Research Article

Received: 18 April 2015

Revised: 23 May 2015

Accepted: 24 May 2015

Published online in Wiley Online Library

Rapid Commun. Mass Spectrom. 2015, 29, 14031410

(wileyonlinelibrary.com) DOI: 10.1002/rcm.7236

Metals and possible sources of lead in aerosols at the Dinghushan

nature reserve, southern China
Xiao-min Zhu1,2, Yuan-wen Kuang1*, Jiong Li1, Reiner Schroll3 and Da-zhi Wen1
1

Key Laboratory of Vegetation Restoration and Management of Degraded Ecosystems, South China Botanical Garden, Chinese
Academy of Sciences, Xingke Road 723, Guangzhou 510650, P.R. China
2
University of Chinese Academy of Sciences, Beijing 100049, P.R. China
3
Institute of Soil Ecology, Helmholtz Zentrum Mnchen, German Research Center for Environmental Health (GmbH), 85764
Neuherberg, Germany
RATIONALE: Aerosols play an important role in depositing metals into forest ecosystems. Better understanding of forest
aerosols with regard to their metal content and their possible sources is of great signicance for air quality and forest
health.
METHODS: Particulate matter with an aerodynamic diameter less than 2.5 m (PM2.5) in aerosols was collected every
month for 20 months using moderate-volume samplers in the Dinghushan (DHS) nature reserve in southern China.
The concentrations of metals (Al, Cd, Mn, Ni, Pb, and Zn) as well as the Pb isotopic ratios in the PM2.5 samples were
measured by inductively coupled plasma mass spectrometry (ICP-MS).
RESULTS: Moderate pollution with aerosol PM2.5 was detected at the DHS nature reserve with the air mass from
mainland China being the predominant PM2.5 source. The high enrichment factors (EFs) for the heavy metals Pb, Cd,
and Zn, as well as the PM2.5 mass concentrations, coupled with backward trajectory analysis, indicated the
anthropogenic origins of the PM2.5 and of the heavy metals in the PM2.5. The Pb isotopic ratios revealed the contributions
from various Pb sources, which varied between seasons.
CONCLUSIONS: Industrial emissions and automobile exhaust from the Pearl River Delta (PRD) primarily contributed to
the anthropogenic Pb in PM2.5, although there was occasionally a contribution from coal combustion during the wet
season. Pb isotopic ratios analyses are helpful for air quality assessment and Pb source tracing. Copyright 2015 John
Wiley & Sons, Ltd.

Aerosols, especially the fraction with aerodynamic diameters

less than 2.5 m (PM2.5), are often the carriers of certain
pathogenic bacteria and many atmospheric pollutants (toxic
metals, NOX, PAHs, etc.) that are damaging to human
health.[15] Signicant relationships between high concentrations of PM2.5 and the increasing risk of respiratory
symptoms and cancer as well as increased mortality rates
have been reported.[6,7] Because of its adverse effects on
visibility and even global climate change, haze pollution
caused by particulate matter has attracted increasing
interest.[8,9] For instance, persisting periods of haze in certain
large Chinese cities have been closely related to aerosol
concentrations.[10]
As a result of rapid industrialization and urbanization, the
air quality in many Chinese cities (especially in city-clusters
such as the Yangtze River Delta, the Beijing-Tianjin Area
and the Pearl River Delta PRD) has deteriorated in recent

Rapid Commun. Mass Spectrom. 2015, 29, 14031410

Copyright 2015 John Wiley & Sons, Ltd.

1403

* Correspondence to: Y.-W. Kuang, Key Laboratory of

Vegetation Restoration and Management of Degraded
Ecosystems, South China Botanical Garden, Chinese
Academy of Sciences, Xingke Road 723, Guangzhou 510650,
P.R. China.
E-mail: kuangyw@scbg.ac.cn

years due to the prodigious emissions of air pollutants.[1114]

