Ecotoxicology and Environmental Safety 159 (2018) 120–126

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Occurrence, characteristics and sources of polycyclic aromatic hydrocarbons T

in arable soils of Beijing, China
⁎ ⁎
Hang Liua, Xiaolu Yua, Zirui Liub, , Ying Suna,
a
Beijing Key Laboratory of Farmland Soil Pollution Prevention and Remediation, College of Resources and Environmental Science, China Agricultural University, Beijing
100193, China
b
State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry (LAPC), Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing
100029, China

A R T I C LE I N FO A B S T R A C T

Keywords: This study investigated the occurrence and sources of polycyclic aromatic hydrocarbons (PAHs) from arable soils
Polycyclic aromatic hydrocarbons in Beijing and compared them with 4 other types of soils: soil from uncultivated land, an incineration plant, a
Arable soils suburb and a woodland. The total concentrations of PAHs ranged from 189.3 to 888.7 μg/kg (mean: 518.2 μg/kg
Source identification for greenhouses and 455.2 μg/kg for fields). The seven carcinogenic PAHs accounted for 11.2–81.3% of
Positive matrix factorization
Σ15PAHs in arable soils. Benzo[a]pyrene toxic equivalent (BaPeq) concentrations were 82.8 μg/kg and 85.4 μg/
kg in greenhouses and fields, respectively. Greenhouses and fields were both dominated by PAHs with 3 and 4
rings. Acenaphthene (ACE), indeno[1,2,3-cd] pyrene (IcdP) and benzo[ghi]perylene (BghiP) were the major
compounds. These results showed that there was insignificant difference between the soil from greenhouses and
fields and both had low carcinogenic potential risk. The diagnostic ratios suggested that the arable soils were
mainly contaminated by coal/biomass combustion. Based on a positive matrix factorization (PMF) model, six
sources were identified including coal combustion, waste incineration, tar, diesel combustion, biomass burning
and gasoline combustion. Coal and gasoline combustion contributed over 40% of the measured PAHs in arable
soils. Diesel combustion, tar and waste incineration were the main sources of pollution for soil from the un-
cultivated land, woodland and incineration plant/suburban. It was concluded that PMF was effective in de-
termining the source apportionment. Urbanization and the evolution of human activities have caused PAH
sources to become more complicated in industrial areas compared to regions with little human disturbance.
Because of this, various factors need to be considered to control the PAH contamination in arable soils.

1. Introduction reported in multi-industrial cities in South Korea (Kwon and Choi,

Sixteen polycyclic aromatic hydrocarbons (PAHs) were identified as
priority controlled organic pollutants by the Unite States Environmental
Protection Agency (USEPA) in 1983, seven of which were classified as
carcinogens. Exposure to PAHs has been implicated in cancer and other
diseases including reproductive disorders (Bolden et al., 2017). Re-
search has also found that China has higher pollution levels and that
higher cancer risks can be tied to elevated PAH levels (Hong et al.,
2016).
Soil is the most important sink for PAHs in the environment with
wet-dry deposition as the common source. It is reported that PAHs can
stay in the soil matrix for a long time because of the strong absorption
between soil particles and organic matter (Chen et al., 2017). The
concentrations of PAHs in soils can be an indicator of the pollution
degree of the environment (Yuan et al., 2015). PAHs in soils have been
2014), urban traffic soils in India (Suman et al., 2016), a large steel-
smelting manufacturer in northern China (Liu et al., 2017), and urban
soils in Shanghai (Wang et al., 2013). Because of their presence in
largely populated areas and their carcinogenic toxicity to human
health, verifying the sources of PAHs is important in minimizing their
risks to human health.
PAHs mainly originate from the incomplete combustion of fossil
fuels and organic materials, the most significant being anthropogenic
sources such as vehicle exhaust, agricultural fires and other industrial
sources. At present, various methods have been used to identify source
characteristics and estimate the contributions of specific sources.
Diagnostic ratio is a relatively simple method used but may cause some
errors due to the various physicochemical behaviors of PAHs in the
environment (Jautzy et al., 2013). To quantitatively identify the con-
tributions of PAH sources, principal component analysis (PCA) and

⁎
Corresponding authors.
E-mail addresses: liuzirui@mail.iap.ac.cn (Z. Liu), sunying@cau.edu.cn (Y. Sun).

https://doi.org/10.1016/j.ecoenv.2018.04.069
Received 18 March 2018; Received in revised form 21 April 2018; Accepted 28 April 2018
0147-6513/ © 2018 Elsevier Inc. All rights reserved.
H. Liu et al.
positive matrix factorization (PMF) have been widely used. However,
the occasional occurrence of negative factor loadings limits the appli-
cation of PCA (Ma et al., 2010). Different from the traditional factor
analysis method, the PMF method can integrate non-negativity con-
strained factor analysis for each factor score. Furthermore, source fin-
gerprinting and non-negative decomposition matrix were dispensable
(Jaeckels et al., 2007). Because of this, it is widely applied in source
apportionment of organic compounds as a receptor model. The model
has been used to identify PAH sources in both agricultural and in-
dustrial soils (Okuda et al., 2010; Liu et al., 2016), both of which were
found to be reasonably stable to explore the source apportionment of
PAHs.
