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Atmospheric Environment 88 (2014) 297e305

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

The characteristics, seasonal variation and source apportionment of


VOCs at Gongga Mountain, China
Junke Zhang a, b, Yang Sun a, Fangkun Wu a, Jie Sun a, Yuesi Wang a, *
a
State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry (LAPC), Institute of Atmospheric Physics,
Chinese Academy of Sciences, Beijing 100029, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

h i g h l i g h t s
 This is the rst time to study the VOCs in the remote station in southwest China.
 Aromatics and alkanes are the major components of VOC.
 The seasonal variation shows higher value in spring and lower value in autumn.
 Anthropogenic sources are the most important sources in the remote area.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 1 November 2012
Received in revised form
4 March 2013
Accepted 18 March 2013
Available online 29 March 2013

The mixing ratio, composition and variability of volatile organic compounds (VOCs) were measured from
2008 through 2011 at Gongga Mountain Forest Ecosystem Research Station (102 000 E, 29 330 N, elevation
1640 m), a remote station in southwest China. Weekly samples were collected in the Gongga Mountain
area and were analyzed using a three-stage preconcentration method coupled with GCeMS. An advance
receptor model positive matrix factorization (PMF) was applied to identify and apportion the sources of
VOCs. The results show that the measured VOC mixing ratio at Gongga Mountain is dominated by aromatics (35.7%) and alkanes (30.8%), followed by halocarbons (21.6%) and alkenes (11.9%). The general
trend of seasonal variation shows higher mixing ratios in spring and lower mixing ratios in autumn. The
effect of alkanes and aromatics on the seasonal variation of total volatile organic compounds (TVOCs) is
signicant. Five sources were resolved by the PMF model: (1) gasoline-related emission (the combination
of gasoline exhaust and gas vapor), which contributes 35.1% of the measured VOC mixing ratios; (2)
solvent use, contributing 21.8%; (3) fuel combustion, contributing 29.1%; (4) biogenic emission,
contributing 5.2%; and (5) industrial, commercial and domestic sources, contributing 8.7%. The effect on
this area of the long-range transport of air pollutants from highly polluted areas is signicant.
2013 Elsevier Ltd. All rights reserved.

Keywords:
VOC sources at Gongga Mountain
Seasonal variation
PMF receptor model
Source apportionment

1. Introduction
There is no doubt of the importance of volatile organic compounds (VOCs) in the atmosphere, because they are the important
precursors of secondary air pollutants and secondary organic
aerosols in photochemical processes. Moreover, most of VOCs are
also impact the environment and human health directly (Leuchner
and Rappenglck, 2010; Prez-Rial et al., 2010).
The study of VOCs is still very limited in China because most
such studies have focused on mega-cities or city clusters, such as
Beijing (Song et al., 2007; Yuan et al., 2009; Su et al., 2011), the Pearl

* Corresponding author. Tel.: 86 (0)1082080530; fax: 86 (0)1062362389.


E-mail addresses: wys@dq.cern.ac.cn, wys@mail.iap.ac.cn (Y. Wang).
1352-2310/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.atmosenv.2013.03.036

River Delta (Chan et al., 2006; Guo et al., 2006, 2011; Ling et al.,
2011) and the Yangtze River Delta (Cai et al., 2010; Geng et al.,
2010; Huang et al., 2011). However, information about the source
characteristics of VOCs in remote areas is insufcient because it is
more difcult and more expensive to observe these areas than
observe areas in cities. However, the study of VOC emissions from
remote areas is crucial because these areas occupy more area than
cities worldwide. Thus, the results of such studies are highly useful
for studying the global temporal and spatial variation of VOCs.
Unfortunately, this type of study is rare in China, especially in the
remote area of the underdeveloped southwestern region of China.
Furthermore, it is not sufcient simply to measure the mixing
ratios of VOCs to develop of an effective control strategy. We also
need to obtain and understand accurate information about the
sources of VOCs. One effective method for studying VOC sources

