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Pollution characteristics of volatile organic compounds in the atmosphere of

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DOI: 10.1039/c2em10884d · Source: PubMed

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Journal of Dynamic Article Links < C
Environmental
Monitoring
Cite this: J. Environ. Monit., 2012, 14, 1145
www.rsc.org/jem PAPER
Pollution characteristics of volatile organic compounds in the atmosphere of
Haicang District in Xiamen City, Southeast China
Zhenchuan Niu, Han Zhang, Ya Xu, Xu Liao, Lingling Xu and Jinsheng Chen*
Received 3rd November 2011, Accepted 18th January 2012
DOI: 10.1039/c2em10884d

The compositions, spatial distributions, seasonal variations and ozone formation potential (OFP) of
volatile organic compounds (VOCs) were investigated in the atmosphere of Haicang District, Xiamen
City, Southeast China. Twenty-four types of VOCs were measured in this study, and ethanol,
methylene chloride, toluene, ethyl acetate and isopropyl alcohol were the abundant species based on
concentration rank. The concentrations of total VOCs (TVOCs) in industrial areas were higher than
those in residential and administrative areas and background site. For industrial areas, the TVOCs
concentrations in summer were higher than those in winter, which might result from higher emissions
from industrial activities because of stronger evaporation in summer. In contrast, non-industrial areas
showed higher concentrations in winter due to the unfavorable meteorological conditions. The spatial
distribution of BTEX (benzene, toluene, ethylbenzene and xylene) followed the order of industrial areas
> residential and administrative areas > background site, and the concentrations in summer were lower
than those in winter for most sites. The high ratios (8.9–14.0) of T/B in this study indicated that
industrial emissions were the main sources in this district. X/B ratios were used to assess the ages of air
parcels and provided evidence of the transport of air parcels among these sites. Total OFP (TOFP)
showed the trend of increase with the increase of TVOCs, and toluene was found as the major
contributor to TOFP.

1 Introduction nogenic. For example, benzene, methylene chloride and chloro-

Volatile organic compounds (VOCs) in ambient air, from both
biogenic and anthropogenic sources, have aroused more and
more concern due to their negative impacts on the atmospheric
environment and human health.1,2 VOCs participate in complex
photochemical reactions in the presence of sunlight, producing
ozone, peroxyacetyl nitrate and organic acids.3–6 The photo-
chemical products of VOCs lead to an increase in the formation
of airborne toxic chemicals and secondary organic aerosol
(SOA).7 Many VOCs have been reported to be toxic or carci-
Key Lab of Urban Environment and Health, Institute of Urban
Environment, Chinese Academy of Sciences, Xiamen, 361021, China.
E-mail: jschen@iue.ac.cn; Fax: +86 592 6190765; Tel: +86 592 6190765
methane have been respectively classified as known (Group A),
probable (Group B) and possible (Group C) human carcino-
gens.8 Exposure to VOCs can induce a wide range of acute and
chronic effects on human health, such as respiratory damage,
sensory irritation, nervous system impairment, and cancer.2,9–11
The sources of VOCs are both anthropogenic and biogenic.
Biogenic sources are mainly from the emission of vegetation,12
while anthropogenic sources in cities include combustion of fossil
fuels, emissions of vehicle exhaust, volatilizations from the use of
solvents, and gas leakages from petroleum products.4,13–15 With
the rapid economic development, vehicle exhausts and industrial
activities have become the main sources of VOCs in urban areas
due to the elevated consumption of fossil fuels, petroleum
products and organic solvents.1,2,4,13–16

Environmental impact
The compositions, spatial distributions, seasonal variations as well as ozone formation potential (OFP) of volatile organic
compounds (VOCs) were investigated in Haicang District in Xiamen, Southeast China. Results showed that VOC concentrations in
industrial areas were higher than those in non-industrial areas. In industrial areas, the concentrations in summer were higher than in
winter, while non-industrial areas showed contrary results. The higher ratios of T/B indicated that industrial emissions were the main
sources. Benzene series were found to be the major contributors to TOFP, and the values of TOFP increased with TVOCs at most
sites. This study will be in favor of taking mitigation measures to control the VOC pollution in this rapid economic developing area.

