those in southerner cities according to the data obtained in 44 major cities in China during the last 10 years (Tan and Duan, 2013). Non-ferrous metal mining and smelting plants are one of the main sources of atmospheric heavy metals and are widely distributed in China (Wei et al., 2009). Lead and zinc smelting belong to non-ferrous smelting. There are five lead and zinc production bases: the northeast, the northwest, Yunnan and Sichuan, the Hunan, and the
N
61
U
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J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 8 ) XXX –XXX
121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170
The weather of Zhuzhou is influenced by the prevalence of a 175 subtropical humid monsoon climate. Northwesterly winds are 176
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213
F
189
1.1.2. Air sample collection, pretreatment and instrumental analysis A total of 81 samples were collected using an Anderson eightstage cascade impactor (Model 20–800, Tisch Environmental Inc., Cleves, OH, U.S.A), which provides a high-resolution size distribution of atmospheric particles. The atmospheric particles were separated into the following size ranges based on particle aerodynamic diameter (dae): < 0.4 (backup filter), 0.4–0.7, 0.7–1.1, 1.1–2.1, 2.1–3.3, 3.3–4.7, 4.7–5.8, 5.8–9.0 and 9.0–10 μm. The system provides a high resolution size distribution of atmospheric particles. The cascade impactor was operated at a constant flow rate of 28.3 L/min. An iron carapace was placed over the inlet of the impactor to provide protection from rain and to prevent the ingress of coarse resuspended materials. Quartz filters (QMA, Φ81 mm; Whatman, Florham Park, NJ, USA) were used on all stages (Oh et al., 2011), and were baked at 450°C in a furnace before use. The sampling filter was placed at a constant temperature (25 ± 0.5°C) and humidity (35% ± 2% RH) in a glass chamber for equilibration 48–72 hr before and after sampling, and was thereafter weighed (accurate to 0.01 mg) using an electronic microbalance (Type CPA225D, Sartorius, Göttingen, Germany). In order to get rid of the high background values effect of the quartz filters and make sure quality control of the samples, blank samples were
O
188
R O
187
P
186
D
185
collected synchronously before the end of the sampling process. PM mass concentrations were determined by gravimetric analysis before and after PM sampling. Each sampling filter was folded (the loaded particles inside) and individually wrapped in aluminum foil bags to avoid material loss. All samples were stored in a refrigerator at − 20°C prior to analysis. All observed results were blank corrected. Half of each filter was cut and digested by a mixture of acids in a microwave digestion system (MARS 5; CEM Corp., Matthews, NC, USA) as follows: the loaded filters were dissolved with 8.1 mL of HNO3 (65%)/H2O2(30%)/HF(40%) (6/2/ 0.1 V/V/V, Suprapur grade, Merck, Germany) in a closed vessel at 180°C for 8 hr; and extracts were filtered through 0.45 μm Polytetrafluoroethylene (PTFE) filters. The net digested solution was diluted to a volume of 25 mL using ultrapure water (MilliQ, 18.2 MΩ cm, Millipore, United States of America) for further metal analysis. To avoid matrix effects, a series of blanks (procedural blanks and field blanks) were prepared using the same digestion method. The reagents for standard solutions used in this study were AR grade. The concentrations of Pb, Cr, Cd, As and Ti were analyzed by an inductively coupled plasma mass spectrometry (ICP-MS) (Agilent 7500, Agilent Technologies, Santa Clara, CA, USA). Calibration was carried out in accordance with the reference external standards (Environmental Calibration Standard, Part 5183–4688; Agilent Technologies) and the instrument was optimized daily as per the manufacturer's manual. The multielement standard stock solution containing 10 or 1000 mg/L of Pb, Cd, Cr, As and Ti in nitric acid was diluted in 2% HNO3 to obtain five calibration standards (1, 10, 25, 50 and 100 μg/L) plus a blank that covered the expected range for the samples. The detection limit of the 5 elements was: Pb (0.0002 μg/L), Cd (0.00008 μg/L), Cr (0.001 μg/L), As (0.0004 μg/L) and Ti (0.00008 μg/L). The recoveries of the 5 elements were in the range of 90%– 110%. The precision was 1–3% RSD (relative standard deviation). More information associated with the instruments and data processing can be found in previous reports (Zhang et al., 2014; Pan and Wang, 2015).
E
184
T
183
C
182
E
181
R
180
O R
179
predominant in winter, and southeasterly or southerly winds are frequent in summer. The sampling site was on a roof of a teaching building at campus of the No. 8 High School of Zhuzhou, Hunan Province (113°06′48″E, 27°52′10″N) (Fig. 1), which is located near an industrial park downwind in winter, and the building is about 20 m above the ground. The distance between the sampling site and the industrial park is within 10 km. The samples were collected approximately every 47.5 hr (starting at 9:00 a.m. and ending at 8:30 a.m. on the third day). The sampling period was from 24 December 2011 to 11 January 2012.
