Environmental Pollution 141 (2006) 107e114

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Distributions and Concentrations of PAHs in Hong Kong Soils

H.B. Zhang a,b, Y.M. Luo a,c, M.H. Wong a,b,*, Q.G. Zhao a,c, G.L. Zhang a,c
a
Soil and Environment Joint Open Laboratory between Institute of Soil Science, Chinese Academy of Sciences
and Hong Kong Baptist University, Soil and Environmental Bioremediation Research Center,
State Key Laboratory of Soil and Sustainable Agriculture, Nanjing 210008, China
b
Croucher Institute for Environmental Science and Department of Biology, Hong Kong Baptist University,
Kowloon Tong, Hong Kong
c
Graduate School of the Chinese Academy of Sciences, Beijing 100039, China
Received 10 December 2004; accepted 2 August 2005

Baseline information is provided on levels, distributions and possible sources of PAHs in Hong Kong soils.

Abstract

Surface soil (0e10 cm) samples from 53 sampling sites including rural and urban areas of Hong Kong were collected and analyzed for 16
EPA priority polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations were in the range of 7.0e410 mg kgÿ1 (dry wt), with higher
concentrations in urban soils than that in rural soils. The three predominant PAHs were Fluoranthene, Naphthalene and Pyrene in rural soils,
while Fluoranthene, Naphthalene and Benzo(b C k)fluoranthene dominated the PAHs of urban soils. The values of PAHs isomer indicated
that biomass burning might be the major origin of PAHs in rural soils, but vehicular emission around the heavy traffic roads might contribute
to the soil PAHs in urban areas. A cluster analysis was performed and grouped the detectable PAHs under 4 clusters, which could be indicative of
the PAHs with different origins and PAHs affected by soil organic carbon contents respectively.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Hong Kong soil; Cluster analysis; PAH profile; PAH isomer ratio

1. Introduction The typical level of endogenous total PAHs in soils is in the

Polycyclic aromatic hydrocarbons (PAHs) are a class of
several hundred individual compounds containing at least 2
condensed rings, and 16 of them have been identified as
‘‘priority pollutants’’ by the United States Environmental
Protection Agency (US EPA). Many of PAHs possessing of
mutagenic, carcinogenic, and teratogenic properties are ubiq-
uitously distributed in the environment (Xue and Warshawsky,
2004). Wild and Jones (1995) estimated that at least 90% of
the environmental PAH burden in Great Britain is stored in
soils. This estimate excludes contaminated sites such as gas-
work sites, petroleum refineries, or wood preservation plants.
* Corresponding author. Croucher Institute for Environmental Science and
Department of Biology, Hong Kong Baptist University, Kowloon Tong,
Hong Kong. Tel.: C852 3411 7746; fax: C852 3411 7743.
E-mail address: mhwong@hkbu.edu.hk (M.H. Wong).
range 1e10 mg kgÿ1 resulting from plant synthesis and natural
fires (Edwards, 1983). However, concentrations and patterns
of PAHs varied markedly between temperate and tropical soils
due to the faster microbial degradation and photo-oxidation
and enhanced volatilization in tropical soils (Smith et al.,
1995; Wilcke et al., 1999a,b). Typical concentrations in
tropical soils of Thailand are in the range 11e347 mg kgÿ1
dominated by naphthalene, phenanthrene and perylene
(Wilcke et al., 1999b), while 108e54 500 mg kgÿ1 (the sum
14 PAHs) in temperate soil of Wales, dominated by high
molecular weight PAHs such as fluoranthene, 1,2-dibenzan-
thracene and chrysene were reported (Jones et al., 1989).
The major PAH source is incomplete combustion of organic
materials (Jenkins et al., 1996; Wilcke et al., 2002; Kim
et al., 2003). This occurs naturally in vegetation fire, volcanic
activities, and diagenetic processes. Moreover, most PAHs in
urban areas are produced by anthropogenic combustion of