This journal is ª The Royal Society of Chemistry 2012 J. Environ. Monit., 2012, 14, 1145–1152 | 1145
 The identification of the compositions, concentrations, sources
and behaviors of VOCs is very important for the development of
an efficient air pollution abatement strategy. Levels of VOCs
have been widely measured, such as in America,17 Canada,3,18
France,2,19 Spain,1,13,16,20 Belgium,21 Australia,22 Latin America,23
Egypt,24 Turkey14 and Korea.25,26 In China, the concentrations of
atmospheric VOCs were also studied in the cities of Beijing,27
Tianjin,11 Hong Kong,28–30 Taipei31 and Guangzhou.32 However,
the study of VOCs in the atmosphere of the Southeast Chinese
mainland is limited.33–35 Moreover, most studies focused on
aromatic hydrocarbons, and only a few studies provided the
information of ambient levels of other VOCs such as halogenated
hydrocarbons.16 Xiamen is a famous coastal tourist city and also
an important window for foreign contacts in China, thus a good
air quality is desirable. Therefore, the objective of this research is
to investigate the VOCs pollution characteristics in a district of
Xiamen, including the compositions, spatial distributions,
seasonal variations, and ozone formation potential (OFP) of
VOCs.
2 Materials and methods
2.1 Sites description
Investigations were conducted in Haicang (24.48
N, 118.04
E),
a district of 173.6 km2 located in the west of Xiamen City, Fujian
Province (Fig. 1), with 140 000 residents. Xiamen, a coastal city
in the southeast of China, has a typical sub-tropical oceanic
monsoon climate with long, hot and humid summers and short
and mild winters. The intense rainfall in summer, from May to
September, accounts for 70.4% of the total amount of annual
precipitation, while the proportion is only about 10.4% in the dry
winter period from October to January.36
Haicang is an important investment zone for Taiwanese
business in China. With the rapid economic development, many
biochemical and petrochemical factories were established in this
area. The emission of VOCs is inevitable during production
despite some mitigation measures which have been taken. Based
on the land use types, six sites were selected for the sampling of
VOCs, which were southern industrial area (SI), Xinyang
industrial area (XI), harbor and storage area (HS),
Fig. 1 Sampling sites and surrounding areas in Xiamen City, China:
Southern industrial area (SI), Xinyang industrial area (XI), harbor and
storage area (HS), administration area (AD), Xinyang residential area
(XR) and background site (BS).
1146 | J. Environ. Monit., 2012, 14, 1145–1152
administration area (AD), Xinyang residential area (XR) and
background site (BS) (Fig. 1). SI is located in the southeast of
Haicang with an area of 17.7 km2, characterized by metallurgical
and petrochemical industries. XI is the key industrial area of
Haicang with more than 40 factories of fine chemicals, plastic,
rubber and building materials within an area of 29.6 km2. HS is
located in the south of Haicang with an area of 12.4 km2 and is
characterized by port transportation, energy industry and
warehousing (bonded storage). AD is the urban area of Haicang,
with government agencies, schools, commerce and trade, public
communication, etc. XR is a major suburb of Xiamen with
facilities such as residential buildings, hospital, hotel, recreation,
etc. BS is located in the Tianzhu Mountain Scenery, about 20 km
to the northwest of the urban area, with 1500 species of plants
and a percentage of 96.8% for forest coverage.
2.2 Sample collection
The samples of VOCs were collected from the six sites in summer
and winter, over the periods from May to July 2010, and
November 2010 to January 2011. In the middle of each month,
samples were collected between 08:30 and 10:30 (GMT + 0800)
on three consecutive days. Pre-cleaned 3.2 liter Summa canisters
(Entech, USA) were used for sampling at each site. The pressure
inside the canister is much lower than the atmosphere, thus the
ambient air automatically flows into the canister without extra
pumps. The cleaning system (Entech 3100, USA) was used to
wash the canisters by high pure nitrogen gas. The height of the
sample inlet at each site was 1.5 m above the ground. Meteoro-
logical data, including ambient temperature, relative humidity,
wind speed and direction were recorded during sampling periods.
2.3 Analysis methods and quality control
The measurement of VOCs followed the procedures of USEPA
Method TO-15.37 A 400 mL of sample from each canister was
loaded into a cryogenic preconcentration system (Entech 7100A,
USA), which has 3 Modules. In Module 1, the sample was
trapped cryogenically on glass beads at 180
C cooled by liquid
nitrogen, and then warmed to 10
C to desorb the sample, leaving
liquid H2O in first trap. In Module 2, the sample was transferred
to a Tenax trap cooled to 30
C, letting CO2 pass through, and
then heated to 180
C to desorb the sample. Finally, sample was
transferred by carrier gas (helium gas) to a cold trap cooled to
160
C in Module 3, and then the trap was heated rapidly to
50
C to desorb the sample, which was introduced to a gas
chromatography-mass spectrometry (GC-MS) system (Shimazu
QP 2010, Japan). The compounds were separated by a 60 m 
0.25 mm  1.8 mm film thickness capillary column (Agilent DB-
624, USA). The oven temperature program was set for: 1 min at
33
C, first ramp at 3
C min1 to 42
C, second ramp at 4
C
min1 to 60
C, thirdly at 8
C min1 to 150
C, fourthly at 4
C
min1 to 200
C, and finally at 20
C min1 to 230
C (6 min hold).
The identification and quantification of targeted compounds
were based on the retention time and the peak area of the cor-
responding standard, respectively. Calibration curves were
obtained by using different levels of VOC standard gases
(Spectra Gases, USA, 1 ppm), which were diluted by a Dynamic
Diluter (Entech model 4600, USA). Correlation coefficients for
This journal is ª The Royal Society of Chemistry 2012
calibration curves ranged from 0.987 (1,3,5-trimethylbenzene) to
0.998 (ethyl acetate). Method detection limits (MDLs) ranged