N C
178
Changsha
U
177
Zhuzhou city
Xiangtan Zhuzhou
Fig. 1 – Distribution of the sampling site.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251
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273
All samples were stored in a refrigerator at 0°C prior to analysis. A solid sample of 0.5000 g was weighed accurately and placed into a PTFE flask. Each sample was digested with 7 mL of HF (Suprapur grade, Merck, Germany) and 5 mL HNO3/HCl(1.25/ 3.75, V/V, Suprapur grade, Merck, Germany), and was capped, placed in a water bath, heated at 90°C for 8 hr, open the lid before cooling the digestion tank to room temperature; followed by digestion with boric acid and 40 mL ultra-pure water for 1 hr (90°C). Again, the lid was opened before the digestion tank was cooled to room temperature and the final digested solution in the PTFE flask was transferred to a volumetric flask and diluted to 1000 mL with ultrapure water. Extracts were filtered through 0.45 μm PTFE filters prior to analysis. This analysis method was based on the OHM (ontario-hydro method, US, EPA). To avoid matrix effects, a series of blanks were prepared using the same digestion method. The concentrations of Pb, Cr, Cd and As were determined by ICP-MS. The source samples analysis process was similar
264 265 266 267 268 269 270
274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290
t1:1 t1:2 t1:3
C
263
E
262
R R
261
O
260
C
259
Table 1 – Atmospheric emission source sampling location and number of samples.
N
258
Meteorological parameters (i.e., temperature, wind speed, wind direction, dew point, cloud cover, visibility and precipitation) were collected from the Institute of Meteorological Science of Hunan Province (Table 2, Fig. 2). During the sampling period, the weather conditions were without snow or rain, and the wind force was below 3–4°.
294
1.4. Enrichment factors analysis
F
1.2.2. Sources samples pretreatment and instrumental analysis
257
293
Determination of the enrichment factor (EF) for elements in aerosols was been taken into consideration to evaluate anthropogenic versus crustal sources (Wang et al., 2005). The objective of this study was to elucidate the accumulation characteristics of heavy metals in fine mode and coarse mode particles, and to identify the sources of atmospheric heavy metals in Zhuzhou based on the calculated EF. The EF calculation methodology for heavy metals is as follows: EF ¼
ðXi =XR Þaerosol ðXi =XR Þcrust
System
t1:5 t1:6 t1:7 t1:8 t1:9 t1:10 t1:11 t1:12 t1:13 t1:14 t1:15 t1:16 t1:17 t1:18
Zinc smelting system
Sample site
Number
Acid ash Calcined Kiln slag Leaching slag Zinc oxide Lead concentrate Lead acid front ash Lead burning agglomerate Lead coke Dust collector of lead blast furnace Lead slag Lead coal powder Lead zinc oxide Lead water quenching slag
3 3 6 6 6 5 5 5 6 6 5 6 6 5
U
t1:4
Lead smelting system
295 296 297 298 299 300
O
272
256
1.3. Meteorological data collection
R O
271
There are many factories in the industrial park which locates in an upwind direction of the environment sampling point such as non-ferrous smelting companies dominated by lead and zinc smelting, coal-fired power plants, chemical industry, etc. (Zeng et al., 2007); however, the lead and zinc smelting factories significantly outnumber the others. There is only one coal-fired power plant (620 MW) located in the industrial park. According to the air pollution source census data in 2011, the annual output of a lead smelting factory (where samples were collected) was 93,000 ton/year, and the annual output of a zinc smelting factory (where samples were collected) was 280,000 ton/year. To understand the emission of heavy metals from the lead-zinc smelting factories, 73 samples of different kinds and different points within the smelting systems of a lead smelting factory and a zinc smelting factory located in the industrial park were collected (Table 1). The source samples were collected during the air sampling period.
P
1.2.1. Sampling site and period
254
D
253 255
to that of the environmental samples. Detailed analysis 291 methods can be seen in Section 1.1.2. 292
301 302 303 304 305 306 307 308 309
ð1Þ
E
1.2. Source sampling methods
where, Xi is the targeting element i; XR is a reference element of crustal material; (Xi/XR)aerosol and (Xi/XR)crust refer to as the concentration ratio of element Xi to XR in the aerosol sample and in the crust, respectively. In this study, Ti was used as the reference element and the abundance of elements in the upper continental crust (UCC) was taken from a previous publication (Zhang et al., 2014). EF ≤ 10 indicates heavy metals mainly from natural sources such as earth crust; 10 < EF ≤ 100 indicates moderate anthropogenic enrichment; and EF > 100 is considered to be of anthropogenic origin (Koulousaris et al., 2009). The larger the value, the higher the degree of enrichment (Odabasi et al., 2002).