0269-7491/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2005.08.031
108 H.B. Zhang et al. / Environmental Pollution 141 (2006) 107e114
wood and fossil fuels. Other sources of PAH include oil spill
accidents and wastewater discharge from domestic and indus-
trial activities (Tam et al., 2001). In addition to pyrolytic and
petrogenic origins, there are some evidences showing biolog-
ical PAH formation. Naphthalene and perylene are believed
to be produced biologically by woody plants or termites in
Amazonian rain forest (Wilcke et al., 2000, 2003). Concentra-
tions of 4-, 5-, and 6-, ring PAHs are all found significantly
increased in soils under oxygen deficient conditions, it is
thus assumed that PAHs are formed in soils from plant materi-
als and humus precursors under such conditions (Thiele and
Brummer, 2002).
A number of studies have been conducted on the sources
and distributions of PAHs in atmosphere (Zheng et al., 1996;
Zheng and Fang, 2000; Lee et al., 2001), sediments (river, wet-
land and marine) (Zheng and Richardson, 1999; Tam et al.,
2001; Zheng et al., 2002; Wong and Poon, 2003), and marine
shellfish (Richardson, 2003) in Hong Kong. However little is
known about the sources and concentrations of PAHs in soils
of Hong Kong. Soil as a repository of all types of chemical
inputs, is important to the sources and pools of PAHs on the
regional scale. The main objective of this study is to determine
the distributions and concentrations of the 16 EPA priority
PAHs in Hong Kong soils. It is also hoped to identify the
possible sources of these pollutants.
2. Materials and methods
2.1. The study area
Hong Kong is situated at the south-eastern tip of Mainland China, with a total
area slightly over 1100 km2 covering Hong Kong Island, Kowloon, New
Territories and a number of outlaying islands. Out of the total land area,
three-quarters is countryside, including 4 main types of land use: woodlands,
grasslands, farmlands or fallow lands and wetlands (AFCD, 2002). Woodlands
and grasslands are mainly distributed in hills that largely unsettled and
remained fairly natural, while the limited agricultural lands and fallow lands
are scatted at the alluvial plain. Most wetlands can be found in the northwest-
ern part of the New Territories, and half of which is mangrove swamp
(Ashworth et al., 1993). Mai Po mangrove swamp is the most important
wetland in Hong Kong because it has been designed as a site with international
importance (a Rasmar site). The remaining lands (one-quarter) are urban areas
with a population density over 26 000 persons per km2, which mainly central-
ized in the northern part of Hong Kong Island, southern part of Kowloon, Kwai
Chung, and Tsuen Wan Districts.
Most soils of Hong Kong are Oxisols commonly found in the humid
tropics, characterized by strong weathering and leaching (Soil and Conserva-
tion Service, 1999). Hong Kong’s climate is sub-tropical, tending towards tem-
perate for nearly half of the year and the annual average temperature and
relative humidity were 24  C and 78% respectively in 2000 (Hong Kong
Observatory, 2001). The mean annual rainfall ranges from around 1300 mm
at Waglan Island to more than 3000 mm in the vicinity of Tai Mo Shan. About
80% of the rain falls between May and September. October to next April
is relatively arid, and hill fire caused by tomb worship is often occurred in
countryside in this period (AFCD, 2002).
2.2. Soil sampling and preparation
Surface soils (0e10 cm) were collected from the New Territories, Kowloon,
Hong Kong Island, and Lantau Island in December 2000. The sampling sites
and land use of each sampling site are shown in Fig. 1. In total, 53 soil samples
(consisted of 45 in rural areas and 8 in urban areas) were collected, and each
sample consisted of 3 sub-samples collected from the surrounding of each
site (within 1 m2). Among the 45 rural soil samples, most of them were collected