In recent years, urbanization and industrialization have both de-
veloped rapidly, to the point that industry is now supporting agri-
culture. Characteristics of PAHs in agricultural soils at a coke produc-
tion base in Shanxi (Duan et al., 2015) and coal production area in
Xinzhou (Zhao et al., 2014) showed that the PAH pollution was affected
by the nearby industrial production. The emissions of solid fuels (i.e.,
straw and firewood) from rural areas and other agricultural activities
also contributed significantly to PAHs in soils (Wang et al., 2015a).
These studies showcase how pollution degree and sources of PAHs in
arable soils are becoming more and more complicated due to the in-
fluence of urbanization.
Urban agriculture is a practice widely spread in Beijing. One report
about the distribution and sources of PAHs has shown that PAHs were
widespread in urban soils in Beijing (Peng et al., 2011). However,
knowledge about the PAH contamination in arable soils is less avail-
able. PAH contamination in arable soils may contribute to food chain
contamination and presents a human health risk through the con-
sumption of contaminated meat or vegetables (Wang et al., 2015b). So,
it is important to investigate the sources of PAHs in arable soils to
control arable soil quality and reduce human exposure to these toxic
chemicals. The aims of this study were as follows: (1) to measure the
concentrations of PAHs in arable soils in Beijing, (2) to identify the
possible sources by PMF, (3) to compare the pollution degree and
sources with different types of soils.
2. Material and methods
2.1. Soil sampling
A total of 41 arable soil samples were collected in June 2015
(Beijing). Another 4 types of soils were collected from uncultivated
land, an incineration plant, a suburb and a woodland as comparison
(Table S1). One sample was collected in the uncultivated land and
woodland, respectively and two samples were collected in the in-
cineration plant and suburb in two seasons, respectively. Arable soil
samples were divided into greenhouse and field samples. The un-
cultivated land was an open space in a rural area. Samples from the
incineration plant and suburb were collected 0.5 km and 3 km away
from the chimney of the incineration plant, respectively. The woodland
was located in Beijing Songshan National Nature Reserve. At each
10 m × 10 m sampling site, 5 subsamples were taken at a depth of
0–10 cm and bulked together to form one composite sample. All the
samples were air-dried at room temperature for one week, sieved to
100-mesh size particles and stored in amber glass containers at − 4 °C
until analysis.
2.2. Sample preparation
Each soil sample was weighed to 2.0 g and Soxhlet extracted for
24 h with 100 mL n-hexane/dichloromethane (V/V = 1:1). The extracts
were concentrated by rotary vacuum evaporation and then solvent-
exchanged with n-hexane for 2 mL. The concentrated extracts were
cleaned using silica gel column chromatography (25 cm × 1 cm in-
ternal diameter). The glass chromatography column fitted with a
121
Ecotoxicology and Environmental Safety 159 (2018) 120–126
Teflon® stopcock was packed with glass wool from the bottom, then 5 g
silica gel, followed by 2 cm anhydrous sodium sulfate. After adding the
sample extract, the column was eluted with 15 mL n-hexane and then
30 mL n-hexane/dichloromethane (V/V = 3:2). The first fraction con-
taining n- hexane was discarded and the second fraction containing
PAHs was collected. Next, the collected PAH fraction was vacuum-
evaporated and solvent-exchanged with n-hexane and then con-
centrated to 1 mL under a stream of nitrogen before analysis by gas
chromatography/mass spectrometry (GC/MS).
2.3. Gas chromatography/mass spectrometry
The determination of PAHs was performed on an Agilent GC7890/
5975 MSD equipped with HP5-MS column (30 m × 250 µm ×
0.25 µm). The carrier gas was helium. The oven temperature program
was as follows: the initial temperature of 50 °C was held for 2 min, in-
creased at a rate of 20 °C min−1 to 200 °C and held for 2 min, and then
increased at a rate of 6 °C min−1 to 240 °C and then held for 2 min. The
temperature was finally increased at a rate of 3 °C min−1 to 290 °C then
held for 3 min. A 10 μL sample extract was injected in splitless mode.
The injector and ion source were maintained at 280 °C and 230 °C, re-
spectively. Ionization was carried out using the electron impact (EI)
mode and data was acquired using the selective ion monitoring (SIM)
mode. Identification of PAHs was based on the selected ions and the
relative retention time between samples (Table S2 and Fig. S1).
2.4. Quality control
The PAHs were quantified using the external standard method. The
recoveries based on matrix-spiked samples (PAH standards spiked into
3 pre-extracted soil) were 52.1 − 124.1%. The detection limit was
calculated as three times the noise level of the chromatogram for the
blank sample. The detection limits and recoveries of the PAHs are listed
in Table S3. The assay results of naphthalene are usually inaccurate
because of the unstable nature and susceptibility to environmental and
operational factors and so they were not used in the data analysis.
Therefore, the data analysis included only 15 of the 16 PAHs.
2.5. Positive matrix factorization (PMF) model
In this study, PMF analysis was used to analyze the relationships
among the 15 PAHs (excluding naphthalene) and was carried out using
the US EPA PMF 3.0 model (USEPA, 2008). The PMF model was de-
veloped by Paatero and Tapper (1994) and utilized non-negativity
constraints for obtaining physically realistic meanings. It defines a
n × m data original matrix X, where n represented the number of
samples and m represented the number of chemical species, could be
factorized into two matrices, namely G (n × p) and F (p × m) with an
unexplained part E (n × m).
X = G⋅F + E (1)
p
x ij = ∑k =1 gik fkj + eij (2)
where xij was the concentration of the jth chemical species measured in
the ith sample, gik was the contribution of source k to the ith sample, fkj
was the concentration of the jth chemical species in source k, and eij was
the residual for each sample and species.