298

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

involves the use of receptor models (Song et al., 2007; Lanz et al.,
2009; Chan et al., 2011; Ling et al., 2011), such as positive matrix
factorization (PMF). This receptor model has been successfully
tested in comparison with other receptor models for VOCs (Song
et al., 2007; Sauvage et al., 2009; Yuan et al., 2009) and particulate matter (PM) (Leuchner and Rappenglck, 2010; Chan et al.,
2011). A very effective statistical method, it can apportion
ambient concentration data to sources by identifying the intrinsic
characteristics of the data while limiting all of the elements in the
factor score (source proles) and the factor loading (source contributions) matrix to positive values, making this method especially
useful in environmental source analysis (Yuan et al., 2009).
In this paper, the mixing ratios, composition and seasonal variations of VOCs at Gongga Mountain, a station in a remote area of
southwest China, are rst presented. We then use the PMF receptor
model to identify VOC source types and to apportion their contributions. To the best of our knowledge, this paper is the rst to study
VOCs at a remote station in southwest China.
2. Experiment and methods
2.1. VOC sampling and analysis
The measurements were performed at the standard meteorological eld of the Gongga Mountain Forest Ecosystem Research
Station (102 000 E, 29 330 N, elevation 1640 m) in Hailuogou Scenic
Area, a remote site located in southeast Ganzi Tibetan Autonomous
Prefecture in Sichuan province. This scenic area is famous for its
large areas of glaciers and virgin forest and its large number of rare
animal and plant resources. The forest area in Hailuogou is
approximately 70 km2 and the total resort area is approximately
200 km2. The principal tourist seasons are spring and summer. There
are approximately 30,000 inhabitants in the vicinity of the scenic
area. During the tourist seasons, the population is several times
more numerous than the local residents. This station is approximately 130 km to the northeast of Yaan and 250 km from Chengdu,
the capital of Sichuan province (Fig. 1). There are two major roads in
the north and east, 500 m and 400 m from the station, respectively. A
gas station is located 1000 m to the north of the station.
Air samples were collected twice a day every Tuesday from Jan.
2008 to Dec. 2011. A total of 380 samples were collected during the
measurement period (approximately 40 samples were excluded for
various reasons). The monitoring site is shown in Fig. 1. A pump was
used to draw, ambient air samples from a gas inlet through a PFATeon tube (OD: in). These samples were collected in preevacuated 1 L electropolished canisters. A 3 min integrated

sample was taken for each canister sample at 8:00 and 14:00.
Ambient air was collected at a ow rate of 1 L min1. After the
canisters were pressurized to 60 psig, the valve was closed and the
pump turned off. The samples were returned to Beijing for analysis
within 7 days of collection.
Measurements of VOCs were made using an Entech 7100A
preconcentrator (Entech Inc., USA) followed by a GCeMS system
(Finnigan Trace GC/Trace DSQ). The details of the VOC analysis
procedures have been described previously by Mao et al. (2009)
and will be described briey here.
A 500 mL sample was concentrated in an Entech 7100A preconcentrator, a three-stage preconcentration was utilized to
remove the water, carbon dioxide, nitrogen and oxygen in air
samples. The VOCs were further focused with a capillary focusing
trap for rapid injection prior to the analytical column. A DB-5 MS
fused-silica capillary column (60 m  0.25 mm  0.25 mm, Agilent
Technologies Inc.) coupled with a quadrupole mass spectrometer
detector (Finnigan Trace 2000/DSQ. Thermosher Inc. USA) was
used for qualication and quantication.
Forty VOCs were identied and quantied. Each target species
was identied by its retention time, mass spectrum and USEPA
standard gases. The quantication of the target VOCs was performed with multi-point external standard curves and modied
using Relative Responsible Factors (RRFs). The calibration curves
were prepared using 100 ppbv external standard gases (Scott
Specialty, TO14 standard; alkanes and alkenes) and 100 ppbv internal standard gases of dibromomethane at ve different diluted
concentrations plus nitrogen (0e100 ppbv). Internal standard gas
was added to each sample to trace the analytical procedure (Mao
et al., 2009). Five sets of replicate samples were collected to
check the precision and reliability of the sampling and analysis
methods. The RSD was within 10% for the target compounds in all
ve replicates. For most samples, the VOC species were above the
detection limit of 5e10 pptv.
2.2. Positive matrix factorization (PMF)
2.2.1. Principles and application of PMF
The PMF method is comprehensively described by Paatero and
Tapper (1994) and Paatero (1997) and has been used in many
VOC source identication studies (Song et al., 2007; Sauvage et al.,
2009; Yuan et al., 2009). In this paper, PMF 3.0 (USEPA, 2008) was
used to apportion the contributions from emission sources. Several
concepts that are relevant to the understanding of this work are
briey described here. For additional details about the method, the
reader is referred to the publications cited above and to the PMF 3.0
user manual.
An ambient data set can be viewed as an i by j data matrix X in
which i samples and j chemical species are represented. The goal of
multivariate receptor modeling is to identify a number of sources p,
the species prole f of each source and the amount of mass g
contributed by each source to each individual sample as well as the
residuals eij:

Xij

p
X

gjk fkj eij

k1

where eij is the residual for each sample/species.