from 0.13 to 0.61 ppbv for the mixed standard gases. Mid-range
standard gases were analyzed with 5 repeat determinations to
check the reproducibility, and the average deviation of 5 runs
was less than 10%. Recoveries of 97–105% were achieved. 5 field
blanks and 5 laboratory blanks of the canisters pre-cleaned by
high purity nitrogen gas were tested to determine contamination
levels during the sampling and analytical processes. Mid-range
standard gas was introduced to GC-MS system every day to
check the calibration curve.
2.4 The method to evaluate the ozone formation potential
Several methods are used to evaluate the photochemical reaction
of VOCs, including the concentration-based method,4 OH
radical reactivity method38 and maximum incremental reactivity
(MIR).39 Generally, MIR is widely used in the assessment of the
ozone formation from VOCs. In this study, we used MIR
method to evaluate the total OFP (TOFP) of the VOCs. The
equation is described as follow:
X tration of TVOCs in SI, XI, HS, XR and AD was 6.3, 5.6, 3.1, 2.9
TOFP ¼ Ci  Mi (1)
i and 2.2 times higher than that in BS, respectively, possibly due to
where TOFP is the sum of OFP of individual VOC; Ci is the
concentration of species i; Mi is the MIR factor of species i
proposed by Carter.39
2.5 Data analysis
Data were presented as mean values with standard deviations. As
shown in Table 1, the standard deviations in this study were
higher than the mean values for some compounds, such as
methylene chloride, ethanol, ethyl acetate, o-xylene, toluene,
benzene, etc., which were related with great variations of VOC
concentrations generated from the fugitive emissions from
industries. For example, the concentrations of ethyl acetate in SI
were in the range of 0.5–728.0 mg m3, methylene chloride in SI in
the range of 1.7–249.6 mg m3, toluene in SI in the range of 2.5–
120.3 mg m3, etc. The standard deviations in the study of Olson
et al.17 and Gee and Sollars23 also exceeded the mean values for
some concentrations. Therefore, the data in this study could be
acceptable. Analysis of correlation was performed between VOC
concentrations and meteorological parameters using SPSS 11.5,
and statistical significance was considered at p < 0.05.
3 Results and discussion
3.1 Compositions of VOCs
The compositions and concentrations of VOCs at different
sampling sites in Haicang are summarized in Table 1. Twenty-
four compounds belonging to five chemical categories were
measured in this study: aromatic hydrocarbons, oxygenated
compounds, halogenated hydrocarbons, alkanes, and sulfur
hydrocarbons. Aromatics, halogenated and oxygenated species
accounted for the majority (91.7% to 99.5%) of the total VOCs
(TVOCs) in the atmosphere of Haicang, whereas the percentage
of sulfur hydrocarbons was very small, usually less than 1%
(Fig. 2). Among these compounds, fifteen compounds (Table 1)
This journal is ª The Royal Society of Chemistry 2012
are considered as hazardous air pollutants (HAPs) defined by the
USEPA.9
The concentrations of all components at each site were ranked
to find the top five abundant compounds (TOP5). At the
sampling sites, ethanol, methylene chloride, toluene, ethyl
acetate, and isopropyl alcohol were found as the TOP5
compounds. In other studies, toluene was also observed as an
abundant compound, such as in Cairo24 and Schleswig-
Holstein.40 The total concentrations of TOP5 accounted for 67–
89% of the TVOCs at the sampling sites, and these compounds
are commonly used as raw materials and solvents in industrial
activities or additives in gasoline, indicating that the dominating
components in this district might originate from the industrial
activities and vehicle exhaust.
3.2 Spatial distributions of TVOCs
The highest concentration of TVOCs was found in SI (1029.6 
1962.8 mg m3), followed by XI (936.7  617.1 mg m3), HS (576.4
 444.8 mg m3), XR (551.5  397.8 mg m3), AD (447.7  454.7
mg m3) and BS (140.6  100.9 mg m3) (Table 1). The concen-
strong industrial and traffic emission in these areas. Generally,
for each chemical category, the concentrations in different areas
ranked in the order of industrial areas (XI, SI and HS) > resi-
dential and administrative areas (AD and XR) > background site
(BS). Most investigations in cities also concluded that the VOC
concentrations in industrial and urban areas were higher than
those in rural areas, such as in Edmonton (Canada),3 Greater
Cairo,24 Hong Kong28,41 and Ulsan (Korea),42 as a result of more
emission sources in industrial and urban areas. However, the
average concentrations measured in the satellite towns of
Dongguan in China were not significantly different than that in
the urban area, because of the emission from a great deal of
domestic workshops in the satellite towns.32
3.3 Variations of TVOCs between summer and winter
Though no significant (p > 0.05) correlations were found between
the TVOCs concentrations and ambient temperatures and wind
speeds in this study, the highest concentrations in industrial areas
were still observed in July, and the relatively lower concentra-
tions in non-industrial areas were in May and June. The small
variations of temperatures and wind speeds during the sampling
campaign could not explain the behavior of VOCs due to the
fugitive emissions of industries, but Khoder et al. demonstrated
that the daytime temperatures were significantly (p < 0.05)
positively correlated with the VOCs concentrations in Greater
Cairo.24 Ras et al. reported similar results in Tarragona (Spain)
where no relationship was found between VOCs and wind
speeds, but some higher measurements were taken at low wind
speeds.16
Seasonal variations of TVOCs concentrations between
summer and winter at each site are illustrated in Fig. 2. The
concentrations of TVOCs in industrial and non-industrial areas
had distinct seasonal characteristics. For SI, XI and HS, the
concentrations of TVOCs in summer were higher than those in
winter. The high temperature in summer is more favorable for
J. Environ. Monit., 2012, 14, 1145–1152 | 1147
Table 1 Concentrations of VOC species at different sampling sites in Haicang (mg m3)a