Recently, more concern has been placed on the spatialtemporal variability, the concentrations of the pollutants,
and the characterization and source identication of aerosol
particulate matter in many large cities.[10,1518] China has
promulgated a new ambient air quality standard (GB30952012) to strengthen air quality monitoring; in this standard,
PM2.5 has been listed for mandatory monitoring since 2012
in 74 major cities and in all cities starting in 2016 (Ministry
of Environmental Protection, P.R. China, 2013).
It is known that the formation and characterization of
aerosols in the forest atmosphere could both be affected by
natural and anthropogenic emission sources derived from
both primary emissions and secondary processing.[19,20] At
the same time, aerosols play an important role in depositing
metals into forest ecosystems.[21,22] The aerosol concentrations
in forests have been frequently investigated;[23,24] however,
the characteristics and sources of the metals in PM2.5 have
been relatively neglected. Better understanding of the forest
aerosols with regard to their metal content and possible
sources is of great signicance for air quality and forest health.
Aerosol pollution has frequently occurred in Guangzhou,
Hong Kong and many other urban and suburban areas
within or near the PRD of southern China.[2527] Certain trace
metals are possibly transported through aerosols from urban

X.-M. Zhu et al.

to suburban areas in the PRD.[28] To date, however, the
ambient air quality, heavy metal content and possible
contributors to Pb in forest aerosols in the PRD have seldom
been evaluated. In this study, we have analyzed the PM2.5
mass concentration, metal content and Pb isotopic ratios in
forest aerosols at a nature reserve (Dinghushan, DHS) in
southern China. The goals of this study were: (1) to assess
the forest aerosol concentration as well as the heavy metal
concentrations in PM2.5 at DHS, and (2) to explore the
possible sources of PM2.5 and aerosol Pb at DHS.

EXPERIMENTAL
Site description
The Dinghushan (DHS) nature reserve (11230391123341E,
230921231130N) is located on the northwestern edge of
the PRD (Fig. 1) and has a monsoon-inuenced humid
subtropical climate according to the updated word map of
the Kppen-Geiger climate classication (with symbols
Cwa in which C, w, and a, respectively, represent
temperate, with dry winter, and with hot summer).[29] The
annual average temperature, precipitation and relative
humidity at DHS are 20.9 C, 1956 mm and 81.5%,
respectively, with a distinct dry season (from October to
March) and a distinct wet season (from April to September,
when approximately 70% of the precipitation occurs).[30]
Except for the wind speed, the meteorological conditions
including the temperature, relative humidity, precipitation
and barometric pressure at DHS showed signicant variations
(one-way analysis of variance (ANOVA), P <0.05) between
the dry and wet seasons from 2005 to 2011.[31] The Asian
monsoon appears from the southwest (South China Sea and
Pacic Ocean) in the wet season and from the northeast
(mainland of China) in the dry season.[25] This nature reserve
has experienced long-term (more than three decades)
exposure to atmospheric pollutants (e.g., atmospheric

nitrogen deposition and heavy metal deposition) stemming

from the increased numbers of industries and vehicles in the
PRD.[27,32]
Particulate matter sampling
The aerosol PM2.5 was sampled at a ow rate of 100 L min
1
using a moderate-volume sampler (TH-150CIII; Tianhong
Instrument Co., Ltd, Wuhan, China) equipped with an
impactor as the PM2.5 separator. The sampler was xed on
top of a building (10 m above ground level) in an area of
DHS where no anthropogenic activities could inuence the
quality of the aerosols. Quartz ber lters with diameters of
9.0 cm (Whatman QMA; GE Healthcare Life Sciences,
Amersham, UK) were attached to the hopper of the sampler
to continuously trap PM2.5 for 24 h, collecting an air volume
of 144 m3 during the sampling period. The lters were
weighed before sampling to calculate the aerosol mass
concentration. After sampling, the lters were stored in a
desiccator under constant temperature for at least 24 h and
reweighed with a precision balance (AL204; Mettler-Toledo,
Columbus, OH, USA). In total, 12 samples of PM2.5 were
collected from February 2010 to September 2011 except for
rainy days or during an instrument failure.
Sample digestion
The PM2.5 lters were digested with a mixture of
concentrated nitric acid (HNO3) and hydrogen peroxide
(H2O2) according to the method of Lee et al.[28] and the
national standards of P.R. China (GB/T 1526494) for the
measurement of aerosol metal concentrations. One half of
each quartz lter was diagonally cut for digestion. For each
sample, the lter equivalent was soaked in a 10 mL mixture
of concentrated HNO3 and H2O2 (v/v 1:1) for 2 h and then
heated to boiling for 10 min. After cooling, another 10 mL of
concentrated H2O2 was added, and the solution was heated
until nearly dry. Subsequently, 20 mL of diluted HNO3
(with a concentration of 1%) was added and the solution
was kept boiling for 10 min. The solution was then diluted
with 1% HNO3 solution into 50 mL volumetric asks and
nally ltered through polyethersulfone (PES) membrane
lters (pore size: 0.45 m, diameter: 13 mm; Membrana
GmbH, Wuppertal, Germany) before metal concentration
and Pb isotopic ratio analyses. Clean quartz lters were
digested in the same manner and served as blanks. Milli-Q
water (18.2 Mcm; Millipore, Merck KGaA, Darmstadt,
Germany) was used to dilute chemical reagents.
Metal concentrations and Pb isotopic ratios measurement