The PMF solution minimizes the objective function Q based on
these uncertainties (u):

Q
Fig. 1. Location of the sampling site and some important cities around it.

"
#2
Pp
n X
m x 
X
g f
ij
k1 ik kj
uij
i1 j1

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

To nd the number of sources, it is necessary to test different


numbers of sources and to nd the optimal value corresponding to
the most reasonable results. If the number of sources is estimated
properly, the theoretical Q value should be approximately the
number of degrees of freedom or approximately the total number
of data points. However, the Q value may deviate from the theoretical value if the number of sources is not well determined, (Guo
et al., 2011).
The PMF 3.0 model also provides the rotational freedom
parameter (Fpeak) function, which can control whether more
extreme values are assumed for the factor loadings (by assigning
positive Fpeak values) or for the factor scores (by assigning negative
Fpeak values) (Chan et al., 2011). In this analysis, an average of
approximately 98% of the scaled residuals calculated by PMF was
between 3 and 3, indicating a good t of the modeled results. The
factors also showed oblique edges, a property that has been proposed as an additional check of the rotation (Paatero et al., 2005).
2.2.2. Data pre-processing and the choice of species
Not all VOC species were used in this source apportionment
analysis. There are three principles for choosing the right species
for the model. (1) In the mixing ratios le, species with more than
25% of samples missing or below the minimum detection limits
(MDLs) were rejected. (2) Species that are highly reactive were
excluded because they react and are lost quickly in the ambient
atmosphere. Including them may bias the model. An exception to
this approach is the inclusion of special species that are important
tracers of certain emission sources, even though they react quickly
and become lost in the ambient atmosphere, such as isoprene, an
important biogenic tracer (Brown et al., 2007). (3) Certain species at
low mixing ratios that are not typically tracers of emission sources
were also rejected. Eventually, 28 VOC species were selected for the
source apportionment analysis because they are the most abundant
species and/or are typical tracers of various emission sources.
The PMF 3.0 model requires two input les: one for the
measured mixing ratios of the species and one for the estimated
uncertainty of the mixing ratios. Data below the MDL were replaced
by half the MDL values, and their uncertainties were set as 5/6 of
the MDL. Missing data were replaced by the geometric mean of the

299

measured mixing ratios of that species, and their uncertainties


were set at four times the geometric mean (Polissar and Hopke,
1998). The uncertainties for the normal data points were
substituted with 20% of the mixing ratio values, as suggested by
Buzcu and Fraser (2006).
3. Result and discussion
3.1. General characteristics of the VOCs
Forty VOC (C4eC12) species were measured in the samples
collected at Gongga Mountain from Jan. 2008 to Dec. 2011, including
alkanes, aromatics, alkenes and halocarbons. The means and standard deviations of the mixing ratios of these compounds are listed in
Table 1. Benzene, chloromethane, isopentane, toluene and isoprene
were the most strongly dominant compounds, with average mixing
ratios of 0.72  0.64 ppbv, 0.62  0.34 ppbv, 0.47  0.50 ppbv,
0.44  0.33 ppbv and 0.40  0.59 ppbv, respectively.
The mixing ratio for the total volatile organic compounds
(TVOCs) was 8.75  5.76 ppbv. This value is higher than that of
Mount Tai (Table 2), where the mixing ratio observed was
6.95  5.71 ppbv (Mao et al., 2009). However, this value is much
lower than the result obtained in Shanghai (32.35  19.76 ppbv), a
mega-city in China. The NMHC mixing ratio was 6.33  4.63 ppbv at
Gongga Mountain. This value is higher than that at Jianfeng
Mountain (4.78  1.85 ppbv), a background site in Hainan province,
and is lower than that at Dinghu Mountain (23.40  9.84 ppbv), a
remote station in Guangdong province (Tang et al., 2007). Therefore, the TVOCs or NMHCs at Gongga Mountain were at an intermediate level compared with other background or remote sites but
were much lower than the emissions of large cities.
The contributions of the four main hydrocarbon groups to the
TVOC mixing ratio at Gongga Mountain are given in Fig. 2. Aromatics (35.7%) provided the largest contribution to the TVOCs,
followed by alkanes (30.8%), halocarbons (21.6%) and alkenes
(11.9%). The contributions of the four main hydrocarbon groups to
the TVOCs are similar to the results for Mount Tai. The contribution
of aromatics was largest (34%), and the percentage of alkenes was
the lowest, at only 11% (Mao et al., 2009).