Species XI SI HS XR AD BS

Aromatic hydrocarbons
Benzene* 20.3  42.4 4.7  2.7 19.1  26.5 6.9  2.8 6.3  7.0 4.2  1.9
Toluene* 180.3  172.5 65.8  109.5 178.9  173.2 102.5  116.9 77.6  99.8 42.9  39.1
Ethylbenzene* 23.3  41.7 5.9  3.9 6.7  4.6 12.2  6.8 4.4  3.7 5.3  4.5
m,p-Xylene* 14.3  21.5 6.7  3.5 9.6  9.3 10.1  4.2 4.6  3.9 5.5  5.0
o-Xylene* 14.3  20.3 20.4  42.5 7.2  6.3 10.8  8.1 8.7  10.2 3.9  3.0
4-Ethyltoluene 1.1  0.9 0.7  0.6 2.1  2.2 1.2  0.6 0.7  0.6 0.7  0.6
1,3,5-Trimethylbenzene 1.0  0.8 0.7  0.6 2.3  2.4 1.2  0.6 0.7  0.5 0.7  0.6
1,2,4-Trimethylbenzene 4.1  2.8 3.0  1.6 8.0  8.5 4.9  2.2 2.6  1.6 2.8  2.5
Oxygenated compounds
Ethanol 191.4  188.0 232.4  381.0 116.6  140.1 148.5  99.8 91.7  82.0 21.8  16.5
Acrolein* 2.1  1.8 1.9  1.8 6.0  5.8 3.2  3.3 2.7  3.6 1.8  1.5
Isopropyl alcohol 23.8  17.0 38.7  90.8 5.2  3.5 13.5  10.7 8.7  8.1 2.7  1.5
Ethyl acetate 167.8  159.9 463.0  1064.1 85.5  134.2 77.9  62.9 93.2  187.5 18.5  8.8
1,4-Dioxane* 7.2  6.8 58.8  145.5 4.7  5.5 7.2  9.5 7.2  9.8 2.6  3.8
Naphthalene* 7.4  7.4 9.6  13.0 12.4  11.0 7.5  7.0 9.1  11.7 4.3  4.0
Halogenated hydrocarbons
CFC-12 1.6  1.0 2.3  1.1 1.8  1.2 2.3  0.8 2.0  0.5 2.1  1.3
Chloromethane* 1.7  1.5 1.4  0.7 1.6  0.6 2.0  1.3 1.4  0.8 1.4  1.4
CFC-11 1.9  0.8 2.0  0.6 1.9  0.7 2.1  0.8 1.8  0.6 1.9  0.8
Methylene chloride* 219.1  339.6 102.0  245.5 69.8  157.7 119.6  265.2 112.0  281.4 8.2  6.6
Carbon tetrachloride* 1.2  0.8 0.9  0.3 0.9  0.4 0.9  0.4 0.9  0.3 0.9  0.5
1,1,2-Trichloroethane* 0.9  0.9 0.8  0.8 2.0  1.7 0.8  0.8 1.4  1.4 1.9  3.9
1,2-Dichlorobenzene* 1.6  1.6 1.6  1.5 3.2  2.6 2.2  1.8 1.8  1.6 1.9  1.8
Alkanes
Hexane* 23.2  19.9 4.0  2.9 26.8  45.9 9.1  8.6 6.6  8.6 8.0  11.1
Heptane 25.7  59.4 1.3  1.1 5.7  7.3 4.3  2.5 1.1  1.0 1.7  0.7
Sulfur hydrocarbons
Carbon disulfide* 1.5  1.2 1.0  0.8 1.1  0.6 1.1  1.0 0.7  0.5 1.0  0.9
TVOCs 936.7  617.1 1029.6  1962.8 576.4  444.8 551.5  397.8 447.7  454.7 140.6  100.9
a
Components with * are hazardous air pollutants (HAPs).