1404

Figure 1. Location of the Dinghushan (DHS) nature reserve

in the Guangdong Province, P.R. China. Major cities
(Guangzhou and others) within the Pearl River Delta are
shown on the map.

wileyonlinelibrary.com/journal/rcm

The concentrations of Al, Cd, Mn, Ni, Zn, and Pb as well as

the isotopic ratios of Pb in the digestion solutions were
separately measured by inductively coupled plasma mass
spectrometry (ICP-MS), using a model 7500cx instrument
(Agilent Technologies, Santa Clara, CA, USA). On-line
internal standards (45Sc, 103Rh, 115In, and 209Bi) were analyzed
simultaneously with the samples for bias correction,
revealing a relative standard deviation (RSD) from lower
than 1% to around 3%. The experimental quality was
controlled using blank lters and standard reference
materials (National Institute of Standards and Technology
[NIST] SRM 1648a Urban Particulate Matter; Gaithersburg,

Copyright 2015 John Wiley & Sons, Ltd.

Rapid Commun. Mass Spectrom. 2015, 29, 14031410

Application of Pb isotope analysis

MD, USA). Five replicates of the SRM 1648a yielded
recoveries between 95.5% and 105.0% for the metals
measured.
After the concentration measurement, the sample solutions
were diluted with 3% HNO3 to obtain concentrations of
approximately 25 ng mL
1 Pb, to produce the best counting
statistics within the linear range of a pulse-counting detector
for Pb isotope detection.[33] The maximum peak pattern was
set at 20 points, and the integration time was set at 0.3 s per
point for 206Pb, 207Pb, and 208Pb, in agreement with the
parameters described in a previous study.[34] The Pb isotopic
ratio of each sample was calculated as the average of
10 continuous readings for which the RSDs were less than 1%.
Solutions (25 ng mL
1 Pb) of the reference material (NIST SRM
981 Common Lead Isotope) were measured after every 10 samples
for calibration and quality control. The averages of the measured
207
Pb/206Pb and 208Pb/206Pb ratios were 0.9170 0.00031 and
2.1729 0.0049, respectively, comparable with the respective
reference values of 0.91464 0.000037 and 2.1681 0.0008.

Backward trajectories analysis

A backward trajectories analysis introduced by the Air
Resource Laboratory (ARL) of the US National Ocean and
Atmosphere Administration (NOAA; College, MD, USA)
was used to trace the air mass sources at DHS. The 72-h
backward trajectories ended at 06:00 universal time
coordinated (UTC), covering each sampling date, and at a
height of 500 m above ground level (AGL), half the height of
planetary boundary layer (PBL) and representative of general
transport conditions in the PBL.[28] The Hysplit (Hybrid
Single Particle Lagrangian Integrated Trajectory) model from
NOAA was applied to obtain the backward trajectories at
DHS.[35,36] The meteorological conditions from GDAS (global,
2006 to present) were applied for the archive trajectories.

Data analysis
The seasonal variances of aerosol mass concentrations, heavy
metal concentrations, and Pb isotopic ratios in PM2.5 samples
between the dry and wet seasons and between air ow
categories were determined via one-way ANOVA using SPSS
18.0 software (IBM Corporation, Armonk, NY, USA). The
gures were drawn using SigmaPlot 10.0 software (Systat
Software GmbH, Erkrath, Germany).