311 310
2. Results and discussion
325 324
2.1. Mass concentration of aerosol particles in different sizes
326
According to Zhuzhou city's air quality daily, PM10 was the main pollutants in the ambient atmosphere (PM2.5 was monitored after 2016). The concentration of PM10 in spring (from March to May), summer (from June to August), autumn (from September to November) and winter (from December to February of the following year) in 2011 was 84.2 ± 30.1, 73.4 ± 28.0, 93.2 ± 53.1, 97.6 ± 43.0 μg/m3, respectively. During the sampling period, the concentration of PM10 was 138.4 ± 43.0 μg/m3, higher than the winter average, which indicated it was representative of the pollution process. The concentration of PM was 177.3 ± 33.2 μg/m3 in this experiment, which was similar to the PM10 concentration in the Chang-Zhu-Tan city clusters (162–191 μg/m3) (Zhang et al., 2014). The concentration level of atmospheric particles was
327
T
252
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
312 313 314 315 316 317 318 319 320 321 322 323 Q7
328 329 330 331 332 333 334 335 336 337 338 339 340
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t2:1
Table 2 – Meteorological conditions during sampling periods.
t2:3 t2:2
t2:4
Date
Temperature (°C)
Dew point (°C)
Rain fall (mm)
Cloudy
Visibility (km)
t2:5 t2:6 t2:7 t2:8 t2:9 t2:10 t2:11 t2:12 t2:13
24 Dec 2011 9:00–26 Dec 8:30 26 Dec 2011 9:00–28 Dec 8:30 28 Dec 2011 9:00–30 Dec 8:30 30 Dec 2011 9:00–1 Jan 2012 8:30 1 Jan 2012 9:00–3 Jan 8:30 3 Jan 2012 9:00–5 Jan 8:30 5 Jan 2012 9:00–7 Jan 8:30 7 Jan 2012 9:00–9 Jan 8:30 9 Jan 2012 9:00–11 Jan 8:30 a
0–12.2 5.7–12.9 6.1–9.1 5–8.3 4–7.7 1.1–6.9 3.2–6.1 3.5–6.3 5.2–8.5
−9.3 to −2.8 −7–0.3 −0.6–4.4 2.5–4 2.2–5 −6.5–1.1 −2.8–0.5 −3.2 to −0.5 −1.8–0.6
0 0 0–0.01 0–3 0–3 0 0 0 0
0–7 6–8 8–8 7–8 8–8 7–8 8–8 7–8 8–8
6–14 8–15 3–7 0.6–5 0.9–6 1–14 8–12 5–10 3–7
t2:14
a
350 351 352 353 354 355 356 357 358 359 360 361 362 363 364
O
F
Wind Frequency
NNW NW WNW W
Wind Speed (10-1 m/sec)
0.5
2.2. Concentration characteristics of heavy metals in atmospheric particles
371
Four heavy metals (Cr, Cd, As and Pb) were measured in the composite mixture of particles. The average concentrations of Cr, As, Cd and Pb were 37.3 ± 8.8 ng/m3, 17.3 ± 8.1 ng/m3, 4.8 ± 3.1 ng/m3 and 141.6 ± 49.1 ng/m3, respectively. The concentrations of heavy metals in aerosols were segregated into two size fractions, and they were designated as fine mode and coarse mode, respectively. The results suggested that (with the exception of Cr (53.4%)) mass percentages of As, Cd and Pb were low in the coarse mode, with values varying from 24.2% for Pb to 27.8% for Cd (Table 3). For the contribution of each particle size fraction to the total metal concentration in aerosols (except for Cr) the fine mode contributed to a larger mass fraction (> 70%) for As, Cd and Pb. The ratios of coarse mode to fine mode for As, Cd and Pb were 0.4, 0.4 and 0.3, respectively, which was similar to the PM coarse to fine mode ratio of 0.5. The ratio of coarse to fine mode for Cr was 1.1.
373
P
R O
365
D
349
the atmosphere, making it difficult for particles to grow to 1.0 μm or larger (Hu et al., 2005). Compared with other's result, this experiment result with particle peak size range of 1.1– 2.1 μm indicated that the aerosol particles in the study area originate predominantly from anthropogenic sources, mainly industrial processes.