from the ocean and the faster chemical removal by OH radicals

because of more sunlight and higher temperatures, while the
higher concentrations in winter may be affected by Asian
monsoons brought in pollutant air from the continent during the
cold season.3,28
As shown in Fig. 2, the concentrations of oxygenated
compounds in summer are lower than those in winter at most
sites, due to the above reasons. The seasonal variations of
aromatic hydrocarbons and halogenated hydrocarbons will be
discussed in detail in later paragraphs.

3.4 Concentrations and ratios of aromatic hydrocarbons

Fig. 2 Seasonal variations of TVOCs concentrations at six sampling
sites.
the evaporation of industrial raw materials and solvent, as well as
the leakage from the production and storage cans in harbor,
which may result in higher concentrations in summer. Similar
results were also reported by Cheng et al. in Edmonton, Canada3
and Lee et al. in Hong Kong.30
On the contrary, for AD, XR and BS, the concentrations in
summer were lower than those in winter, and a similar
phenomenon was also observed in residential and commercial
areas in Edmonton3 and Hong Kong.28,30 The lower concentra-
tions in summer may result from the combination of clean air
3.4.1 Concentrations of BTEX. Aromatic hydrocarbons,
such as BTEX (benzene, toluene, ethylbenzene and xylene),
attract a lot of interest in the field of VOCs studies due to their
carcinogenicity. In this study, BTEX accounted for the majority
of aromatic hydrocarbons (Table 1), so they will be discussed in
detail later. Benzene is likely responsible for leukaemia,43 and the
annual mean limit value in European Union is 5 mg m3,44 but the
concentrations of benzene at most sites in this study (Table 1)
exceeded this limit value. As shown in Table 2, the arithmetic
mean of benzene concentrations in Haicang exceeded the values
in Beijing,45 Dongguan,32 Guangzhou,32 Hong Kong,28,29 Ulsan42
and Seoul,26 and also exceeded those in many European and
North American cities, such as Mortsel,21 Dunkerque,2 Pam-
plona,20 Tarragona,16 New York17 and Edmonton,3 while lower
than the levels of some Asian and South American cities in

1148 | J. Environ. Monit., 2012, 14, 1145–1152 This journal is ª The Royal Society of Chemistry 2012
Table 2 Comparison of arithmetic means of BTEX concentrations among different cities (mg m3)a