from woodlands and grasslands, 7 were from farmlands and 2 from wetlands (Mai
Po mangrove swamp), and the other 8 urban soil samples were collected mostly
from urban parks located in Hong Kong Island, Kowloon, Sha Tin, Tai Po, Tun
Men and Tsuen Wan, while one sample was colleted from the reclamation site
in Ma On Shan seaside. All the samples were freeze-dried and sieved to
!2 mm after removing stones and residual roots, then stored in desiccators prior
to analysis of PAHs.
2.3. Sample extraction and cleanup
Sample extraction, cleanup and analysis of PAHs were conducted in the
State Key Laboratory of Pollution Control and Resource Reuse in Nanjing
University, following the methods described by Ma et al. (2003). Soil samples
(7.5 g dry weight) were placed into a centrifugal tube, with a mixture of 20 ml
n-hexane, 5 ml methanol and 5 ml distilled water and sonicated for 1 h in an
ultrasonic shaking apparatus. The mixture was then centrifuged and the extract
collected. The same extraction was repeated once again by adding 20 ml
n-hexane to the filter residue. The two extract solutions were then combined
and anhydrous sodium sulfate was added for drying, and then concentrated
to around 1 ml by rotary evaporation. The concentrated extracts were cleanup
using a chromatographic column consisting of 1 g of activated silica gel
(0.07 ml distilled water was added), and then eluted with 8 ml n-hexane, after
that the eluent was further concentrated to about 1 ml. The solution was finally
concentrated to around 0.1 ml under a gentle steam of pure nitrogen. 10 ml
9-phenylanthracene (20 ppm) was added to the solution as an internal standard
prior to transferring to a glass of microvial for GC injection.
2.4. PAH analysis
The concentrations and profiles of PAH compounds were analyzed using
an Agilent6890 gas chromatograph (HP-5 quartz capillary column:
30 m, 0.33 mm ID ! 0.25 mm film thickness) with a flame ionization detector
(GC/FID). The oven temperate was initially set at 80  C and held for 1 min,
ramped at 25  C/min to 160  C, 3  C/min from 160 to 300  C, and held for
2 min. High purity (99.99%) nitrogen gas was used as the carrier gas.
Identification and quantification of 16 PAH compounds were based on
matching their retention time with a mixture of PAH standards. The 16 PAH
compounds were Naphthalene (Naph), Acenaphthylene (Acel), Acenaphthene
(Ace), Fluorene (Flu), Phenanthrene (Phe), Anthracene (Ant), Fluoranthene
(Fla), Pyrene (Pyr), Benzo(a)Anthracen (BaAnt), Chrysene (Chry), Benzo(b)-
Fluoranthene (BbFla), Benzo(k)Fluoranthene (BkFla), Benzo(a)Pyrene (BaP),
Inde(1,2,3)Pyrene (IPyr), Dibenz(a,h)Anthracene (DahA), Benzo(g,h,i)Pery-
lene (BghiP). Among the analyzed 16 EPA PAH compounds, only 15 were
identified (DahA was not identified). Out of the detected 15 PAHs, the peaks
of Benzo(b)Fluoranthene and Benzo(k)Fluoranthene were extremely close and
therefore difficult to be distinguished, so these two compounds were calculated
as one, namely Benzo(b C k)Fluoranthene (B(b C k)Fla). The 14 PAHs were
then used for the calculation of the total PAHs.
2.5. Quality control
The detection limit ranged from 0.005 to 0.09 mg kgÿ1. Three laboratory
blanks were run with the samples and concentrations of PAHs in soils were
corrected accordingly. The procedure was also checked for recovery efficien-
cies by analyzing soil samples spiked with PAH standards. The average recov-
ery of the internal standards ranged from 90 to 116%. All readings were
recorded in duplicate and the variation of PAH concentrations of replicated
samples was less than 10%.
2.6. Soil physical and chemical analyses
The methods of soil analyses methods were based on the methods de-
scribed in Lu (2000). Soil pH was measured using 10.0 g air-dried soil (passed
through a 60 mesh) suspended in 25 ml deionized water using a pH meter.
 H.B. Zhang et al. / Environmental Pollution 141 (2006) 107e114 109