The objective function (Q) related to the residual and uncertainty is
minimized using weighted least-squares by PMF, which is defined as
2
n m eij ⎞
Q= ∑i =1 ∑ j=1 ⎜⎛ u ⎟
⎝ ij ⎠ (3)
where eij is the difference between the observations and the model and
uij is the uncertainty for each observation. The robust Q value is selected
to reduce the impact of outliers in the fitting of the model. The
H. Liu et al. Ecotoxicology and Environmental Safety 159 (2018) 120–126

Table 1
Detection of 15 PAHs in arable soils (dry weight, n = 41).
Abbreviation Max Min Mean Detectable
(μg/ (μg/ (μg/kg) ratio (%)
kg) kg)

Acenaphthylene ACY 22.7 0.3 6.4 100.0

Acenaphthene ACE 129.8 1.1 47.2 100.0
Fluorene FLO 79.3 N. Da 31.4 87.8
Phenanthrene PHE 125.2 N. D 41.0 87.8
Anthracene ANT 347.6 N. D 48.7 87.8
Fluoranthene FLA 94.6 1.2 38.9 100.0
Pyrene PYR 111.5 2.4 23.7 100.0
Benzo[a]anthracene BaA 104.6 0.4 26.8 100.0
Chrysene CHR 124.4 3.2 35.3 100.0
Benzo[b]fluoranthene BbF 93.7 N. D 24.1 95.1
Benzo[k]fluoranthene BkF 78.6 N. D 26.9 97.6
Benzo[a]pyrene BaP 68.1 N. D 23.1 95.1
Dibenz[a,h]anthracene DahA 88.8 1.5 33.8 100.0
Indeno[1,2,3-cd] pyrene IcdP 111.3 2.0 47.5 100.0
Benzo[ghi]perylene BghiP 122.8 12.3 51.2 100.0
Σ15PAHsb 888.7 189.3 489.6
Σ7PAHsc 472.3 46.2 214.6

a
Not detected.
b
Concentration of the total 15PAHs.
c
Concentration of the total seven carcinogenic PAHs (BaA, CHR, BbF, BkF, BaP, IcdP, and DahA).

theoretical Q value should be approximately equal to the number of 665.8 μg/kg (Jiang et al., 2011), which was a little higher than the
data entries in the concentration file for a model (Ma et al., 2010). The concentrations measured in our study. The PAH contamination in this
task of the PMF model is to minimize this function. The uncertainties study was much lower than that reported in vegetable fields in Tianjin
for each sample were calculated using measurement uncertainties (MU) (6250 μg/kg) (Tao et al., 2004) and Pearl River Delta (1480 μg/kg) (Cai
and method detection limits (MDL). When the sample concentration et al., 2007), and higher than agricultural soils in Xinzhou (202 μg/kg)
was ≤ MDL, the uncertainty u was calculated as: (Zhao et al., 2014) and Huanghuai Plain (188 μg/kg) (Yang et al.,
2013). Compared with the studies done abroad, the PAH concentrations
5
u= × MDL
(4) in Beijing were slightly higher than those in Switzerland (225 μg/kg)
6
(Bucheli et al., 2004) and Japan (320 μg/kg) (Honda et al., 2007), but
and when the sample concentration was > MDL, u was calculated as: lower than those in Poland (616 μg/kg) (Maliszewska-Kordybach et al.,
2008) and India (1906 μg/kg) (Agarwal et al., 2009). To date, PAH
u= (MU × Concentration)2 + MDL2 (5) concentrations in soils are not regulated in China and worldwide there
are few existing recommendations or guidelines. According to the
classification method (Maliszewska-Kordybach et al., 2009), 24.4% of
3. Results and discussion
samples were contaminated (600 ~ 1000 μg/kg) and 2.4% were not
contaminated (< 200 μg/kg) in the study area. Overall the average
3.1. Concentrations of PAHs in arable soils
pollution level was weakly contaminated (200 ~ 600 μg/kg).
The average concentration of PAHs in greenhouses was slightly
The total concentrations of the 15 U.S. EPA priority PAHs (except
higher than in open fields (Table 2). This could be attributed to the
for Naphthalene) in arable soils from Beijing ranged from 189.3 to
closed state of greenhouses which is not conducive to PAH diffusion. In
888.7 μg/kg, with an average value of 489.6 μg/kg (Table 1). The total
addition, rain and snow contribute to the migration of PAHs (Parajulee
concentration of the 15 PAHs was in the same order of magnitude. The
et al., 2017) which could reduce the accumulation in surface soils.
low variability of concentrations between greenhouse and field mainly
Fertilizers and irrigation water is used more often in greenhouses and as
because environment factors have alike influence on the fate of organic
a result, a lot of organic pollutants in the fertilizers and irrigation water
compounds such as meteorological conditions, soil properties and type
enter the soils (Wu et al., 2018). This could indicate that anthropogenic
of use. The average detection rate of the 15 PAHs exceeded 85%. All 4-
activities have heavily influenced the PAHs, particularly in green-
and 6-ring compounds, and some other compounds including ACY, ACE
houses.
and DahA were detected in all samples. The previous field survey in
In order to clarify the pollution level of arable soils, another 4 types
Shanghai reported that the total amount of the target PAHs was
of soils were collected from uncultivated land, an incineration plant, a
suburb and a woodland. The total concentrations of all samples were
Table 2
The concentration of PAHs in soils under different land use (μg/kg). higher than those from the endogenous sources (1–10 μg/kg) (Wilcke,
2000), plant synthesis and natural fires. The woodland was set as the
Σ15PAHs Σ7cPAHs Σ15BaPeq blank control because it had the least amount of human disturbance.