Table 1
Average mixing ratios of VOCs samples in the air of Gongga Mountain.
Name
Alkanes
Butane
Isopentane
Cyclopentane
Hexane
2-methylhexane
3-methylhexane
Methylcyclohexane
3-methylheptane
Alkenes
1-butene
Isoprene
c-2-pentene
Limonene
Aromatics
Benzene
Ethylbenzene
Styrene
Isopropylbenzene
1,3,5-trimethylbenzene
Halocarbons
Chloromethane
CFC-11 (trichlorouoromethane)
Dichloromethane
1,2-dichloroethane

Mixing ratio (ppbv)

Name

Mixing ratio (ppbv)

0.20
0.47
0.11
0.09
0.13
0.18
0.14
0.14










0.16
0.50
0.19
0.12
0.36
0.42
0.32
0.35

Isobutane
Pentane
2-methylpentane
Methylcyclopentane
2,3-dimethylpentane
Heptane
2-methylheptane

0.27
0.22
0.08
0.17
0.18
0.14
0.16









0.38
0.40
0.02
0.06






0.47
0.59
0.04
0.08

1-pentene
t-2-pentene
a-pinene

0.05  0.07
0.04  0.06
0.10  0.18

0.72
0.28
0.23
0.07
0.12







0.64
0.42
0.41
0.14
0.24

Toluene
m/p-xylene
o-xylene
Propylbenzene
1,2,4-trimethylbenzene

0.44
0.28
0.31
0.29
0.39







0.33
0.42
0.43
0.44
0.50

0.62
0.28
0.36
0.25






0.34
0.25
0.42
0.36

CFC-114 (tetrauorodichloroethane)
CFC-113 (trichlorotriuoroethane)
Chloroform
Chlorobenzene

0.02
0.09
0.20
0.08






0.03
0.08
0.35
0.15

0.26
0.23
0.10
0.38
0.35
0.30
0.36

300

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

Table 2
Comparison of TVOCs or NMHCs measured at Gongga Mountain and at other
stations.
Station
name

Mount Taia

Jianfeng
Mountainb

Dinghu
Mountainb

Shanghaic

Gongga
Mountain

Station
Background Background Background City
Background
type
TVOCs
6.95  5.71
32.35  19.76 8.75  5.76
(ppbv)
NMHCs
4.78  1.85 23.40  9.84
6.33  4.63
(ppbv)
a
b
c

Mao et al. (2009).


Tang et al. (2007).
Cai et al. (2010).

3.2. Seasonal variation patterns of VOCs


The seasonal trend characteristics of VOCs are valuable for understanding important processes in atmospheric transport and
chemistry. In this study, winter is dened as the three-month
period from December to February; spring, from March to May;
summer, from June to August; and autumn, from September to
November.
The seasonal variations of the mixing ratios of the total and the
four main hydrocarbon groups are shown in Fig. 3. As shown, there
is a large and statistically signicant variation in VOC levels (only
considering the mean values). The mixing ratios were generally
high in spring (12.9 ppbv) and low in autumn (6.44 ppbv). This
result is different from those of studies in several cities, which all
found that the mixing ratios of most VOCs were high in winter and
low in summer (Ho et al., 2004; Parra et al., 2009). In addition, note
that the error range for the mixing ratios of the total and the four
main hydrocarbon groups are wide. The signicant difference may
disappear if these errors are considered. The following discussion
will only focus on the difference in mean values.
Several factors affect the seasonal variation of VOCs in the atmosphere. These factors include the following: (1) Photochemical
removal (primarily by the hydroxyl (OH) radical). The chemical
removal of VOCs by OH radicals is faster in warmer seasons than in
cooler seasons. Because more sunlight and higher temperatures in
warmer seasons will result in higher chemical removal reaction
rates (Ho et al., 2004). (2) The dilution due to atmospheric mixing.
The mixing layer in warmer seasons is much higher than in cooler
seasons. The dilution of airborne pollutants from ground source
emissions in warmer seasons is stronger than in cooler seasons.
However, another, more important factor inuences the seasonal
variation of VOCs at Gongga Mountain. Because the site is a tourist
attraction, the principal sources of VOC emissions will change with
the tourism seasonal variations signicant. The highest and the
lowest values appeared in spring and autumn as the result of
all of the above factors. Spring is a favorable season for tourism.
Many local sources could introduce VOCs into the air. Moreover,