Country Cities Benzene Toluene Ethylbenzene m,p-Xylene o-Xylene

China HaicangThis study 10.3 108.0 9.6 8.5 10.9

Beijing45 8.4 11.4 5.1 9.7 3.7
Dongguan32 4.4 25.1 5.0 7.0 2.4
Guangzhou32 7.2 24.1 5.8 7.2 2.7
Hong Kong28 1.8 10.7 1.7 2.7 0.9
Hong Kong29 2.8 24.6 2.1 2.8 2.1
Hong Kong30 10.7 79.5 11.9 15.8 7.7
Egypt Cairo24 46.1 110.4 22.6 72.5 36.5
Korea Ulsan42 5.8 16.0 3.8 13.9 4.7
Seoul26 4.6 26.7 4.7 10.8 4.7
Pakistan Karachi46 18.2 29.1 — 14.6 5.2
Thailand Bangkok23 18.2 186 36.6 81 28.9
Philippines Manila23 12.6 168 21.9 55.8 16.8
Belgium Mortsel21 2.5 9.5 1.6 3.4 1.3
France Dunkerque2 1.3 3.2 1.3 1.2 0.6
Spain Pamplona20 2.8 13.3 2.2 3.4 2.6
Tarragona16 1.2 3.9 0.9 1.1 0.4
America New York17 7.1 9.5 7.5 7.7 3.0
Canada Edmonton3 3.0 5.8 — 3.7 1.9
Brazil Sao Paulo23 16.7 28.1 6 18.5 6.2
Chile Santiago23 14.8 29.8 6.5 25.2 8.9
a
Unit is transformed from ppbv or pptv to mg m3 from the original publications, and data in the original publications are averaged.

developing countries, such as Cairo,24 Karachi,46 Bangkok,23 (0.6 : 8.4 : 1.0 : 1.7) and BS (0.8 : 8.1 : 1.0 : 1.8) were of similar
Manila,23 Sao Paulo23 and Santiago.23 Generally, similar results magnitude, implying there may be common sources at these sites
for the other BTEX are also clearly noted in Table 2. Therefore, because of the short distance between these sites (Fig. 1).
our data suggested that some mitigation measures should be Compared with HS (2.9 : 26.7 : 1.0 : 2.5), the ratios in SI
taken to control the BTEX emissions in this district. (0.8 : 11.2 : 1.0 : 4.6) and AD (1.4 : 17.6 : 1.0 : 3.0) were more
similar.
3.4.2 Temporal–spatial variations of BTEX. The spatial The ratios of toluene/benzene (T/B) or benzene/toluene (B/T)
distribution of BTEX showed the order of XI (252.5 mg m3) > could reveal the source information of BTEX. A T/B ratio of 2.0
HS (221.5 mg m3) > XR (142.5 mg m3) > SI (103.5 mg m3) > AD indicates that BTEX are mainly emitted from vehicle exhaust,
(101.6 mg m3) > BS (61.8 mg m3), which was in agreement with and a higher ratio would suggest that there were additional
the studies in many other cities, such as Edmonton,3 Pamplona,20 sources besides vehicle exhaust. A ratio reaching 10 and above
Cairo,24 Hong Kong30 and Ulsan.42 These results indicated that implies that there were strong industrial sources nearby.21,30,32,41
industrial areas had higher BTEX levels than non-industrial In this study, the T/B ratios varied from 8.9 to 14.0, with the
areas. average of 10.5, suggesting other sources of BTEX, like industrial
Fig. 2 obviously shows that the concentrations of aromatic emissions, as an explanation for such high values. Gee and Sol-
hydrocarbons in summer are lower in comparison to those in lars suggested that there could be other additional VOC sources
winter for most sites (except HS). As found in many other cities, resulting in the unusually low B/T ratio (0.1) in Bangkok and
such as Dunkerque,2 Edmonton,3 Pamplona20 and Seoul,26 the Manila.23
total concentrations of BTEX in this study showed higher Benzene has lower reactivity than xylene, leading to a longer
concentrations during winter and lower during summer. The atmospheric lifetime, so the X/B ratio indicates the aging of air
seasonal variations may mainly ascribe to the reduced dilution parcel and provides an evidence of transport.2,4 A higher ratio
processes and photochemical reactivity in winter. Furthermore, means a fresh air mass, i.e., the sources are closer to the sampling
as well as the reasons mentioned above, the Asian monsoons may
also have influence on the variations.
Table 3 BTEX ratios at different sites
3.4.3 The ratios of BTEX, T/B and X/B. The ratios of BTEX, X/B
T/B and X/B are presented in Table 3. The average BTEX ratios
in this study were (1.1 : 11.2 : 1.0 : 2.0), and ratios for other B:T:E:X T/B Summer Winter
studies were (1.9 : 10.1 : 1.0 : 1.8) and (1.9 : 10.4 : 1.0 : 1.5)
XI 0.9 : 7.7 : 1.0 : 1.2 8.9 1.2 2.8
during winter, (0.9 : 8.3 : 1.0 : 2.2) and (0.8 : 29.6 : 1.0 : 1.8) SI 0.8 : 11.2 : 1.0 : 4.6 14.0 9.7 2.6
during summer at two sites in Hong Kong,29 and HS 2.9 : 26.7 : 1.0 : 2.5 9.4 0.7 2.0
(2.01 : 4.94 : 1 : 4.95), (2.03 : 4.91 : 1 : 4.87) and XR 0.6 : 8.4 : 1.0 : 1.7 14.9 2.9 3.1
AD 1.4 : 17.6 : 1.0 : 3.0 12.3 2.1 2.1
(2.31 : 2.98 : 1 : 2.59) at three sites in Cairo.24 Similar BTEX BS 0.8 : 8.1 : 1.0 : 1.8 10.2 0.7 3.4
ratios indicate that there are common sources among different Arithmetic means 1.1 : 11.2 : 1.0 : 2.0 10.5 2.9 2.7
sites.24 The ratios in XI (0.9 : 7.7 : 1.0 : 1.2), XR