Greenhouse 518.2 ± 213.7b 219.9 ± 148.3b 82.8 ± 9.2b The total concentration was still 3 times higher than 10 μg/kg (Table 2).
Field 455.2 ± 284.9c 207.9 ± 135.6b 85.4 ± 7.4b The concentrations in the suburb and uncultivated land soils were both
Uncultivated land 272 ± 15.7e 52.8 ± 6.1d 27 ± 2.6d about 8 times higher than that of the woodland. The concentration in
Incineration Plant 1114.1 ± 324.9a 464.3 ± 208.4a 152.1 ± 21.5a arable soils was about 15 times higher than the woodland soil but much
Suburb 276.6 ± 78.1d 135.5 ± 29.4c 52.4 ± 13.9c
Woodland 34.5 ± 4.0f 17 ± 2.9e 3.1 ± 0.7e
lower than the urban soils (1202 μg/kg) in Beijing measured by Peng
et al. (2011). The Σ15PAH concentrations in the incineration plant soil
Data are mean ± SD (n = 6). Different letters within the same column indicate were 32 times of that in the woodland soil. Reports about the PAH
significant difference between varied land of use (p < 0.05). concentrations in the incineration plant soil indicated that waste

122
H. Liu et al.
Fig. 1. (a) The distribution of PAHs with different numbers of rings. PAHs with
different numbers of rings varied with shades of the same color, e.g. 3-ring with
red (ACY, ACE, FLO, PHE and ANT), 4-ring with blue (FLA, PYR, BaA and CHR),
5-ring with orange (BbF, Bbk, BaP and DahA), and 6-ring with purple (IcdP and
BghiP). (b) The relative contributions of individual PAH compounds to total
PAHs. (I) total arable soils (n = 41); (II) greenhouses (n = 33); (III) fields
(n = 8).
incineration was one of the main sources of PAH pollution (Sun et al.,
2012).
The potential risk of soil PAHs was estimated based on benzo[a]
pyrene toxic equivalent (BaPeq) concentrations (Kumar et al., 2013).
The BaPeq concentrations in arable soils varied from 10.6 to 167.9 μg/
kg with a mean value of 83.1 μg/kg, which was lower than Xinzhou
(476 μg/kg) (Zhao et al., 2014) and Shanghai (97 μg/kg) (Jiang et al.,
2011) but much higher than Dongjiang (8.3 μg/kg) (Zheng et al., 2014).
The BaPeq concentration in the woodland soil (< 5 μg/kg) indicated
that there was almost no potential risk of PAHs in the untraversed area.
The BaPeq concentration in arable soils was 27 times higher than the
woodland, while in the incineration plant soil the BaPeq concentration
was 50 times higher than the woodland (Table 2). These results showed
that agricultural activities could cause increases in PAH concentrations
and industrial activities posed more serious environmental risks than
agricultural activities. According to Canadian soil quality guidelines for
protection of environmental and human health, the safe BaPeq value is
600 μg/kg for the total amount of eight PAHs including BaA, CHR, BbF,
BkF, BaP, IcdP, DahA, and BghiP (CMCC, 2010). All the samples
showed BaPeq concentrations below the safe value, indicating low risk
to human health from carcinogenic effects.
123
Ecotoxicology and Environmental Safety 159 (2018) 120–126
3.2. Compositional profiles of PAHs
There was a large variation in the range of individual PAH com-
position profiles in different sampling sites (Fig. 1). PAHs with 3 rings
were predominant in greenhouses and fields, accounting for 35% and
32%, followed by 4-ring compounds. ACE, IcdP and BghiP were the
major compounds, accounting for about 10% of the total concentrations
followed by ANT (8.3%), PHE (7.9%), and FLA (7.7%). PHE and FLA
were also reported as the main pollutants in the agricultural soils from
Dongjiang River Basin (Zheng et al., 2014) and Tianjin (Tao et al.,
2004). The proportions of ACE (9.3%) and IcdP (9.6%) in greenhouses
were slightly lower than those in fields (12.1% and 11.4%, respec-
tively). A higher proportion of PHE was obtained in greenhouses (8.4%)
than fields (5.8%). Other major pollutants (i.e., BghiP, ANT and FLA)
distributed similarly in greenhouses and fields. ACY showed the lowest
relative content, accounting for only 1.3%.
Low molecular weight PAHs (2 + 3-ring PAHs) are mainly derived
from low or moderate-temperature combustion processes (Devi et al.,
2016). High molecular weight PAHs (especially for 5 + 6 ring) are
mainly derived from high-temperature combustion processes and exist
in atmospheric particulates with a weak transfer ability (Zhao et al.,
2015). These were found to be more harmful to the environment. In the
woodland soil, PAHs of 5 + 6- ring accounted for only 10%, which
indicated that the woodland soil was less affected by high temperature
combustion. In the uncultivated land, PAHs with high molecular weight
accounted for over 20%. Moreover, PAHs in the arable soils, suburb and
incineration plant mainly came from high temperature combustion
with higher proportions of high molecular weight.