Halocarbons
21.6%

Aromatic
35.7%

Alkanes
30.8%

Alkenes
11.9%

Fig. 2. Contributions of four main hydrocarbon groups to TVOC in the air at Gongga
Mountain.

photochemical removal and dilution are weak due to the lower


temperature. Therefore, the VOCs will accumulate. The highest
value appeared in this season. Although emission sources are also
present in autumn, they are lower than in summer, and the effects
of photochemical removal and the dilution are remain strong. For
this reason, the lowest values of VOCs appeared in autumn. In
winter, although the emission sources are less than in autumn, the
accumulative effect of meteorological factors is strongest. The VOC
emissions from non-tourism sources will accumulate, and the total
in winter will higher than that in autumn. However, the long-term
presence of air masses could result in the transport of VOCs from
large cities to this area in spring than in other seasons, whereas this
effect could be negligible in autumn. We will discuss this topic in
detail in Section 3.4.
Among the four main hydrocarbon groups, the mixing ratios of
alkanes and aromatics were dominant throughout the year and
showed a pattern of variation similar to that of the TVOCs. A correlation analysis found that the relationship between TVOCs and
alkanes or aromatics was signicant (P < 0.01). Consequently, the
seasonal variation of the TVOCs was primarily affected by that of
the alkanes and aromatics. The decisive role of these two hydrocarbon groups has also been identied by other studies (Saito et al.,
2009; Geng et al., 2010).
3.3. Source identication
Five factors were resolved at Gongga Mountain through the
application of the PMF model. Fig. 4 shows the explained variations
(EVs) for all the identied sources. The EV quantity indicates the
importance of each factor element in explaining the total mass of
the element and is particularly powerful for identifying tracer
species if the absolute amounts of chemical species show a significant difference (Yuan et al., 2009).
Source 1 is identied as gasoline-related emissions (the combination of gasoline exhaust and gas vapor). Gasoline is the dominant vehicle fuel, and VOC emissions from gasoline are transported
along the following three pathways: (1) gasoline vapor emitted
from headspace emissions at gas stations and bulk terminals and
from vehicles as diurnal emissions and resting loss; (2) liquid
gasoline arising from spillage, leakage and vehicle operations; and
(3) exhaust released from the tailpipes of gasoline-powered vehicles during gasoline combustion (Watson et al., 2001; Choi and
Ehrman, 2004). Isobutene, isopentane and hexane are the main
constituents of gasoline and are thus good tracers of gasoline
evaporation (Xie and Berkowitz, 2006; Brown et al., 2007). Additionally, BTEX and 2-methylhexane are important component
species of vehicular exhaust, as shown by many studies (Watson
et al., 2001; Guo et al., 2006, 2007). The Hailuogou scenic area attracts large numbers of tourists due to the attractive natural environment and the favorable climate. The number of visitors reached
to 141,000 between January and July in 2009, and the number of
visitors per day can reach approximately 10,000 on Labor Day, a
traditional festival in China. The two roads cited above are the
principal routes into the scenic area. For this reason, the gasoline
exhaust emissions from the trafc sources on the two main roads
and the gas vapor from the gas station are very important contributors to this source at the study site.
High percentages were found for trimethylbenzene and aromatic hydrocarbons, especially for TEX (toluene, ethylbenzene, m/
p-xylene and o-xylene) in Source 2. It is known that TEX is the
primary constituent of solvents (Guo et al., 2004a; Choi et al., 2011).
TEX is often used as a solvent in paints, coatings, synthetic fragrances, adhesives, inks and cleaning agents, in addition to its use
in fossil fuel (Borbon et al., 2002; Chan et al., 2006). 1,2,4trimethylbenzene and 1,3,5-trimethylbenzene are also typical

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

18

10

Mixing ratio(ppbv)

301

16

14

12

TVOCs
Alkanes
Aromatics
Alkenes
Halocarbons

10

4
3

-1
Jan.Feb.Mar.Apr. MayJun. Jul. Aug.Sep.Oct.Nov.Dec.