RESULTS AND DISCUSSION

Mass concentrations of PM2.5
The average PM2.5 concentrations were 34.5 15.7 and 39.4
22.9 g m
3 in the dry (October to March) and wet (April to
September) seasons, respectively (Table 1). The variances of
the DHS PM2.5 mass concentrations during the 20-month
sampling period are shown in Fig. 2. Although there were
relatively higher PM2.5 concentrations during several
sampling dates in different months (sampling dates in January,
May, and September 2011) (Fig. 2), no signicant differences in
the PM2.5 mass concentrations were found between the dry and
wet seasons according to the ANOVA analysis at a P level of 0.05.
As the PM2.5 mass concentration in aerosols is one of the
essential parameters for determining the aerosol quality, the
PM2.5 values determined in this study were considered to
provide a preliminary assessment of the air quality at this
nature reserve.[37] According to the new national ambient
air quality standards (GB 30952012) of P.R. China, the 24-h
average and the annual mean mass concentrations of PM2.5
in the nature reserve should not exceed 35 and 15 g m
3,
respectively. Therefore, it was considered that the ambient
air quality in the DHS reserve was slightly polluted by
PM2.5 in both seasons.

Table 1. The mass concentrations of PM2.5 (g m
3) at Dinghushan and their comparison with other regions (data in parentheses
indicate the average)

Site
Dinghushan

Changbai Mountain
Jianfengling
Guangzhou
Hong Kong
Zhongshan
Yangtze River Delta
Yangtze River Delta
Yangtze River Delta
Shanghai
Chongming Island

Nature Reserve
Feb. 2010-Sep.2011 (dry season)
Feb. 2010-Sep. 2011 (wet season)
Feb. 2010-Sep. 2011 (annual mean)
2-10 Aug. 2006
23-28 Jul. 2007
20-26 Nov. 2007
Pearl River Delta
Summer
Nov. 2000- Feb. 2001
27-29 Nov. 2009 haze period
Yangtze River Delta
Winter
Summer
Summer 2011
Sep. 2003 to Jan. 2005
13-15 Jun. 2006
Beijing
Summer 2009
Winter 2009

Rapid Commun. Mass Spectrom. 2015, 29, 14031410

Mass concentration
(g m
3)
15.7156.64 (34.5)
6.7672.90 (39.4)
6.7672.90 (37.3)
20.770.2 (30.8)
20.770.2 (38.8)
12.726.7 (18.0)
78.1 29.7
27.72116.89 (57.4)
180
89.9
28.8
82
17.8217.9 (94.6)
58150 (89.2)
125 29.0
138 57.8

Copyright 2015 John Wiley & Sons, Ltd.

References
This study
This study
This study
Li et al.[23]
Li et al.[23]
Li et al.[23]
Cao et al.[25]
Ho et al.[38]
Chen et al.[39]
Dong et al.[40]
Dong et al.[40]
Cheng et al.[41]
Wang et al.[12]
Li et al.[23]
Song et al.[18]
Song et al.[18]

wileyonlinelibrary.com/journal/rcm

1405

Beijing
Beijing

Sampling time

X.-M. Zhu et al.

days: (1) mainland China (3 November 2010, 17 December
2010, 12 January 2011, 17 May 2011, 2 June 2011, 29 August
2011, 23 September 2011); (2) South China Sea (3 March
2010, 11 July 2010, 4 July 2011); and (3) East China Sea
(2 February 2010 and 13 April 2011). According to the
backward trajectories, the air mass was more frequently
transported from mainland China during the sampling
dates rather than from the South China Sea. At the
same time, the air ow from mainland China carried
a higher mass of PM2.5 than that from the South China
Sea (Table 2). In both the dry and wet seasons, the air
mass from mainland China contributed to the DHS
aerosols at nearly the same frequency, probably causing
the similar PM2.5 mass concentrations in both seasons
at DHS.
Figure 2. Aerosol mass concentrations and Pb isotopic ratios
(208Pb/206Pb, 208Pb/207Pb, and 206Pb/207Pb) of PM2.5 during
sampling dates from February 2010 to September 2011 (dry
season and wet season are abbreviated as DS and WS,
respectively).