E
348
T
347
C
346
E
345
R
344
O R
343
N
N C
342
comparable with that of Beijing (184.9–210.9 μg/m3) in winter (Duan et al., 2012). The concentration of fine mode (dae ≤ 2.1 μm) and coarse mode (dae ≥ 2.1 μm) was 114.8 μg/m3 (64.8%) and 62.5 μg/m3 (35.2%), respectively during the experiment period, and the average concentration ratio of coarse mode (dae ≥ 2.1 μm) to fine mode (dae ≤ 2.1 μm) was 0.5. The mean mass concentrations of atmospheric particles in different size ranges over the sampling period are presented in Fig. 3. The spectra of atmospheric particles in the range 0–10 μm showed a typical bimodal distribution, with one peak corresponding to the particle size range of 1.1–2.1 μm and the other to the range of 9–10 μm. Fan et al. (2011) studied the PM in Hangzhou, and found that the size distributions of PM showed bimodal distribution with peaks in the particles with size of <0.49 μm and 3–7.2 μm, respectively. Hu et al. (2005) showed that the mass size distribution of Beijing PM in winter and summer was also bimodal with the peak of fine particles mostly in the 0.32– 0.56 μm range, while the peak of the coarse particles appeared in the 3.2–5.6 μm range. Peak of fine particles at 0.7 μm was identified as a droplet mode, which grew out of the condensation mode by the addition of water and sulfate (John et al., 1990). For small particles, the time required for them to grow to larger than 1.0 μm is much greater than the time it takes to remove in
NNE
0.4
NE
0.3
U
341
Field blank samples.
0.2
ENE
0.1 0
E
WSW
ESE SW
SE SSW
c=14.86%
SSE S
Fig. 2 – Rose diagram of wind direction and wind speed in Zhuzhou.
Fig. 3 – Characteristics of atmospheric particles size distribution in winter.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
366 367 368 369 370
372
374 375 376 377 378 379 380 381 382 383 384 385 386 387 388
6
Element
397 398 399 400 401 402 403 404
19.9 ± 9.6 4.8 ± 2.0 1.3 ± 1.1 34.3 ± 16.9
53.4 27.5 27.8 24.2
usually 0.7 μm or less in size (John et al., 1990). In this experiment, the temperature was low (T < 10°C), the light intensity was weak (Cloudy: 6–8) (Table 2), which was not conducive to the formation of secondary particles. During the sampling period, the northwest wind was predominant, and the sampling site is located in the industrial park downwind and the distance is not more than 10 km. The airborne samples were also collected and analyzed in summer at the same site in 2012. It was a good air quality episode during sampling period, and southerly winds were frequent. The sampling site located in the industrial park upwind. The size distribution of PM and heavy metals was irregular. Therefore, it is considered that the atmospheric particles collected at the sampling site are mainly derived from the primary emission of the industrial park. The correlation coefficients matrix is presented in Table 4. There were good correlations between PM and heavy metals
F
The size distribution of the heavy metals was illustrated in Fig. 4. The normalized distribution of As, Cd and Pb showed a bimodal structure and were mainly concentrated in the range of fine mode (1.1–2.1 μm) and coarse mode (9–10 μm), similarly to the PM distribution. The normalized distribution of Cr shows a unimodal structure with higher concentration mainly in the range of coarse mode particles (4.7–5.8 μm). It is generally believed that heavy metals emitted from the source into the atmosphere do not have a chemical conversion process in the ambient atmosphere, but other components in the PM, such as water-soluble ions, undergo an atmospheric chemical process where the atmospheric particles are produced by primary and secondary mixture. The formation of secondary particles in atmosphere is usually occurring under high temperature and high intensity ultraviolet irradiation conditions (Andreas et al., 2003), and the secondary particles are
1.1 0.4 0.4 0.3
E
396
46.6 72.5 72.2 75.8
T
395
17.4 ± 3.4 12.5 ± 6.6 3.5 ± 2.0 107.3 ± 33.5
Cr As Cd Pb
C
394
Percentage (%)
E
393
Concentration (ng/m )
R R
392
Percentage (%)
O
391
Concentration (ng/m )
C
390
course/fine
N
389
3
U
t3:6 t3:7 t3:8 t3:9
Coarse (≥2.1–3.3 μm)
3
O
t3:5
Fine (≤ 1.1–2.1 μm)
R O
t3:4
Table 3 – Fine and coarse mode concentration of heavy metals.
P
t3:3 t3:2
D
t3:1
J O U RN A L OF E N V I RO N ME N TA L S CIE N CE S X X (2 0 1 8 ) XXX –XXX
Fig. 4 – Characteristics of heavy metals size distribution in atmospheric particles in winter.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420
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Table 4 – Correlation matrix for Cr, As, Cd and Pb during sampling.
t4:3
t4:4
PM
t4:5 t4:6 t4:7 t4:8 t4:9
PM Cr As Cd Pb
t4:10
a
As
Cd
Pb
Industry
1 0.004 0.697 a 0.490 a 0.699 a
Pb
1 0.112 0.12 0.121
1 0.812 a 0.857 a
1 0.911 a
1
Elements from crustal sources are primarily associated with coarse mode while metals from anthropogenic sources accumulated in fine mode (Wang et al., 2005; Hu et al., 2005). The higher EF of As, Cd and Pb in fine mode (230–7398) than that in coarse mode (18–593) indicates that anthropogenic sources are a major source of As, Cd and Pb (Table 5). The smaller the particles size, the higher the degree of enrichment. The EF of Cd
431 432 433 434 435 436 437 438
442 443 444 445 446 447
t5:1 t5:2 t5:3
C
430
E
429
R
428
O R
427
N C
426
Table 5 – Enrichment factors of heavy metals in different fraction particles in winter.