Spring

Summer

Autumn

Winter

Fig. 3. Monthly and seasonal average mixing ratios of the total and the four chemical groups of Gongga Mountain.

development of the Gongga area has been rapid. For example, the
number of visitors in the rst seven months of 2009 was 123%
greater than that in the same period in 2008. The tourism zone
requires more hotels, restaurants and other related infrastructure

tracers that are used as solvents (Borbon et al., 2002; Guo et al.,
2004a). In the PMF-derived source prole, 1,2,4-trimethylbenzene
and 1,3,5-trimethylbenzene all account for 75% of the total mass.
This source is therefore assigned to solvent use. In recent years, the

100

Gasoline-related emission

80
60
40
20
0
100
80

Solvent use

60
20
0
100 Fuel combustion
80
60
40
20
0
100 Biogenic emission
80
60
40
20
0
100 Industrial, commercial and domestic
80
60
40
20

Fig. 4. Explained variation of ve identied sources at Gongga Mountain.

-pinene

Limonene

1.2.4-trimethyl-benzene

propyl-benzene

1.3.5-trimethyl-benzene

Isopropylbenzene

Styrene

o-xylene

m/p-xylene

Ethylbenzene

Toluene

Chlorobenzene

Heptane

2,3-dimethyl-pentane

Benzene

2-methyl-hexane

Hexane

1,2-Dichloroethane

Dichloromethane

2-methyl-Pentane

t-2-Pentene

c-2-pentene

Pentane

Isoprene

1-Pentene

Isobutane

Isopentane

0
Chloromethane

% of species

40

302

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

to meet the rapid growth in visitor numbers. Solvent widely are


used extensively in the construction industry. They are the primary
components of coatings, adhesives, paints and cleaning agents as
previously stated.
Source 3 was characterized by a signicant presence of chloromethane (91%) and benzene (41%) (Guo et al., 2004b, 2007).
Chloromethane is a typical species from biomass burning (Ling
et al., 2011). Barletta et al. (2009) also considered chloromethane
a biomass/coal burning tracer, which is consistent with the results
of Wang et al. (2005). Moreira dos Santos et al. (2004) found that
coal combustion could release signicant amounts of benzene into
the atmosphere. Source 3 has, therefore, been assigned to fuel
combustion. At Gongga Mountain, local residents burn large
amounts of straw after the harvest. Moreover, the development of
the tourism industry has promoted the rapid development of many
related industries, and coal is used as the principal fuel by many of
these industries. Therefore, the widespread use of these two types
of fuel is the key reason for their identication as the fuel combustion source.
Source 4 was distinguished by a strong presence of isoprene, apinene and limonene, the indicators of biogenic emissions. In the
derived source prole, isoprene, a-pinene and limonene represent
75%, 77% and 83% of their EVs, respectively. Isoprene can also be
characterized by industrial emissions if it is emitted with other industrial VOCs, such as 2-methylpentane, 3-methylpentane and 1,3butadiene (Buzcu and Fraser, 2006), and if it if emitted by heavy
vehicular trafc (Song et al., 2007). This possible contribution can be
neglected because the correlation coefcient R2 between isoprene
and two important tracers of industrial emissions (1-pentene and c2-pentene) and two important tracers of gasoline-related emissions
(isopentane and hexane) were low (0.03 and 0.158, 0.154 and 0.151).
Therefore, this source was identied as a biogenic emission.
Guo et al. (2004a) found that 1-pentene and cis-2-pentene are
emitted into the air from industrial, commercial and domestic
processes that either use or manufacture the materials or that they
are emitted from the sites where they are formed as byproducts. 1pentene is a product of oil pyrolysis. It can be used for organic
synthesis, dehydrogenation for producing isoprene, and as an additive in high-octane gasoline. Cis-2-pentene is used in organic
synthesis and as a polymerization inhibitor. This source is also
associated with 70% of the total pentane used in the manufacture of
articial ice, anesthetic agents and the synthesis of pentanol and ipentane. In source 5, 1-pentene and cis-2-pentene represent 83%
and 90% of their EVs, respectively. Buzcu and Fraser (2006) also
found that 2-methylpentane is an important emission component
from industrial processes. This species is an important chemical
raw material and can be used as a rubber solvent and a vegetable oil
extraction solvent. It is also an intermediate in organic syntheses.
Therefore, this source was identied as industrial, commercial and
domestic.
The sources resolved by PMF were the results of the interaction
of local emissions and long-term transport from areas around the
site. The topic of local emissions was addressed at the end of each of
the preceding discussions of the sources. A discussion of long-term
transport must involve information on other air masses. For this
reason, long-term transport will be discussed in Section 3.4.
The individual contributions of the ve major VOC sources to
the measured VOC mixing ratios are shown in Fig. 5. This gure
shows that gasoline-related, industrial, commercial and domestic
sources and solvent use are estimated to be the major contributors
to the TVOCs at Gongga Mountain, representing approximately 86%
of the total source. Biogenic emissions play only a minor role,
contributing only 5% of the total VOC mass. The basis of this phenomenon is that there were only three species of emissions from
the biogenic we studied and that the mixing ratios of a-pinene and