This journal is ª The Royal Society of Chemistry 2012 J. Environ. Monit., 2012, 14, 1145–1152 | 1149
site and photochemical processes have lower impact on the
concentrations. In contrast, a lower ratio implies an aged air
mass. In three sampling locations in Cairo, the ratios of (m,p)-X/
E and (o)-X/E in a rural location were lower than those in the
other two intense traffic locations, thereby confirming an origin
of BTEX at the two sites, and that the VOCs in the rural location
were a result from diffusion and dispersion from traffic density
locations.24 In the present study, the highest X/B ratio in summer
was found in SI (9.7), followed by XR (2.9), AD (2.1) and XI
(1.2), and the lowest in BS (0.7) and HS (0.7). The polluted air
masses firstly transported from SI to XR, AD and XI by
southeast wind, and then to BS may provide an explanation for
this trend. Air mass did not diffuse easily from SI to HS for its
windward location in summer, which may have resulted in a low
ratio at BS. In winter, the ratios in BS (3.4) and XR (3.1) were
higher than those at the other sites, which may be related to the
pollutant air mass transported from the continent by northwest
wind in winter.
3.5 Concentrations and seasonal variations of halogenated
hydrocarbons
Halogenated hydrocarbons with long atmospheric life, such as
chlorofluorocarbons (CFCs), are mainly emitted from industrial
activities other than motor vehicles.47 In this study, the concen-
trations of carbon tetrachloride (0.9–1.2 mg m3) were lower than
those in American cities (5.0–6.2 mg m3),48 but somewhat higher
than those in Karachi (0.3–0.7 mg m3) in Pakistan46 and the
Tarragona region (mean 0.6 mg m3) in Spain,16 approaching the
tropospheric background level (1.0  0.1 mg m3) in 199047 and
Hong Kong (0.6–1.0 mg m3).29 The concentrations of chloro-
methane (1.4–2.0 mg m3) were not much different from those in
American cities (1.1–2.8 mg m3)48 and the tropospheric level in
1990 (1.4  0.03 mg m3).47 However, the concentrations of
methylene chloride (8.2–219.1 mg m3) in this study were much
higher than those in American cities (0.2–0.9 mg m3),48 Karachi
(0.09–11.4 mg m3) in Pakistan46 and Hong Kong (1.1–3.1 mg
m3),29 whereas another study in Hong Kong showed higher
concentrations (1.2–355.3 mg m3).30 The concentrations of CFC-
11 (1.8–2.1 mg m3) and CFC-12 (1.6–2.3 mg m3) in this study
were close to the tropospheric level in 1990 (1.8  0.06 mg m3)47
and Karachi (1.8 mg m3, 2.5 mg m3) in Pakistan.46 So, it can be
concluded that the pollution of halogenated hydrocarbons
(except methylene chloride) in this district was not serious.
As shown in Fig. 2, the concentrations of halogenated
hydrocarbons in summer are higher than those in winter (except
at BS), which may be related to the stronger evaporation in
summer, as they are used in large amounts as chemical raw
materials, cleaning agents and refrigerants, such as methylene
chloride, CFC-11 and CFC-12. Mohamed et al. reported that the
concentrations of chloromethane in American cities peaked in
the warm summer month because of sea sprays, whereas the
halogenated compounds were generally not affected by temper-
ature or season.48
3.6 Ozone formation potential (OFP) of VOCs
VOCs are important precursors contributing to the formation of
tropospheric ozone and SOAs. To estimate the role of different
1150 | J. Environ. Monit., 2012, 14, 1145–1152
VOCs towards tropospheric ozone formation, the MIR values of
12 components reported by Carter39 were used to calculate the
OFP according to eqn (1), and the results are summarized in
Table 4. Toluene was found to have the highest OFP value at
most the sampling sites (except SI), though ethanol was found
with the relatively higher concentration than toluene at most sites
(Table 1). This difference may be attributed to the MIR value of
toluene (2.7 g O3 g VOCs1) versus ethanol (1.34 g O3 g VOCs1),
with the higher MIR value contributing more to ozone formation
potential. The MIR value of benzene is only 0.42 g O3 g VOCs1,
thereby having the lowest OFP value at most sites (Table 4). The
studies in Southern Taiwan,4 Beijing,27 Tianjin27 and Hong
Kong49 also found that BTEX had the main contribution to the
ozone formation.
Fig. 3 shows the relationship of TVOCs and TOFPs at six sites.
Except SI, the values of TOFP increased with increasing of
TVOCs at the other sites. The decrease of TOFP in SI was related
with a lower BTEX concentration (103.5 mg m3) at this site, and
previous studies indicated that BTEX had a predominant
contribution to the ozone formation.4,27 Therefore, in this
developing area, more attention should be paid to BTEX, espe-
cially toluene, in the perspective of an efficient air pollution
abatement strategy.
4 Conclusions
The investigation of pollution characteristics of VOCs was
carried out in Haicang District, Xiamen City, where the main
industries were characterized by petrochemical and biomedical
enterprises. The major conclusions were as follows.
Twenty-four compounds were measured in this study, among
which ethanol, methylene chloride, toluene, ethyl acetate, and
isopropyl alcohol were the relatively abundant species at the six
sampling sites. SI had the highest concentrations of TVOCs,
followed by XI, HS, XR, AD and BS. For SI, XI and HS, the
concentrations of TVOCs in summer were higher than those in
winter, which may result from the faster evaporation of raw
materials and solvents in industrial activities due to higher
temperature in summer. On the other hand, the concentrations in
AD, XR and BS in summer were lower than those in winter,
which may be related with the unfavorable meteorological
conditions in winter.
The concentrations of BTEX were higher than those in many
other cities. The spatial distribution of BTEX followed the order
of XI (252.5 mg m3) > HS (221.5 mg m3) > XR (142.5 mg m3) >
SI (103.5 mg m3) > AD (101.6 mg m3) > BS (61.8 mg m3).
Seasonal variations showed lower concentrations in summer
with higher concentrations in winter for most sites. The T/B
ratios in this study were high (8.9–14.0), suggesting that indus-
trial emissions were the main sources of BTEX. X/B ratios were
used to assess the aging of air parcels and trace sources, and it
was concluded that the transport of air mass among these sites
was affected by wind direction of monsoon. BTEX was respon-
sible for the largest contribution to OFP, and the TOFP values
increased with the increase of TVOCs concentrations at most
sites.
Compared to BTEX, most halogenated hydrocarbons had
relative low concentrations, and concentrations in summer were
higher than those in winter at most sites. In conclusion, the
This journal is ª The Royal Society of Chemistry 2012
Table 4 OFP values of VOCs at different sites (g O3 g VOCs1)