U
425
t5:4
Particle size
Cr
As
Cd
Pb
t5:5 t5:6 t5:7 t5:8 t5:9 t5:10 t5:11 t5:12 t5:13 t5:14 t5:15
<0.4 μm 0.4–0.7 μm 0.7–1.1 μm 1.1–2.1 μm 2.1–3.3 μm 3.3–4.7 μm 4.7–5.8 μm 5.8–9 μm 9–10 μm Fine (≤1.1–2.1 μm) Coarse (≥2.1–3.3 μm)
143 85 47 40 20 14 31 6 5 59 14
241 246 225 215 42 19 12 9 11 230 18
8158 8102 7237 7283 1284 573 302 394 475 7398 593
845 976 935 809 121 54 31 40 43 848 56
t5:16 t5:17
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
t6:6
Lead and zinc smelting 24,744.91 14,607.63 18,116.3 2750.93 industry Coal-fired power industry 1639.17 2779 48.75 662.46
t6:7
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
t6:9 t6:10
t6:8
was the largest in fine mode (>103) and coarse mode, especially in fine mode, which indicates that this element was contributed mostly by anthropogenic sources. The following were Pb and As in fine mode, whose EF exceeded 100. Both elements originated mainly from anthropogenic sources.
448
2.4. Source identification
453
O
441
424
Cr
R O
2.3. Enrichment factors analysis
423
Cd
P
440
422
T
439
except for Cr. The correlation coefficients matrix showed that As, Cd, and Pb originated from similar sources and that industrial activities relating to fossil fuel combustion and lead and zinc smelting were the main sources of these metals. Duan et al. (2012) analyzed the size distribution of heavy metals in winter in Beijing and concluded that the concentrations of As, Cd and Pb were found mostly in fine mode and were mainly fossil fuel combustion related. Cr was found to be multi-modal and mainly from re-suspended soil, vehicle emissions and coal combustion. There wasn't non-ferrous metal smelting and however much coal was burned for heating in winter in Beijing, then As, Cd and Pb came mainly from fossil fuel. In this experiment, there were lead and zinc smelting factories near the sampling site, then the lead and zinc smelting factories were the important source for As, Cd and Pb in atmosphere. Wei et al. (2009) indicated that the same sources (smelting) and spreading processes, such as aerosols and atmospheric particles from smelting chimneys, demonstrated the same dispersion pattern as As, Cd and Pb.
t6:5
F
.Correlation is significant at the 0.01 level (2-tailed).
As
t6:1 t6:2 t6:3 t6:4
Total emissions
449 450 451 452
There are three coal-fired power plants in Chang-Zhu-Tan city clusters, which are Changsha coal-fired power plant (1200 MW, located in Changsha), Zhuzhou coal-fired power plant (620 MW, located in Zhuzhou), Xiangtan coal-fired power plant (1800 MW, located in Xiangtan). There are 41 lead and zinc smelting factories in Chang-Zhu-Tan city clusters, 5, 34 and 2 in Changsha, Zhuzhou and Xiangtan, respectively. Most of lead and zinc smelting factories are located in industrial park in Zhuzhou. For the whole of China, coal-fired power plants are considered to be important sources of Cd, Pb and Cr in atmospheric particles due to their large amount of coal (Tian et al., 2012). But for Zhuzhou city, the number of lead and zinc smelting factories is much more than that of coal-fired power plant, and the annual output of a lead smelting factory and a zinc smelting factory was more than ninety thousand tons per year. According to the survey of atmosphere heavy metal emissions from coal-fired power industry and from lead and zinc smelting industries in Chang-Zhu-Tan city clusters in 2011 (Table 6), Pb, As, Cd and Cr from the lead and zinc smelting industries were significantly higher than those from coal-fired power plants, indicating that coal-fired power is not the main source of atmospheric heavy metals in this region,
454
Table 7 – The concentration of heavy metals in samples from the lead smelting factory (mg/g).
t7:1 t7:2
D
421
Cr
Table 6 – Atmospheric heavy metal emissions from coalfired power industries and from lead and zinc smelting industries in Chang-Zhu-Tan city clusters in 2011 (kg).