industrual,
commercial and
domestic, 9%
biogenic
emission, 5%

fuel combustion,
29%

gasoline-related
emission, 35%

solvent use,
22%

Fig. 5. Individual contributions of the ve major sources to the measured VOCs.

limonene were only 0.10  0.18 ppbv and 0.06  0.08 ppbv,
respectively. This nding is similar to those of previous studies in
remote or background sites, such as those at Linan (Guo et al.,
2004b) and Yufa (Yuan et al., 2009).
3.4. The effect of long-range transport
The long-range transport of air pollutants (clean air) from highly
polluted areas (clean areas) could increase (decrease) the VOC
mixing ratios at the study site. This transport will affect the sources
at the sampling site in conjunction with the local sources. The
Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT)
model is a useful air trajectory model, especially for studying the
long-range transport of air masses (Mao et al., 2009; Cheng et al.,
2010). This model was used to calculate 36 h back-trajectories for
each day during different seasons in 2011. The back-trajectories
were calculated every 6 h. The air mass direction can be divided
into four categories in terms of the original direction, namely, 0 e
90 , 90 e180 , 180 e270 and 270 e360 .
Only one air mass in the 0 e90 category was present in spring
(Fig. 6a). It originated from Xian, a large city in central China, and
passed over Hanzhong and several cities of Sichuan, including
Guangyuan, Mianyang, Deyang and Chengdu, before ultimately
arriving at Gongga Mountain. The transport of pollutants from
these cities via the air masses could signicantly promote the level
of VOCs in the air at the study site. Two air masses were associated
with the 180 e270 direction. The air masses originated from the
northeastern part of India and passed over northern Myanmar and
the clean air area in Yunnan province, China. Two air masses were
associated with the 270 e360 direction. These air masses originated from several underdeveloped areas of China, including Qinhai province and the Tibet Autonomous Region. The effect on the
sampling site of the air masses that originate from the latter two
directions was to dilute the mixing ratio of VOCs in the atmosphere.
In summer, two air masses were associated with the 0e90
direction (Fig. 6b). The original and effect of the longer of these two
air masses (7th) was similar to that of the 0e90 air mass in spring.
The shorter air mass originated from and passed several small
counties or towns. Only one air mass was associated with the 90 e
180 direction. This air mass originated from Guizhou province, an
underdeveloped province in China. Three air masses were associated with the 180 e270 direction. The third of these air masses
originated from Yunnan province, a clean area in China. The other
two air masses originated from northern Myanmar, also a clean
area. The effect of the air masses originating from the latter two
directions was to dilute the VOCs in the atmosphere.
One air mass originated from the east of China in autumn
(Fig. 6c). This air mass was very short and may have transported
small amounts of pollutants from nearby towns. However, its effect
was very limited. The major air masses in autumn were associated

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

303

Fig. 6. The main air masses of different seasons at Gongga Mountain in 2011. a: spring; b: summer; c: autumn; d: winter.