Because the DHS reserve is a rural environment that lies

84 km to the northwest of the center of the PRD (i.e.,
Guangzhou), it is not surprising that the average PM2.5 levels
at DHS were far lower than those in the city-clusters of the
Pearl River Delta and the Yangtze River Delta and in
Beijing (Table 1).[12,18,23,25,3841] In comparison with other
nature reserves in China, DHS had lower mean
concentrations of PM2.5 than the Changbai Mountain in
northeastern China but much higher PM2.5 than
Jianfengling in southern China (Table 1).[23] No seasonal
variations in the PM2.5 concentrations were found at DHS
despite the signicant differences in meteorological
conditions between the dry and wet seasons at this nature
reserve.[31] The Asian monsoon from the northeast in winter
and southwest in summer seemed not to be the main
meteorological factor inuencing the seasonal PM2.5
concentrations at DHS.[25]
Backward trajectories
To trace the aerosol sources, 72-h backward trajectories of air
mass ending at DHS were calculated (Supplementary
Material S1S12, see Supporting Information). Three
categories of aerosol ows covered the following sampling

Metals in PM2.5
The concentrations of Al, Cd, Mn, Ni, Pb, and Zn in PM2.5
sampled from February 2010 to September 2011 are
presented in Table 3. The average concentrations of these
metals in PM2.5 throughout the sampling period were in
the following order: Al > Zn > Pb > Mn > Ni > Cd.
Similar to the seasonal patterns of the PM2.5 mass
concentration, the concentrations of the studied metals in
PM2.5 did not show any signicant variations between the
dry and wet seasons. However, the air mass from mainland
China carried signicantly higher Cd and Pb concentrations
than that from the South China Sea (Table 2), as was the
case for the mass concentrations.
The seasonal variation in heavy metals in aerosols could be
affected by the sources, the transportation, and the
meteorological conditions.[37] In this study, the metal concentrations in PM2.5 did not show any signicant difference
between the dry and wet seasons, which was similar to
the seasonal patterns of metals in total suspended
particles at Guangzhou and Foshan, where the dominant
sources of metals in aerosols were local emissions around
the cities.[27,28] During a haze period (October 2004) in
Zhaoqing, where DHS is located, the air pollutants
including particulate matters had mainly diffused from
the central PRD.[42] Anthropogenic emissions within the
PRD are potentially releasing metals into PM2.5, which
could be transported into DHS. To identify the sources
and evaluate the inuence of the anthropogenic emissions

Table 2. Heavy metal concentrations (Cd and Pb), mass concentrations, and Pb isotopic ratios in PM2.5 from different air
mass categories. Data are shown as mean SD. Signicant differences were found for the Cd, Pb, and PM2.5 mass
concentrations between categories
Cd
Categories
Mainland China
South China Sea
East China Sea

Pb
ng m
3

5.06 2.3a*
0.82 0.21b
2.48 0.74ab

Mass concentration
g m
3

149.26 41.34a
44.55 21.43b
97.97 31.66ab

48.67 16.2 a
18.90 10.5b
25.35 13.65ab

206

Pb/207Pb

1.1620 0.0019
1.1837 0.0455
1.1566 0.0043

208

Pb/207Pb

2.0318 0.0428
2.0489 0.0502
2.0494 0.0666

208

Pb/206Pb

2.3610 0.0491
2.4236 0.0325
2.3782 0.0519

1406

*For certain metals or mass concentrations, data marked with the same letter indicate no signicant differences between
categories according to ANOVA analysis at P level of 0.05.

wileyonlinelibrary.com/journal/rcm

Copyright 2015 John Wiley & Sons, Ltd.