Fig. 1. Map of soil sampling sites in Hong Kong.

Total organic carbon (TOC) was measured using potassium bichromate oxida- soil CEC and TOC concentrations followed a similar pattern,
tion process. Total nitrogen was determined by Kjeldahl method. The analysis with the lowest values found in urban soils. The higher
of particle-size distribution was carried out using the pipette method, and clas-
sification of the soil texture was based on Soil Survey Division Staff (1993).
contents of coarse fraction and lower contents of soil CEC
Cation exchange capacity (CEC) was analyzed by ammonium acetate and TOC of urban soils suggested the human disturbance in
saturation. the urban areas (Jim, 2002). Although the C/N ratios of
different soils were similar, the farmland soils had a lower
2.7. Statistical analyses
C/N ratio on average, suggesting that the organic matter
content was more N-rich. In general, urban soils were
Statistical analyses including ANOVA test and cluster analysis were per- disturbed strongly by human activities, farmland and wetland
formed using SPSS 11.0 for windows. The KolmogoroveSmirnov (KeS) soils were moderately affected, while woodland and grassland
test was performed to test the frequency distribution of data set of PAHs con- soils were not affected.
centrations. The variables of not normally distributed were log-transformed to
achieve normal distribution prior to the statistical analyses conducted. Arith-
metic means and geometric means were both provided for expressing the 3.2. Concentrations and distributions of PAH
average concentrations of PAHs. ANOVA test companied with LSD method in Hong Kong soils
were adopted for multiple comparison. Cluster analysis was carried out for
identifying homogeneous groups of individual PAHs in Hong Kong soils.
The raw data was firstly performed with principal components analysis PAHs were detected in all soil samples, and the KeS test
(PCA) before execution of the cluster analysis, and then the scores resulted result indicated that concentrations of total PAH, Phe, Fla
from the PCA were hierarchically clustered using weighted average linkage
between the groups and the Pearson correlation for the cluster intervals Table 1
(Atanassova and Brümmer, 2004). The main characteristics of soils in Hong Kong
Soil properties Land-use patterns
3. Results and discussion Woodland Grassland Farmland Wetland Urban areas
Sand (%) 42.9 38.3 40.9 2.3 79.1
3.1. Major characteristics of Hong Kong soils Silt (%) 33.0 40.8 43.9 55.7 12.0
Clay (%) 24.1 20.9 15.2 42.0 8.9
The properties of the collected surface soils, including soil Textural class Loam Loam Loam Silty clay Loamy sand
USDA
texture, pH, CEC, TOC, C/N ratio are presented in Table 1.
pH (H2O) 4.62 4.70 6.23 6.35 7.52
The texture ranged from silty clay in wetlands to loamy CEC (cmol kgÿ1) 10.2 10.9 8.57 9.75 3.77
sand in urban areas, while most rural soils were loam. The TOC (g kgÿ1) 23.8 21.0 12.3 29.2 5.32
pH (H2O) values of woodland and grassland soils ranged Total nitrogen 1.25 1.18 1.07 1.93 0.28
from strongly to moderately acidic, farmland and wetland soils (g kgÿ1)
C/N ratio 19.0 17.8 11.5 15.1 18.9
were near neutral, while urban soils were more alkaline. The
110 H.B. Zhang et al. / Environmental Pollution 141 (2006) 107e114
and Pyr were normally distributed (P ! 0.05) in soils. The total
concentrations of PAH varied from 7.00 to 410 mg kgÿ1 (dry
wt), with a arithmetic mean of 54.6 mg kgÿ1 (dry wt) and geo-
metric mean of 37.6 mg kgÿ1(dry wt). It was higher than the
total PAH concentrations (1e10 mg kgÿ1 dry wt) of typical en-
dogenous soils resulted from plant synthesis and natural fires
(Edwards, 1983). When comparing with the target value set
by Dutch government for unpolluted soils (20e50 mg kgÿ1)
(Van Brummelen, 1996), most rural soils (7.0 to 69.3 mg kgÿ1
dry wt) were within the target value. However, total PAHs con-
centrations of urban soils (especially samples from Hong
Kong Island) were much higher (O100 mg kgÿ1). Fig. 2 is
the map of total PAH concentrations in Hong Kong soils,
showing that total PAH concentrations higher than 50 mg kgÿ1
were mostly found in urban areas, such as Hong Kong Island,
Kowloon, and Tsuen Wan. The maximum concentration of
410 mg kgÿ1 was detected in the Zoological and Botanical
Garden of Hong Kong Island, which might be due to the
high traffic volumes of the area (Lee, 2001). The soil samples
from Tusen Wan, a former industrial district also contained
a rather high level (O200 mg kgÿ1), as expected.
Table 2 compares the mean concentrations of PAHs in the 5
land use types. Soil PAH concentrations of all soil samples from
rural areas including woodland, grassland, farmland and wet-
land were not significantly different, but they were all signifi-
cantly (P ! 0.05) lower than those contained in urban soils
with the sole exception of Naph, which was almost similar in
all Hong Kong soils (around 6.0 mg kgÿ1 dry wt). The average
total concentration of soil PAHs in urban areas was around
5 folds of those in rural soils, and concentrations of
Fig. 2. Map of total PAHs concentrations in Hong Kong soil.
B(b C k)Fla and Chry in urban soils were 36 and 18 folds
respectively of those in rural soils. It is demonstrated that rural
soil in Hong Kong are not or little polluted by PAHs that emitted
from the urban areas due to the similar concentrations of soil
PAHs among the four using lands of rural areas and much lower
than those in urban areas.
It is commonly observed that PAH concentrations in soils
are affected by soil properties such as TOC, with higher con-
centrations accompanied with high TOC (Wilcke, 2000;
Wilcke and Amelung, 2000; Tam et al., 2001; Ribes et al.,
2003). In this study, such correlation was not revealed between
soil properties and PAH concentrations. However, concentra-
tions of Flu, Phe and BaP showed a significant variance be-
tween two TOC levels (Table 3). The relatively higher
concentrations of these three PAH compounds were always
detected in soils with TOC contents higher than 30 g kgÿ1
(dry wt), but it was not the case of the reverse, which indicated
that soil PAHs in these soils were not biologically formed
from the precursors of soil humus, which just make a role of
prohibiting the PAHs degradation or volatilization from soil
through sorption of the PAHs (Chiou et al., 1998; White and
Pignatello, 1999). The poor correlations between PAHs and
soil properties in this study might associate with the relatively
lower concentrations of PAHs in Hong Kong soils compared
with other reports all carried out in heavily PAH contaminated
sediments (Kim et al., 1999; Yang, 2000). Simpson et al.
(1996) showed that the relationship between total PAHs and
organic carbon was only significant for highly contaminated
sites where total PAH concentration was great than
2000 mg kgÿ1. A weak correlation between TOC and PAH
 H.B. Zhang et al. / Environmental Pollution 141 (2006) 107e114 111