E
t4:1 t4:2
Lead smelting system
As
Cd
Cr
Pb
Lead concentrate Lead acid front ash Lead burning agglomerate Lead coke Dust collector of lead blast furnace Lead slag Lead coal powder Lead zinc oxide Lead water quenching slag
8.73 97.27 12.2 0.28 83.23 0.91 0.21 3.76 0.26
9.65 121.04 13.19 0.06 102.33 0.29 0 1.91 0.02
0.23 0.04 0.6 1.6 0.04 1.79 0.06 0.05 1.26
28.59 116.15 115 3.09 98.35 28.72 1.15 83.99 6.36
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476
t7:3
t7:4 t7:5 t7:6 t7:7 t7:8 t7:9 t7:10 t7:11 t7:12 t7:13 t7:14 t7:15
8
Cr
Pb
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Acid ash Calcined Kiln slag Leaching slag Zinc oxide
3.48 2.44 0.36 2.59 7.55
3.47 2.28 0 2.34 8.28
0.14 0.22 0.98 0.17 0.07
16.89 13.68 1.48 25.23 68.81
t8:10 t8:11
Cr: chromium; As: arsenic; Cd: cadmium; Pb: lead.
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3. Conclusions
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The size distribution of As, Cd, Pb and Cr in atmospheric particles and factory samples was discussed in this study. Based on the measurements and analyses the following summary and conclusions can be given.
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(1) The size distribution of particulate matter was similar between As, Cd and Pb in PM, displaying a bimodal with peak at 1.1–2.1 and 9–10 μm, while the size distribution of Cr in PM was different with those on the lead and zinc smelting affected area. More than 70% of As, Cd and Pb in PM was observed in the fine mode (dae ≤ 2.1 μm) while only 46.6% of Cr in PM was in fine mode. (2) EF values for Cd were the highest, followed by As and Pb. The smaller the particle size, the higher the degree of enrichment. High EF levels of As, Cd and Pb indicated that they were the typical heavy metals in lead and zinc smelting affected area. (3) Most of the As, Cd and Pb from the lead and zinc smelting factories enter into the atmosphere through flue gas, and Cr mainly into the waste residue.
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REFERENCES
Andreas, L., Markku, K., Hans, P., 2003. Secondary organic aerosol formation in the atmosphere via heterogeneous reaction of gaseous isoprene on acidic particles. Geophys. Res. Lett. 30 (30), 379–394. Bi, X.Y., Feng, X.B., Yang, Y.G., Qiu, G.L., Li, G.H., Li, F.L., et al., 2006. Environmental contamination of heavy metals from zinc smelting areas in Hezhang County, western Guizhou, China. Environ. Int. 32, 883–890. Brook, J.R., Dann, T.F., Bumett, R.T., 1997. The relationship among TSP, PM10, PM2.5 and inorganic constituents of atmospheric particulate matter at multiple Canadian locations. J. Air Waste Manage. Assoc. 47 (l), 2–19. Chen, H.W., 2007. Characteristics and risk assessment of trace metals in airborne particulates from a semiconductor industrial area of Northern Taiwan. Fresenius Environ. Bull. 16 (10), 1288–1294. Chen, B., Stein, A.F., Maldonado, P.G., Sanchez de la Campa, A.M., Gonzalez-Castanedo, Y., Castell, N., et al., 2013. Size distribution and concentrations of heavy metals in atmospheric aerosols originating from industrial emissions as predicted by the HYSPLIT model. Atmos. Environ. 71, 234–244. Cyrys, J., Stolzel, M., Heinrich, J., Kreyling, W.G., Menzel, N., Wittmaack, K., et al., 2003. Elemental composition and sources of fine and ultrafine ambient particles in Erfurt, Germany. Sci. Total Environ. 305 (1–3), 143. Davis, J.G., Weeks, G., Parker, M.B., 1995. Use of deep tillage and liming to reduce zinc toxicity in Peanuts grown on flue dust contaminated land. Soil Technol. 8 (2), 85–95. Duan, J.C., Tan, J.H., 2013. Atmospheric heavy metals and Arsenic in China: situation, sources and control policies. Atmos. Environ. 74, 93–101. Duan, J.C., Tan, J.H., Wang, S.L., Hao, J.M., Chai, F.H., 2012. Size distributions and sources of elements in particulate matter at curbside, urban and rural sites in Beijing. J. Environ. Sci. 24 (1), 87–94. Fan, X.B., Liu, W., Wang, G.H., Lin, J., Fu, Q.Y., Gao, S., et al., 2011. Size distributions of concentrations and chemical components in Hangzhou atmospheric particles. China Environ. Sci. 31 (1), 13–18. Fang, G.C., Huang, C.S., 2011. Atmospheric particulate and metallic elements (Zn, Ni, Cu, Cd and Pb) size distribution at three characteristic sampling sites. Environ. Forensic 12 (3), 191–199. Hu, M., Zhao, Y.L., He, L.Y., Huang, X.F., Tang, X.Y., Yao, X.H., et al., 2005. Mass size distribution of Beijing particulate matters and its inorganic water-soluble ions in winter and summer. Environ. Sci. 26 (4), 1–6. Hu, X., Zhang, Y., Ding, Z., Wang, T., Lian, H., Sun, Y., et al., 2012. Bioaccessibility and health risk of arsenic and heavy metals