Rapid Commun. Mass Spectrom. 2015, 29, 14031410

Application of Pb isotope analysis

Table 3. Metal concentrations (ng m
3, mean SD) in
PM2.5 at Dinghushan, southern China, from Feb. 2010 to
Sep. 2011
Concentrations
Al*
Zn
Pb
Mn
Ni
Cd
Sample numbers

Overall

Dry season

Wet season

17.5 12.3 19.5 4.6

16.1 16.1
603.6 74.6 627.4 83.8 579.8 66.6
114.5 57.1 100.2 61.0 124.7 56.6
79.8 26.4 84.9 19.5 76.1 31.4
6.8 7.4
3.8 2.4
8.8 9.2
3.6 2.6
4.1 2.5
3.2 2.7
12
5
7

*Al concentrations in PM2.5 are presented as g m
3.

of those metals, we calculated the enrichment factors

(EFs) of metals in PM2.5 relative to the crustal material
according to Eqn. (1):
EFX

CX =CR aerosol
CX =CR crust

(1)

where CX is the concentration of metal X and CR is the

concentration of a reference element. The aerosol and crust
subscripts refer to particles in the aerosol samples and crustal
material, respectively. The metal concentrations in the crust
are adopted from Wei et al.[43] The element X is not enriched
and is mainly from natural sources, such as the earths crust,
when EFX is less than 10, while the element X may have a
signicant fraction from non-crustal sources or anthropogenic
sources when EFX is greater than 10.[44,45] Generally, Al, Fe
and Si are the common reference elements for crustal
particles in EF calculations based on the crustal chemical
compositions given.[46] In this study, we selected Al as the
reference metal. The EFs for each metal at DHS are
presented in Fig. 3.
The EFs of Cd, Pb, and Zn were clearly greater than 10,
while the EFs of Mn and Ni were less than 10, implying that
Cd, Pb, and Zn were non-crustal dominated and that a
variety of anthropogenic emissions might contribute to their

Rapid Commun. Mass Spectrom. 2015, 29, 14031410

Possible Pb sources in PM2.5

Anthropogenic Pb sources including coal combustion ashes,
industrial emissions, and automobile exhaust were easily
distinguishable from the background values shown by
granite bedrocks, volcanic rocks, and background soils within
the PRD; the former sources showed much lower Pb isotopic
ratios 206Pb/207Pb, 208Pb/206Pb, 208Pb/207Pb, and 208Pb/204Pb
(Fig. 4).[23,27,47,48] Coal ashes are characterized by relatively
lower Pb isotopic ratios (e.g., 208Pb/204Pb) than other
anthropogenic Pb sources (Fig. 4). The Fankou Pb-Zn ore is
the most widely used by industries in southern China and is
therefore considered to be representative of industrial
emissions from the PRD.[27] Comparing the Pb isotopic ratios
between the PM2.5 at DHS and potential Pb sources within
the PRD (as plotted in Fig. 4) is helpful for the interpretation
of their Pb sources. The ratio 206Pb/207Pb is able to
distinguish between natural and anthropogenic Pb sources
in the environment,[49] and combining this ratio with other
Pb isotopic ratios such as 208Pb/206Pb and 208Pb/207Pb can
provide more information about the anthropogenic Pb.[27]
The Pb isotopic ratios in PM2.5 at DHS were in the same
ranges as aerosols sampled within the PRD from previous
studies.[27,48]
While the air ow from mainland China possessed
signicantly higher Pb concentrations than that from the
South China Sea, it presented relatively lower Pb isotopic
ratios (e.g., 206Pb/207Pb, 208Pb/206Pb, and 208Pb/207Pb) that
were closer to those of anthropogenic Pb sources (Table 2).
That is to say, the Pb in PM2.5 at DHS was predominately
transported from mainland China and was mainly derived
from anthropogenic Pb sources. Moreover, the 208Pb/206Pb
ratios found in the PM2.5 samples at DHS were signicantly
lower (P <0.05) in the wet season (2.0079 0.02828) than
in the dry season (2.0826 0.0085). This result implies a
change in the main contribution among anthropogenic Pb
sources between the seasons. In the dry season, the
208
Pb/206Pb ratio in PM2.5 was more related to industrial
emissions and automobile exhaust, while, in the wet season,
the contribution from coal combustion was also important
(Fig. 4(A)). Similar seasonal patterns of aerosol Pb isotopic
ratios between the DHS forest and the central PRD (with
relatively higher Pb isotopic ratios in winter, corresponding
to the dry season, than in summer, corresponding to the
wet season), should provide hints of the effects imposed
by the latter on the former.[48]
Comparing the Pb isotope ratios in PM2.5 with those for the
potential sources, we infer that the anthropogenic Pb sources
(mainly industrial emissions and automobile exhaust but
occasionally coal combustion) as well as natural Pb sources
(background soils) from the PRD have had impacts on the
PM2.5 in the DHS forest. Commonly inuenced by
anthropogenic Pb sources from the PRD, the PM2.5 samples
and contaminated soils collected within the same region both