The concentrations of seven carcinogenic PAHs (Σ7cPAHs) (i.e.,
BaA, CHR, BbF, BkF, BaP, IcdP and DahA) varied from 46.2 to
472.3 μg/kg with a mean value of 214.6 μg/kg, accounting for
11.2–81.3% of Σ15PAHs in arable soils. Similar results were reported in
agricultural soils in Shanxi (208 μg/kg) (Duan et al., 2015) and the UK
(272 μg/kg) (Nam et al., 2008). Lower concentrations were found in the
Dongjiang River Basin (46.4 μg/kg) (Zheng et al., 2014), South Korea
(24 μg/kg) (Kwon and Choi, 2014) and Norway (44.1 μg/kg) (Nam
et al., 2008). Higher contamination levels were observed in Nanjing
(747 μg/kg) (Wang et al., 2015a). There was nearly no difference in the
proportion of Σ7cPAHs between greenhouses and fields (42% and 45%)
(Table 2), indicating that the carcinogenic risk was similar. It seemed
that there was a relatively low PAH contamination in Beijing, but still a
higher carcinogenic risk of PAHs compared with other regions. Similar
to arable soils, the Σ7cPAHs all accounted for over 40% in the soil taken
from the incineration plant and suburb. The proportion of Σ7cPAHs in
arable soils was significant higher than that of uncultivated land. This
was mainly attributed to less artificial influence in the uncultivated
land.
Petroleum Combustion Greenhouse
Field
Uncultivate Field
1.0 Incinerate Plant
Suburb
Woodland
0.8 Biomass/coal
Combustion
FLA/FLA+PYR
0.6
Petroleum
0.4
Combustion
0.2
Petroleum
0.0
0.0 0.2 0.4 0.6 0.8 1.0
ANT/ANT+PHE
Fig. 2. Diagnostic ratio charts for FLA/FLA + PYR, and ANT/ANT + PHE in
soil samples.
H. Liu et al.
Fig. 3. Source profile obtained from PMF.
Fig. 4. Source contribution of each factor to PAHs from different sources (G1-
G33 represented for greenhouses and L1-L8 represented for fields).
3.3. Source identifications
In recent years, many ratios of selected PAH concentrations have
been used for identifying their pyrolytic and petrogenic sources.
Diagnostic ratios of FLA/FLA + PYR and ANT/ANT + PHE have been
used to distinguish the possible sources of PAHs in the environment for
their relative stable properties (Yunker et al., 2002). The ratio of ANT/
ANT + PHE under 0.1 usually exists in petrogenic origins (crude oil and
its refined products). The ratio of FLA/FLA + PYR under 0.4 indicates
that PAHs are mainly from typical petroleum contamination and the
ratio between 0.4 and 0.5 expresses that PAHs are originated from
petroleum combustion. PAHs with a ratio higher than 0.5 originate
from grass, wood or coal combustion.
The ANT/ANT + PHE ratios were all over 0.1 except for five sites
with no detection of ANT (Fig. 2). This indicates that the PAHs were
124
Ecotoxicology and Environmental Safety 159 (2018) 120–126
mainly from combustion sources. For the ratios of FLA/FLA + PYR,
60% were over 0.5 suggesting that PAHs in arable soils were mainly
from biomass and coal combustion (Zhang et al., 2013), including 73%
in greenhouses and 37.5% in fields. About 12% of samples in green-
houses and 37.5% in fields were mainly affected by petroleum com-
bution (FLA/FLA + PYR between 0.4 and 0.5). For the uncultivated
land samples, a ratio between 0.4 and 0.5 suggested that petroleum
combustion was the main source. The incineration plant and suburb
were found to be contaminated by biomass/coal combution. The ratio
of the woodland soil showed that it was mainly contaminated by pet-
roleum and slightly affected by petroleum combution.
PMF was used to model the data in order to further study PAH
source identification. There were six sources identified by PMF model
including coal combustion, waste incineration, tar, diesel combustion,
biomass burning and gasoline combustion (Fig. 3). Factor 1 accounted
for 23.8% of the total measured PAHs and was dominated by ACE, FLA
and BghiP. Since ACE and FLA are generally emitted from coal com-
bustion (Kwon and Choi, 2014), factor 1 could be mainly attributed to
coal combustion. Factor 2 accounted for 14.5% of the total measured
PAHs. It represented the influence of waste incineration with the
dominant compounds of BbF and BkF, both of which were found to be
representative for waste incineration (Okuda et al., 2010). Factor 3
contributed 15.1% with the prominent compounds being FLO and
BghiP. These compounds were recognized as major markers of tar
sources. FLO was reported as an indicator of a coke oven source and
coal tar emissions could also enhance the BghiP concentrations (Kohler
et al., 2000). Factor 4 was responsible for 14.5% with a high loading of
BaA, CHR and IcdP. BaA, CHR, BbF, BkF, IcdP and DahA are usually
used as a marker for diesel internal combustion engine (Khalili et al.,
1995). Consequently, this factor could be attributed to the diesel
combustion source. Factor 5 accounted for 11.6% and was dominated
by PHE, ANT and PYR which are believed to be the main source of
biomass combustion (Jiang et al., 2014). Factor 6 making up 20.5% of
the total variance was characterized by high molecular weight PAHs
H. Liu et al.
with a high loading on IcdP and DahA. High emissions of IcdP and
DahA were observed in the particulate matter of gasoline vehicles ex-
haust (Larsen and Baker, 2003) indicating that factor 6 reflected the
contribution of gasoline combustion.