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therefore, lead and zinc smelting emissions of heavy metals should be given sufficient attention. The content of the four heavy metals had many differences for every sample site, as shown in Tables 7 and 8. Pb was the highest heavy metal at every point, followed by As, Cd and Cr. In the lead and zinc smelting systems, the behaviors of As and Cd were similar, and the concentration of Cr was larger than any other heavy metal in the water quenching slag, slag and kiln slag after smelting. Previous research has shown that emissions from lead-zinc smelting factories are one of principal pollution sources of heavy metals in atmospheric particles (Bi et al., 2006). Exhaust emissions from industrial metallurgical processes may contain variable quantities of As, Cd, Ni and Pb (Wang et al., 2005). Wei et al. (2009) found smelting was the major source of heavy metal for soil contamination, especially for As, Pb and Cd. So it could be derived that Pb, As and Cd from the sample site downwind of the industrial park were connected with the emissions of the lead and zinc smelting systems. However, Cr from the raw ore mainly flows into ore slag and rarely into the atmosphere. Cr in atmospheric particles was not mainly from lead and zinc smelting. Those results were in accordance with other studies in mining and smelting areas (Wei et al., 2009).
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This work was supported by the National Natural Science Foundation of China (No. 41205093), the National Department Public Benefit Research Foundation (No. 201109005), the Fundamental Research Funds for Central Public Welfare Scientific Research Institutes of China (No. 2016YSKY-025) and National Research Program for Key Issues in Air Pollution Control (No. DQGG0304). We are gratefully indebted to the staff of the Zhuzhou Environmental Monitoring Centers for their help and support during these experiments.
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Table 8 – The concentration of heavy metal in samples from the zinc smelting factory (mg/g).
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Please cite this article as: Zhang, K., et al., Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area, J. Environ. Sci. (2018), https://doi.org/10.1016/j.jes.2018.04.018
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Rogula-Kozlowska, W., Blaszczak, B., Szopa, S., Klejnowski, K., Sowka, I., Zwozdziak, A., et al., 2013. PM2.5 in the central part of Upper Silesia, Poland: concentrations, elemental composition, and mobility of components. Environ. Monit. Assess. 185: 581–601. https://doi.org/10.1007/s10661-012-2577-1. Shao, L.Y., Hu, Y., Wang, J., Hou, C., Yang, Y.Y., Wu, M.Y., 2013. Particle-induced oxidative damage of indoor PM10 from coal burning homes in the lung cancer area of Xuan Wei, China. Atmos. Environ. 77, 959–967. Tan, J.H., Duan, J.C., 2013. Heavy metals in aerosol in China: pollution, sources, and control strategies. Journal of Graduate University of Chinese. Acad. Sci. 30 (2), 145–155. Tian, H.Z., Cheng, K., Wang, Y., Zhao, D., Lu, L., Jia, W.X., et al., 2012. Temporal and spatial variation characteristics of atmospheric emissions of Cd, Cr, and Pb from coal in China. Atmospheric Environment. Atmos. Environ. 50, 157–163. Toscano, G., Moret, I., Gambaro, A., Barbante, C., Capodaglio, G., 2011. Distribution and seasonal variability of trace elements in atmospheric particulate in the Venice Lagoon. Chemosphere 85 (9), 1518–1524. Wang, H., Stuanes, A.O., 2003. Heavy metal pollution in air-watersoil-plant system of Zhuzhou city, Hunan province, China. Water Air Soil Pollut. 147 (1–4), 79–107. Wang, X., Sato, T., Xing, B., Tamamura, S., Tao, S., 2005. Source identification, size distribution and indicator screening of airborne trace metals in Kanazawa, Japan. J. Aerosol Sci. 36, 197–210. Wei, C.Y., Wang, C., Yang, L., 2009. Characterizing spatial distribution and sources of heavy metals in the soils from mining-smelting activities in Shuikoushan, Hunan Province, China. J. Environ. Sci. 21, 1230–1236. Wilson, M.R., Lightbody, J.H., Donaldson, K., Sales, J., Stone, V., 2002. Interactions between ultrafine particles and transition metals in vivo and in vitro. Toxicol. Appl. Pharmacol. 184 (3), 172–179. Xie, D.H., Yang, T.B., Liu, Z.Y., Wang, H., 2016. Epidemiology of birth defects based on a birth defect surveillance system from 2005 to 2014 in hunan province, China. PLoS One 11. https://doi.org/10.1371/journal.pone.0147280. Ye, X.J., Hu, D., Wang, H.H., Chen, L., Xie, H., Zhang, W., et al., 2015. Atmospheric mercury emissions from China's primary nonferrous metal (Zn, Pb and Cu) smelting during 1949–2010. Atmos. Environ. 103, 331–338. Zeng, C., Liu, P., Zhao, X., 2007. Mechanism of environmental contamination in old industrial base. J. Anhui Agric. Sci. 35 (28), 8974–8976. Zhang, Y.L., Cao, F., 2015. Fine particulate matter (PM2.5) in China at a city level. Sci. Rep. 5, 14884. Zhang, K., Chai, F.H., Zheng, Z.L., Yang, Q., Li, J.S., Wang, J., et al., 2014. Characteristics of atmospheric particles and heavy metals in winter in Chang-Zhu-Tan city clusters, China. J. Environ. Sci. 26 (1), 147–153.