Copyright 2015 John Wiley & Sons, Ltd.

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1407

Figure 3. The enrichment factors (EFs) of the studied metals

in PM2.5 sampled at Dinghushan from February 2010 to
September 2011. The long horizontal line indicates an EF
value of 10.

occurrence in ambient air. Cd and Pb were considered to be

more related to coal combustion; Ni was a tracer of regional
industrial pollution; and Zn was associated with trafc
factors.[16] In contrast, Mn had rather high concentrations
but showed low EFs (less than 10), suggesting that Mn from
anthropogenic sources was negligible and that it originated
mainly from natural sources, i.e., soil dusts.

X.-M. Zhu et al.

Figure 4. Lead isotopic ratios of possible Pb sources, aerosols and the

contaminated soils within the PRD: coal combustion;[27] auto exhausts;[27]
Pb-Zn ore related to industrial emissions;[27] contaminated soils;[27,47]
background sources including granite and volcanic rocks and background soils
within the PRD;[23] PM2.5 in the dry season at DHS (this study); PM2.5 in the wet
season at DHS (this study); summer aerosols;[48] winter aerosols;[48] Apr. aerosols;[27]
Oct. aerosols.[27]
showed inuences from mixed Pb sources (mainly industrial
emissions and automobile exhaust), as their Pb isotopic ratios
were both similar to those of the above sources (Fig. 4).[47]
Although the relative contributions from the respective
sources were not calculated in this study, a source analysis
of Pb in PM2.5 partly coincided with the anthropogenic Pb
(industrial emissions and coal combustion) and natural soil
Pb in the forest soils at DHS.[47]

CONCLUSIONS

1408

In addition to the mass concentrations and heavy metal

concentrations, the sources of heavy metals in aerosols in
forest ecosystems must be further claried. As a nature
reserve which is located around the central PRD where the
most developed industries and urbanization lie, the DHS
forest is exposed to moderate pollution of aerosol PM2.5. A
backward trajectory analysis of air mass revealed that the
transport of aerosols primarily proceeds from mainland
China to the DHS forest. Among the heavy metals, Pb and
Cd were highly enriched in the PM2.5 and originated from
non-crustal sources. The Pb isotopic ratios indicated that the
anthropogenic Pb in PM2.5 was mainly derived from
industrial and trafc emissions but occasionally coal
combustion in the wet season from the PRD, and natural Pb
sources also contributed to the aerosol Pb. The energy
structure and industrial development in the central PRD are
expected to have contributed to the current aerosol
compositions in this region. The temporal changes in the Pb
source composition have been revealed by a Pb isotopic ratio
analysis of PM2.5. The use of Pb isotopic ratios for tracing Pb

wileyonlinelibrary.com/journal/rcm

sources is recommended, providing more useful and

abundant information and enabling further adjustments to
the regional energy structure to be proposed.

Acknowledgements
This project has been jointly supported by the National
Natural Science Foundation of China (Nos. 30972365,
31170427) and the Knowledge Innovation Program of the
Chinese Academy of Sciences (No. KSCX2-EW-J-28). The
authors wish to thank Dr Q. Q. Chi and Dr H. B. Li for their
great assistance with isotope measurements at the Institute of
Urban Environment, Chinese Academy of Sciences. The
authors also thank the National Ecosystem Research Network
of China-DHS Forest Ecosystem for offering the meteorological
data for DHS. The authors gratefully acknowledge the NOAA
Air Resources Laboratory (ARL) for providing the HYSPLIT
transport and dispersion model and/or READY website
(http://www.ready.noaa.gov) used in this publication.

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