Table 2
Average concentrations (mg kgÿ1 dry weight) of PAHs in soils of Hong Kong
PAH Land-use patterns
Woodland Grassland Farmland Wetland Urban Areas
A.M. G.M. A.M. G.M. A.M. G.M. A.M. G.M. A.M. G.M.
Naph 6.56 5.36 4.62 3.97 4.97 3.43 5.60 5.49 6.24 5.99
Acel 1.13 1.84 1.50 1.61 2.73 2.84 1.90 3.80 2.73 3.29
Ace ND ND Trace Trace ND ND ND ND 0.53 1.05
Flu 2.43 2.04 2.9 2.13 1.24 1.06 1.30 1.30 4.56 4.54
Phe 2.05 1.62 2.11 1.78 1.61 1.74 2.45 4.90 16.7 12.7
Ant 1.06 1.66 0.90 2.13 0.94 3.11 ND ND 3.57 3.95
Fla 8.76 6.98 8.09 8.30 10.3 9.25 3.40 3.38 28.0 23.9
Pyr 3.31 3.75 1.81 3.40 5.33 7.14 11.3 7.56 27.1 21.2
BaAnt 1.51 2.78 1.16 2.76 1.24 1.90 2.15 4.30 8.97 9.28
Chry 0.35 2.04 1.02 4.35 0.07 0.52 2.15 4.30 16.2 11.1
B(b C k)Fla 1.45 1.90 0.99 3.57 ND ND 0.45 0.89 26.7 24.2
BaP 3.39 4.78 4.66 7.33 0.13 0.90 0.85 1.70 9.90 10.7
Ipry 0.04 0.61 0.89 1.56 ND ND 2.05 4.10 8.26 7.18
BghiP 2.24 3.10 4.67 11.2 2.54 2.81 ND ND 9.82 7.88
SPAHs 34.3 30.1 35.4 31.3 31.1 26.91 33.6 29.4 169 134
Numbers of samples 17 19 7 2 8
A.M.: Arithmetic means; G.M.: Geometric means; ND: under detection limit.