with the 180 e270 and 270 e360 directions. The origins and
effects of these air masses were similar to those of the air masses
identied in spring and summer and associated with the same
directions.
In winter, the air masses were associated with the 180 e270
and 270 e360 directions (Fig. 6d). The origins and effects of these
air masses were the same as those of the air masses associated with
the same directions in spring and autumn.
The air masses can be divided into the following two categories:
(1) contaminated air masses, it only appearing in spring and summer (the 5th air mass in spring and the 7th air mass in summer)
which could transport air pollutants from highly polluted areas and
increase the level of VOCs in the Gongga Mountain area; and (2) the
other air masses, which originated from other directions and
diluted the VOCs at the sampling site. The heights associated with
these two categories of air masses differed signicantly. The height
of the air masses belonging to the rst category was always less
than 500 m. This characteristic was not conducive to the dilution of
pollutants in the vertical direction during the transport process. In
contrast, the height of the air masses belonging to the second

category was not stable. It ranged from more than 3000 m to less
than 500 m for different directions or seasons.
The differences between air masses in different seasons can also
be used to explain the seasonal variation at Gongga Mountain. Air
masses carrying high mixing ratios of pollutants only appeared in
spring and summer, and the associated proportions were all 10%
(the 5th air mass in spring and the 7th air mass in summer). While
the scavenging effect is stronger in summer than spring, due to the
higher temperature and mixing layer. For this reason, the effect of
long-term transport on the VOCs in the Gongga Mountain area is
stronger in spring than in summer. All of the air masses appearing
in autumn and winter can be viewed as dilute air masses. Therefore,
the mixing ratio of VOCs in autumn and winter is lower than in
spring (especially) and summer.
Note that the station at which this study was conducted would
be considered a remote station in a relative sense. The air masses
traveling to the site from several large cities have some effects, as
discussed above. Therefore, the source tracers cannot be used as the
source apportionment if these tracers experienced a loss during
transport. Accordingly, we analyzed the correlations between

304

J. Zhang et al. / Atmospheric Environment 88 (2014) 297e305

several important tracers belonging to the same source. For


gasoline-related emissions, we analyzed isopentane, hexane and 2methylhexane; for solvent use, we analyzed toluene, ethylbenzene,
xylene, 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene; for
fuel combustion, we analyzed chloromethane and benzene; and for
industrial, commercial and domestic sources, we analyzed 1pentene, c-2-pentene and 2-methylpentane. The ranges of the R2
statistic for the tracers for gasoline-related emissions, solvent
sources, fuel combustion sources and industrial, commercial and
domestic sources were 0.43e0.78, 0.51e0.89, 0.34 and 0.45e0.60,
respectively. The R2 values for chloromethane and benzene were
lower. The reason for this difference is that chloromethane and
benzene primarily represent emissions from biomass and coal
burning, respectively, although they are the tracers for the combustion source. As the above discussion indicates, we found that the
correlations for the important tracers corresponding to every
source were still reliable although some of them represented
transport from certain cities. Therefore, these data could be used in
the PMF analysis.
4. Conclusions
Field measurements of volatile organic compounds (VOCs) were
conducted at the Gongga Mountain Forest Ecosystem Research
Station, an important remote station in southwest China, from
2008 to 2011. The VOC mixing ratios at Gongga Mountain were
dominated by alkanes and aromatics, followed by halocarbons and
alkenes. The VOCs showed obvious seasonal variation, with higher
mixing ratios during spring and lower mixing ratios during
autumn. The effect of alkanes and aromatics on the seasonal variation of the TVOCs was signicant. A positive matrix factorization
(PMF) model was used to investigate the contributions of the VOC
sources. Five stable sources were identied on the basis of ngerprint species in the source proles by the PMF model: gasolinerelated emissions (the combination of gasoline exhaust and gas
vapor), solvent use, fuel combustion, biogenic emissions and industrial, commercial and domestic sources. The rst three sources
were found to be the strongest VOC contributors in this area, representing approximately 86% of the total source material. The effect
on this area of the long-range transport of air pollutants from
highly polluted areas should not be ignored. This process has a
signicant effect on sources and seasonal variations. Note that this
study reports the results of preliminary research on this topic. We
need more precise studies in the future, such as more intensive
sampling and analysis of the sources in different seasons, because
the effect of air masses on the sampling site differs over the four
seasons.
Acknowledgements
This work was funded by the CAS Strategic Priority Research
Program Grant NO. XDA05100100 and the National Natural Science
Foundation of China Grants No. 41021004, 41175107 and 41275139.
We gratefully acknowledge this nancial support. The authors also
acknowledge the additional support provided by all members of
the Gongga Mountain campaign science team.
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