The PMF results showed that the main sources of PAHs were coal
combustion (23.8%) and gasoline combustion (20.5%). This finding
could be explained by the fact that coal burning is the main method of
cooking and heating in rural areas of Beijing. In fields, the contribution
of factor 1 (50%) near the residential area (L6) (Fig. 4) reflected that
the open air was more susceptible to coal burning. In recent years,
straw gasification was used for heating greenhouses in the winter in-
stead of coal. The improvement measure reduced the contribution of
coal burning in the greenhouses; however, tar was produced through
biomass combustion which resulted in a higher contribution of tar
sources in the greenhouses. The sites with the highest PAH concentra-
tion in the greenhouses (G26) and field (L3) showed the highest con-
tribution of factor 6 (40% and 33%). They were believed to be polluted
by traffic emission as they were located on a roadside. Overall, it could
be seen that the daily routines of agricultural areas as well as the
agricultural industry made a great contribution to PAHs in arable soils.
The variation in the composition of soil PAHs in different regions
was related to the soil environment and pollution sources (Fig. 4).
There were four sources of pollution identified in the woodland (i.e.,
coal combustion, tar, biomass burning and gasoline combustion), and
tar was the main contributor. This could be attributed to the significant
inhibitory effect of tar on the poplar ulcer disease. Coal burning also
made a great contribution to PAHs. In the uncultivated land, the
number of sources of PAHs was the same as the woodland but the types
were different. Diesel combustion was the main source in uncultivated
land, probably derived from the emissions of diesel vehicles on the
road. There was almost no contribution of biomass burning to PAH
concentrations because the sample site was near a leisure area for the
local villagers. Compared to the woodland soil, arable soils included
diesel combustion and waste incineration as pollution sources. It
seemed that diesel combustion from agricultural activities have in-
creased the emission of PAHs. Compared with incineration plants,
arable soils have coal and biomass burning as pollution sources. PAHs
were not only from agricultural activities and daily life, but also from
industrial activities in arable soils. Coal and petroleum combustion
made a higher contribution in Beijing soils and biomass combustion
was obviously lower than that of traditional agricultural areas reported
by Zheng et al. (2014) and Wang et al. (2015a) (24% and 27%). It can
be concluded that the transformation of agricultural production pat-
terns has changed the origin and composition of PAHs in arable soils.
PMF is able to fully consider the distribution characteristics of each
compound and create more accurate and comprehensive results. While
the diagnostic ratios could not estimate the contribution of an in-
dividual sample, especially in the range of FLA/FLA + PYR > 0.4, PMF
gave the quantitative results of source profiles for each factor. With the
ratios of FLA/FLA + PYR > 0.5 identified as biomass/coal combustion,
it was determined that biomass/coal combustion took up 40% of the
total contribution calculated by PMF in arable soils (Fig. 3). The pol-
lution source indentification of uncultivated land and woodland by
diagnostic ratio was consistent with PMF. However, the PMF found that
the incineration plant and suburb soils were mainly affected by waste
incineration. Diagnostic ratio limited the specific sources of PAHs be-
cause only a few individual compounds were considered.
4. Conclusion
The concentrations and sources of PAHs from arable soils in Beijing
were analyzed and compared with soils from uncultivated land, an in-
cineration plant, a suburban area and a woodland. The contamination of
arable soils was moderate compared to the other samples: lower than that
of the incineration plant and higher than those of the uncultivated land,
suburb, and woodland. There was a relatively low PAH contamination and
125
Ecotoxicology and Environmental Safety 159 (2018) 120–126
low risk to human health from carcinogenic effects. The major sources of
arable soils were categorized as pyrogenic origins. A PMF model was
successfully applied to identify the PAH sources. The results indicated that
the source apportionment differed between the soils. The main sources in
arable soils were coal and gasoline combustion. It was also found that
fields were more affected by pollution sources than greenhouses. This
study reveals it is necessary to pay more attention to the PAH con-
tamination in arable soils associated with urbanization.
Acknowledgements
This work was supported in part by the National Key Research and
Development Program of China (2016YFD0501404) and the Beijing
Municipal Science and Technology Project (No. Z151100001115008).
We thank Rory Vu Mather who is studying at Washington University
in St. Louis for his linguistic assistance during the preparation of this
manuscript.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.ecoenv.2018.04.069.
References
Agarwal, T., Khillare, P.S., Shridhar, V., Ray, S., 2009. Pattern, sources and toxic potential
of PAHs in the agricultural soils of Delhi, India. J. Hazard Mater. 163, 1033–1039.
Bolden, A.L., Rochester, J.R., Schultz, K., Kwiatkowski, C.F., 2017. Polycyclic aromatic
hydrocarbons and female reproductive health: a scoping review. Reprod. Toxicol. 73,
61–74.
Bucheli, T.D., Blum, F., Desaules, A., Gustafsson, Ö., 2004. Polycyclic aromatic hydro-
carbons, black carbon, and molecular markers in soils of Switzerland. Chemosphere
56, 1061–1076.
Cai, Q., Mo, C., Li, Y., Zeng, Q., Katsoyiannis, A., Wu, Q., Férard, J., 2007. Occurrence and
assessment of polycyclic aromatic hydrocarbons in soils from vegetable fields of the
Pearl River Delta, South China. Chemosphere 68, 159–168.
Chen, W., Wang, H., Gao, Q., Chen, Y., Li, S., Yang, Y., Werner, D., Tao, S., Wang, X.,
2017. Association of 16 priority polycyclic aromatic hydrocarbons with humic acid
and humin fractions in a peat soil and implications for their long-term retention.
Environ. Pollut. 230, 882–890.
CMCC, 2010. Polycyclic aromatic hydrocarbons. Canadian soil quality guidelines for
protection of environmental and human health. Canadian soil quality guidelines.