was also observed in Welsh rural soils (Jones et al., 1989).
Therefore, it was assumed that in such a not heavily PAHs
contaminated site just like Hong Kong soil, concentration of
PAHs will not be significantly affected by soil TOC concentra-
tion until it reached a certain level.
3.3. PAH profile in Hong Kong soils
The PAH profile of Hong Kong soils is presented in Table 2.
Fla (four-ring PAH), Naph (two-ring PAH) and Pyr (four-ring
PAH) were dominated in rural areas, each accounting for 25.1,
15.7 and 10.6% of the total concentrations respectively, while
Fla, Pyr and B(b C k)Fla(five-ring PAH) were dominated in
urban soils, and each accounting for 16.6, 16.0 and 15.8%
of the total concentration respectively. Fig. 3 further shows
that in urban soils, high weight molecular PAH (O5 rings
PAH) dominated the PAH profiles, with average concentra-
tions higher than that of low weight molecular PAH(2e3 rings
PAH), compared with rural soils, in which average concentra-
tions of 2e3 rings PAHs were higher or equal to that of S5
rings PAH. The different PAH sources of rural and urban soils
are due to the fact that BbFla, BkFla and other 5 rings PAH
such as Chry and BaP are typical markers for fossil fuel com-
bustion (Wilcke, 2003).
Profiles of PAHs also varied within rural areas, e.g. Fla,
Naph, and BaP were dominated in woodland soils whereas
Fla, BghiP and BaP in grassland soils. BaP in these two soils
were relatively higher than other soils due to their higher
concentrations of TOC, which might act as a strong adsorption
matrix for BaP (Chiou et al., 1998). The three predominant
soil PAHs in the human affected farmland and wetland
soils were Naph, Fla and Pyr. The concentration of Pyr was
significantly (P ! 0.05) higher in these two soils than that
in woodland or grassland soils, as it is one of the major
combustion products of fossil fuels and other organic matters
(Wilcke et al., 2000). Oil spill and leakage from boats
and ships, and discharge from municipal and industrial
wastewater and runoff might be attributing to relatively
higher Pyr concentration in the wetland soils (Tam et al.,
2001). Bioformation of Pyr from plant materials and humus
precursors takes place under reducing conditions, and
wetland soil is often waterlogged, which may account partly
160.0
2-3 rings PAH
140.0 4 rings PAH
5 rings PAH
120.0
PAHs Conc.(ug/kg)

Table 3 100.0
Compare means of selected PAHs based on two different Total Organic
Carbon levels 80.0
ÿ1
Selected PAHs TOC Levels (g kg ) Sig. 60.0
(mkgÿ1 dry
!30 O30 40.0
weight)
N Mean Std. N Mean Std.
20.0
Deviation Deviation
Flu 35 1.93 1.80 11 4.12 5.50 0.045 0.0
Phe 35 1.65 1.38 11 3.16 3.10 0.027 Woodland Grassland Farmland Wetland Urban Area
BaP 35 2.06 3.26 11 6.96 4.92 0.000
Fig. 3. Soil PAHs concentrations in different land utilizations.
112 H.B. Zhang et al. / Environmental Pollution 141 (2006) 107e114

for the relatively higher concentration of Pyr (Thiele and Petroleum Grass/Wood/Coal
Petroleum Combustion Combustion
Brummer, 2002). Fla and Naph, which were the major PAHs 1.20
Rural soil
produced in vegetation fires (Freeman and Cattell, 1990; Urban soil
1.00
Kim et al., 2003; Lemieux, 2004) were almost dominated in
all rural soils. This is due to the frequently occurred hill fire

Ant/(Ant+Phe)
0.80 Combustion
in the countryside (from October to next April) resulting
from the activities of grave worship and barbecue (AFCD, 0.60
2002). It is therefore believed that vegetation fire is the major
origin of PAHs in the soils of Hong Kong countryside. 0.40