E
T
C
E
R
O R
N C
688
(Cd, Co, Cr, Cu, Ni, Pb, Zn and Mn) in TSP and PM2.5 in Nanjing, China. Atmos. Environ. 57, 146–152. John, W., Wall, S.M., Ondo, J.L., Winklmavr, W., 1990. Models in the size distributions of atmospheric inorganic aerosol. Atmos. Environ. 24A, 2349–2359. Karanasiou, A.A., Sitaras, I.E., Siskos, P.A., Eleftheriadis, K., 2007. Size distribution and sources of trace metals and n-alkanes in the Athens urban aerosol during summer. Atmos. Environ. 41 (11), 2368–2381. Kaupp, H., McLachlan, M.S., 2000. Distribution of polychlorinated dibenzo-P-dioxins and dibenzifurans (PADD/Fs) within the full size range of atmospheric particles. Atmos. Environ. 34, 73–83. Koulousaris, M., Aloupi, M., Angelidis, M.O., 2009. Total metal concentration in atmospheric precipitation from the Northern Agean Sea. Water Air Soil Pollut. 201 (4), 389–403. Lim, J.M., Lee, J.H., Moon, J.H., Chung, Y.S., Kim, K.H., 2010. Airborne PM10 and metals from multifarious sources in an industrial complex area. Atmos. Res. 96 (1), 53–64. Liu, X.T., Zhai, Y.B., Zhu, Y., Liu, Y.N., Chen, H.M., Li, P., et al., 2015. Mass concentration and health risk assessment of heavy metals in size-segregated airborne particulate matter in Changsha. Sci. Total Environ. 517, 215–221. Long, Y.Z., Dai, T.G., Chi, G.X., Yang, L., 2012. Assessment of heavy metals in sediment cores from Xiangjiang River, Chang-Zhu-Tan region, Hunan Province, China. J. Cent. South Univ. 19:2634–2642. https://doi.org/10.1007/s11771-012-1321-x. Lyu, Y., Zhang, K., Chai, F.H., Cheng, T.T., Yang, Q., Zheng, Z.L., et al., 2017. Atmospheric size-resolved trace elements in a city affected by nonferrous metal smelting: indications of respiratory deposition and health risk. Environ. Pollut. 224, 559–571. Masiol, M., Squizzato, S., Ceccato, D., Pavoni, B., 2015. The size distribution of chemical elements of atmospheric aerosol at a semi-rural coastal site in Venice (Italy). The role of atmospheric circulation. Chemosphere 119, 400–406. Mohanral, R., Azeez, P.A., Priscilla, T., 2004. Heavy metal in airborne particulate matter of urban coimbatore. Arch. Environ. Contam. Toxicol. 47B, 162–167. Odabasi, M., Muezzinoglu, A., Bozlaker, A., 2002. Ambient concentrations and dry deposition fluxes of trace elements in Izmir, Turkey. Atmos. Environ. 36 (38), 5841–5851. Oh, M.S., Lee, T.J., Kim, D.S., 2011. Quantitative source apportionment of size-segregated particulate matter at urbanized local site in Korea. Aerosol Air Qual. Res. 11, 247–264. Pan, Y.P., Wang, Y.S., 2015. Atmospheric wet and dry deposition of trace elements at 10 sites in Northern China. Atmos. Chem. Phys. 15 (2), 951–972. Pandey, P., Patel, D.K., Khan, A.H., Barman, S.C., Murthy, R.C., Kisku, G.C., 2013. Temporal distribution of fine particulates (PM2.5, PM10), potentially toxic metals, PAHs and Metal-bound carcinogenic risk in the population of Lucknow City, India. J. Environ. Sci. Health A Tox. Hazard. Subst. Environ. Eng. 48 (7), 730–745.
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