Devi, N.L., Yadav, I.C., Shihua, Q., Dan, Y., Zhang, G., Raha, P., 2016. Environmental
carcinogenic polycyclic aromatic hydrocarbons in soil from Himalayas, India: im-
plications for spatial distribution, sources apportionment and risk assessment.
Chemosphere 144, 493–502.
Duan, Y., Shen, G., Tao, S., Hong, J., Chen, Y., Xue, M., Li, T., Su, S., Shen, H., Fu, X.,
Meng, Q., Zhang, J., Zhang, B., Han, X., Song, K., 2015. Characteristics of polycyclic
aromatic hydrocarbons in agricultural soils at a typical coke production base in
Shanxi, China. Chemosphere 127, 64–69.
Honda, K., Mizukami, M., Ueda, Y., Hamada, N., Seike, N., 2007. Residue level of poly-
cyclic aromatic hydrocarbons in Japanese paddy soils from 1959 to 2002.
Chemosphere 68, 1763–1771.
Hong, W.J., Jia, H., Ma, W., 2016. Distribution, fate, inhalation exposure and lung cancer
risk of atmospheric polycyclic aromatic hydrocarbons in some Asian countries.
Environ. Sci. Technol. 50, 7163–7174.
Jaeckels, J.M., Bae, M., Schauer, J.J., 2007. Positive Matrix Factorization (PMF) analysis
of molecular marker measurements to quantify the sources of organic aerosols.
Environ. Sci. Technol. 41, 5763–5769.
Jautzy, J., Ahad, J.M.E., Gobeil, C., Savard, M.M., 2013. Century-long source appor-
tionment of PAHs in Athabasca oil sands region lakes using diagnostic ratios and
compound-specific carbon isotope signatures. Environ. Sci. Technol. 47, 6155–6163.
Jiang, Y., Hu, X., Yves, U.J., Zhan, H., Wu, Y., 2014. Status, source and health risk as-
sessment of polycyclic aromatic hydrocarbons in street dust of an industrial city, NW
China. Ecotox Environ. Saf. 106, 11–18.
Jiang, Y., Wang, X., Wu, M., Sheng, G., Fu, J., 2011. Contamination, source identification,
and risk assessment of polycyclic aromatic hydrocarbons in agricultural soil of
Shanghai, China. Environ. Monit. Assess. 183, 139–150.
Khalili, N.R., Sheff, P.A., Holsen, T.M., 1995. PAH source fingerprints for coke ovens,
diesel and, gasoline engines, highway tunnels, and wood combustion emissions.
Atmos. Environ. 29, 533–542.
Kohler, M., Künniger, T., Schmid, P., Gujer, E., Crockett, R., Wolfensberger, M., 2000.
Inventory and emission factors of creosote, Polycyclic Aromatic Hydrocarbons (PAH),
and phenols from railroad ties treated with creosote. Environ. Sci. Technol. 34,
4766–4772.
Kumar, B., Verma, V.K., Kumar, S., Sharma, C.S., 2013. Probabilistic health risk assess-
ment of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in urban
soils from a tropical city of India. J. Environ. Sci. Heal A 48, 1253–1263.
H. Liu et al.
Kwon, H., Choi, S., 2014. Polycyclic aromatic hydrocarbons (PAHs) in soils from a multi-
industrial city, South Korea. Sci. Total Environ. 470, 1494–1501.
Larsen, R.K., Baker, J.E., 2003. Source apportionment of polycyclic aromatic hydro-
carbons in the urban atmosphere: a comparison of three methods. Environ. Sci.
Technol. 37, 1873–1881.
Liu, G., Niu, J., Guo, W., An, X., Zhao, L., 2016. Ecological and health risk-based char-
acterization of agricultural soils contaminated with polycyclic aromatic hydro-
carbons in the vicinity of a chemical plant in China. Chemosphere 163, 461–470.
Liu, W., Wang, Y., Chen, Y., Tao, S., Liu, W., 2017. Polycyclic aromatic hydrocarbons in
ambient air, surface soil and wheat grain near a large steel-smelting manufacturer in
northern China. J. Environ. Sci.-China 57, 93–103.
Ma, W., Li, Y., Qi, H., Sun, D., Liu, L., Wang, D., 2010. Seasonal variations of sources of
polycyclic aromatic hydrocarbons (PAHs) to a northeastern urban city, China.
Chemosphere 79, 441–447.
Maliszewska-Kordybach, B., Smreczak, B., Klimkowicz-Pawlas, A., 2009. Concentrations,
sources, and spatial distribution of individual polycyclic aromatic hydrocarbons
(PAHs) in agricultural soils in the Eastern part of the EU: poland as a case study. Sci.
Total Environ. 407, 3746–3753.
Maliszewska-Kordybach, B., Smreczak, B., Klimkowicz-Pawlas, A., Terelak, H., 2008.
Monitoring of the total content of polycyclic aromatic hydrocarbons (PAHs) in arable
soils in Poland. Chemosphere 73, 1284–1291.
Nam, J.J., Thomas, G.O., Jaward, F.M., Steinnes, E., Gustafsson, O., Jones, K.C., 2008.
PAHs in background soils from Western Europe: influence of atmospheric deposition
and soil organic matter. Chemosphere 70, 1596–1602.
Okuda, T., Okamoto, K., Tanaka, S., Shen, Z., Han, Y., Huo, Z., 2010. Measurement and
source identification of polycyclic aromatic hydrocarbons (PAHs) in the aerosol in
Xi'an, China, by using automated column chromatography and applying positive
matrix factorization (PMF). Sci. Total Environ. 408, 1909–1914.