3.4. Sources of PAHs in Hong Kong soils
It is essential to identify the origin and potential sources of
soil PAH in order to assess the environmental risk caused by
PAHs. A number of studies demonstrated the usefulness of
PAH isomer ratios in source identification (Zheng and Fang,
2000; Lee et al., 2001; Zheng et al., 2002). The ratio of Ant/
(Ant C Phe) is one of the frequently used PAH isomer ratios
in distinguishing between combustion and petroleum sources.
The ratio !0.1 is taken as an indication of petroleum while
a ratio O0.1 indicates a dominance of combustion (Budzinski
et al., 1997). However, Fraser et al. (1998) demonstrated that
Ant undergoes more rapid photochemical reaction in the
atmosphere than Phe, suggesting that the original composition
information will not persevered during atmospheric transport.
In order to assess sources of PAHs in soils more accurately,
the ratio of Fla/(Fla C Pyr) are used as Fla and Pyr
isomer pair degrade photolytically at comparable rates
(Behymer and Hites, 1988). Yunker et al. (2002) suggested
that a Fla/(Fla C Pyr) ratio !0.4 indicates petroleum input,
ratio between 0.4e0.5 liquid fossil fuel (vehicle and crude
oil) combustion and ratio O0.5 grass, wood or coal combus-
tion. In this study, the Ant/(Ant C Phe) ratios ranged from
0e1.0, while Ant in many samples were not detected, it is
therefore difficult to judge the sources of PAHs in these
soils samples only with a Ant/(Ant C Phe) ratio of 0 which
may be due to the photolytic degradation prior to Phe before
deposition onto soils. The ratios of Fla/(Fla C Pyr) in this
study ranged from 0.16e1.0. The minimal value was found
in a farmland soil sample as shown in Fig. 4, indicating that
the input of PAHs was derived from petroleum. The sample
0.20
Petroleum
0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20
Fla/(Fla+Pyr)
Fig. 4. PAH cross plot for the ratio of Ant/(Ant C Phe) vs. Fla/(Fla C Pyr).
and urban areas, a PAHs pattern of aerosol derived from Zheng
et al. (1996) was used to compare with the data obtained from
soils samples collected in the present study (Fig. 5). Taking
into account of different units used in these two studies, a rel-
ative concentration in percentage of individual PAH to total
PAHs were employed. The PAH pattern in rural soils was de-
viated from that found in aerosol characterized by vehicular
exhaust contamination. While the low molecular weight
PAHs such as Phe and Ant may be degraded in soils or lost
by volatilization after deposition, this is hardly the case for
the high-molecular weight PAHs (Wild and Jones, 1995).
Even the pattern of specific vehicular exhaust, high-molecular
weight PAHs in rural soils is different from that in aerosol of
Hong Kong, however, which in urban soil is different to that in
rural soil. The specific vehicular exhaust original PAHs such
as Chry, B(b C k)Fla and BaPyr in urban soil were shown
the resemble trend with that in Hong Kong aerosol. Therefore,
PAHs in Hong Kong urban soils may mainly origin from the
emission of vehicular exhaust, while that in rural soils, bio-
mass combustion may be the predominant source.
30.0
rural soil
Percentages of individual PAHs

urban soil
25.0 aerosol
site was located at a farm near the Tolo Harbour in Ma On
to total PAHs (%)

Shan area, and irrigation with domestic or industrial 20.0

wastewater containing petroleum might be the main source
of soil PAHs. Soil samples with Fla/(Fla C Pyr) ranged 15.0
from 0.4e0.5 was only found once in urban soils, while
most other urban soil samples had a Fla/(Fla C Pyr) ratio 10.0

near 0.5 and an Ant/(Ant C Phe) ratio O0.1, which suggested

5.0
that petroleum combustion was the predominant sources of
soil PAHs in urban areas (Fraser et al., 1998). However, 0.0
most rural soils had Fla/(Fla C Pyr) ratio O0.5, indicating
Chry