Compounds XI SI HS AD XR BS

Toluene 486.7 177.7 483.1 209.4 276.8 99.3

Ethanol 256.5 311.4 156.2 122.8 199.0 29.3
m,p-Xylene 106.0 49.9 71.3 34.4 74.9 40.5
o-Xylene 92.8 132.6 46.9 56.3 70.2 25.2
Heptane 89.8 4.6 20.0 3.9 15.0 6.0
Ethylbenzene 62.9 15.9 18.1 12.0 32.8 14.2
1,2,4-Trimethylbenzene 36.9 26.3 70.4 22.9 43.0 25.0
Hexane 22.7 3.9 26.2 6.5 9.00 7.9
Isopropyl Alcohol 12.9 20.9 2.78 4.7 7.3 1.5
1,3,5-Trimethylbenzene 10.4 7.1 22.7 6.6 11.8 6.9
Naphthalene 8.7 11.2 12.4 10.7 8.8 5.0
Benzene 8.5 2.0 8.0 2.6 2.9 1.8
TOFPa 1194.8 763.5 938.1 492.8 751.5 262.6
a
TOFP ¼ Total Ozone Formation Potential.

7 J. R. Odum, T. P. W. Jungkamp, R. J. Griffin, H. J. L. Forstner,

Fig. 3 The relationship of TVOCs and TOFP at six sites.
results in the present study might be helpful to control the VOCs
pollution in this area with a rapid economic development.
Acknowledgements
We thank the anonymous reviewers for their helpful comments
and suggestions. We also thank Xiangrui Kong from University
of Gothenburg, Sweden, for the help in English editing of this
paper. This research was financially supported by Program of
Bureau of Science and Technology, Haicang District, Xiamen,
China (No: 350205Z20095001), Commonweal Program of
Environment Protection Department of China (No: 201009004),
and the Knowledge Innovation Program of the Chinese
Academy of Sciences (No: KZCX2-EW-408).
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