Paatero, P., Tapper, U., 1994. Positive matrix factorization: a non-negative factor model
with optimal utilization of error estimates of data values. Environmetrics 5, 111–126.
Parajulee, A., Lei, Y.D., Kananathalingam, A., McLagan, D.S., Mitchell, C.P.J., Wania, F.,
2017. The transport of polycyclic aromatic hydrocarbons during rainfall and snow-
melt in contrasting landscapes. Water Res 124, 407–414.
Peng, C., Chen, W., Liao, X., Wang, M., Ouyang, Z., Jiao, W., Bai, Y., 2011. Polycyclic
aromatic hydrocarbons in urban soils of Beijing: status, sources, distribution and
potential risk. Environ. Pollut. 159, 802–808.
Suman, S., Sinha, A., Tarafdar, A., 2016. Polycyclic aromatic hydrocarbons (PAHs) con-
centration levels, pattern, source identification and soil toxicity assessment in urban
traffic soil of Dhanbad, India. Sci. Total Environ. 545, 353–360.
Sun, S., Li, Y., Zhou, Y., Wang, H., Sun, Y., 2012. Pilot study on PAHs of the atmosphere
Around the refuse incineration plant based on the technology of passive sampling.
Environ. Sci. 33, 4018–4024.
126
Ecotoxicology and Environmental Safety 159 (2018) 120–126
Tao, S., Cui, Y.H., Xu, F.L., Li, B.G., Cao, J., Liu, W.X., Schmitt, G., Wang, X.J., Shen, W.R.,
Qing, B.P., Sun, R., 2004. Polycyclic aromatic hydrocarbons (PAHs) in agricultural
soil and vegetables from Tianjin. Sci. Total Environ. 320, 11–24.
US EPA, 2008. EPA positive matrix factorization (PMF) 3.0 fundamentals & user guide.
[Online available at 〈http://www.epa.gov/heasd/products/pmf/pmf.htm〉].
Wang, C., Wu, S., Zhou, S., Wang, H., Li, B., Chen, H., Yu, Y., Shi, Y., 2015a. Polycyclic
aromatic hydrocarbons in soils from urban to rural areas in Nanjing: concentration,
source, spatial distribution, and potential human health risk. Sci. Total Environ. 527,
375–383.
Wang, Y., Luo, C., Wang, S., Liu, J., Pan, S., Li, J., Ming, L., Zhang, G., Li, X., 2015b.
Assessment of the air–soil partitioning of polycyclic aromatic hydrocarbons in a
paddy field using a modified fugacity sampler. Environ. Sci. Technol. 49, 284–291.
Wang, X., Miao, Y., Zhang, Y., Li, Y., Wu, M., Yu, G., 2013. Polycyclic aromatic hydro-
carbons (PAHs) in urban soils of the megacity Shanghai: occurrence, source appor-
tionment and potential human health risk. Sci. Total Environ. 447, 80–89.
Wilcke, W., 2000. SYNOPSIS Polycyclic Aromatic Hydrocarbons (PAHs) in Soil — a
Review. J. Plant Nutr. Soil Sc. 163, 229–248.
Wu, B., Guo, S., Li, X., Wang, J., 2018. Temporal and spatial variations of polycyclic
aromatic hydrocarbons (PAHs) in soils from a typical organic sewage irrigation area.
Sci. Total Environ. 613, 513–520.
Yang, B., Zhou, L., Xue, N., Li, F., Li, Y., Vogt, R.D., Cong, X., Yan, Y., Liu, B., 2013. Source
apportionment of polycyclic aromatic hydrocarbons in soils of Huanghuai plain,
China: Comparison of three receptor models. Sci. Total Environ. 443, 31–39.
Yuan, G., Wu, L., Sun, Y., Li, J., Li, J., Wang, G., 2015. Polycyclic aromatic hydrocarbons
in soils of the central Tibetan Plateau, China: distribution, sources, transport and
contribution in global cycling. Environ. Pollut. 203, 137–144.
Yunker, M.B., Macdonald, R.W., Vingarzan, R., Mitchell, R.H., Goyette, D., Sylvestre, S.,
2002. PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators
of PAH source and composition. Org. Geochem. 33, 489–515.
Zhang, J., Yang, J., Wang, R., Hou, H., Du, X., Fan, S., Liu, J., Dai, J., 2013. Effects of
pollution sources and soil properties on distribution of polycyclic aromatic hydro-
carbons and risk assessment. Sci. Total Environ. 463, 1–10.
Zhao, L., Hou, H., Shangguan, Y., Cheng, B., Xu, Y., Zhao, R., Zhang, Y., Hua, X., Huo, X.,
Zhao, X., 2014. Occurrence, sources, and potential human health risks of polycyclic
aromatic hydrocarbons in agricultural soils of the coal production area surrounding
Xinzhou, China. Ecotoxicol. Environ. Saf. 108, 120–128.
Zhao, X., Kim, S., Zhu, W., Kannan, N., Li, D., 2015. Long-range atmospheric transport
and the distribution of polycyclic aromatic hydrocarbons in Changbai Mountain.
Chemosphere 119, 289–294.
Zheng, T., Ran, Y., Chen, L., 2014. Polycyclic aromatic hydrocarbons (PAHs) in rural soils
of Dongjiang River Basin: occurrence, source apportionment, and potential human
health risk. J. Soil Sediments 14, 110–120.