BaPyr

Ipyr

B(g,h,i)P
Fla
Phe

Ant

BaAnt

B(b+k)Fla
Pyr

grass, wood or coal combustion was the main PAHs source

in Hong Kong rural soils.
Being densely populated with a heavy traffic, it has been
revealed that vehicular exhaust is the main source of aerosol
PAHs in Hong Kong (Zheng et al., 1996). In order to further
demonstrate the differences in sources of soil PAHs in rural
Individual PAHs
Fig. 5. A relative concentration in percentage of individual PAHs to total
concentrations PAHs in the soil of this study and in aerosol from vehicular
emission in Mong Kok, Hong Kong (Zheng et al., 1996).
 H.B. Zhang et al. / Environmental Pollution 141 (2006) 107e114 113

Rescaled Distance Cluster Combine

CASE 0 5 10 15 20 25
Label Num

Ace 1
BaAnt 4
Phe 13
IPyr 11
Pyr 14
B(b+k)Fla 6
Chry 8
Ant 3
Fla 9
Naph 12
Acel 2
B (g,h,i) P 7
BaPyr 5
Flu 10

Fig. 6. Hierarchical dendogram for 14 individual PAHs in Hong Kong soils using average linkage between groups and Pearson correlation as measure interval.

3.5. Cluster analysis
Cluster analysis was performed to identify the homoge-
neous groups of individual PAHs in Hong Kong soils. The re-
sults presented in the dendrogram (Fig. 6) distinguished the 14
individual PAHs into two major groups. The first major group
can be subdivided into two subgroups. The first subgroup con-
sisted of Ace, BaAnt, Phe, IPyr, Pyr, B(b C k)Fla, Chry and
Ant, which were all low in rural soils, but higher in urban
soils, in particular B(b C k)Fla and Chry (which were 36
and 17 times higher in urban soils than those in rural soils).
Therefore, this subgroup represents the typical marks of
PAHs in Hong Kong urban soils. The second subgroup com-
posed of Fla and Naph, which were both anthropogenic and
biopedogenic origins (Atanassova and Brümmer, 2004). It
was found that Fla was the dominated individual PAH both
in rural and urban soils, and the average concentration of
Naph in rural soils was approximately the same to that in ur-
ban soils. Naph is one of the major PAHs produced in vegeta-
tion fires (Freeman and Cattell, 1990), and Lee et al. (2001)
studied PAHs in Hong Kong atmosphere and found that
Naph in atmosphere is mainly existed in gaseous phase and
can be transported to a long distance. These may explain
why concentrations of Naph in both rural and urban soils
were within the same range. The second major group also con-
tained two subgroups. The first one with Acel and B(ghi)P,
which were found in some rural soils with a high concentra-
tion as in urban soils. They may be produced from biomass
burning (Jenkins et al., 1996). The second one comprised of
BaPyr and Flu, with significant correlations with soil TOC,
indicating that soil organic carbon is also a factor controlling
the concentration of PAHs in Hong Kong soils.
4. Conclusions
The concentrations of PAHs in Hong Kong soils ranged from
7.0e69.3 mg kgÿ1 (dry wt) in rural soils and 42.9e410 mg kgÿ1
in urban soils, respectively. Fluoranthene, Naphthalene and
Pyrene were dominated in rural soils, while Fluoranthene,
Naphthalene and Benzo(b C k)fluoranthene in urban soils.
Higher weight molecular PAHs were observed in urban soils.
The profile of PAHs varied slightly among different types of
land use under rural soils. The present results indicated that
the biomass burning might be the major source of PAHs in rural
soils. However, in urban soils, vehicular emission might play an
important role to soil PAH contamination. Using the cluster
analysis, 4 clusters were distinguished, in which, two clusters
each representing the typical marks of PAHs in urban and rural
soils, one cluster indicating that PAHs were derived from both
anthropogenic and biopedogenic origins, and the last one show-
ing the accumulation of PAHs was related to higher organic
carbon concentrations in Hong Kong soils.
Acknowledgements
The authors are grateful for the financial support given by
the Major State Basic Research Development Program of China
(973 Program), No. 2002CB410810/09, and by the Strategic
Research Fund of the Hong Kong Baptist University.
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