Chemosphere 181 (2017) 360e367

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Chemosphere
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Characteristic accumulation of PCDD/Fs in pine needles near an MSWI

and emission levels of the MSWI in Pearl River Delta: A case study
Pei Chen a, *, Xiao Xiao a, Jun Mei b, Ying Cai a, Yuhui Tang a, Ping'an Peng a, c
a
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China
b
School of Pharmacy, Guangdong Medical University, Dongguan, 523808, China
c
University of Chinese Academy of Sciences, Beijing, 100049, China

h i g h l i g h t s

Extremely high levels of PCDD/Fs were found in pine needles near an MSWI.

PCDD/Fs in pine needles mainly depend on atmospheric contents, exposure time and wind direction.

PCDD/Fs adsorbed to pine needle are mainly via gas-phase partition from atmosphere.

Emission sources impact dioxin distribution patterns in pine needles.

Total PCDD/F levels of pine needles cover up the actual photolysis information.

a r t i c l e i n f o a b s t r a c t

Article history: Pine needle samples were collected near a municipal solid waste incinerator (MSWI) in Pearl River Delta,
Received 23 November 2016 southern China, as well as the stack gas and dust samples of the MSWI were simultaneously collected.
Received in revised form Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were analyzed
4 April 2017
following the USEPA Method 1613B. The concentration of PCDD/Fs in the pine needles (137e625 ng/kg,
Accepted 21 April 2017
Available online 22 April 2017
25e51 ng I-TEQ/kg) is the highest level ever detected in China. Congener profile comparison and prin-
cipal component analysis (PCA) confirmed the MSWI as an important emission source of environmental
Handling Editor: Gang Yu PCDD/Fs. The PCDD/Fs in the pine needles mainly depended on the atmospheric concentration, exposure
time and also the wind direction. The accumulation of PCDD/Fs in this species did not occur at a steady
Keywords: rate, and the total concentrations covered up the actual photolysis information. Gas-phase partitioning of
MSWI compounds in the atmosphere was the dominant process through which PCDD/Fs were adsorbed onto
Pine needle the pine needle surface in contrast with particle-phase deposition, and subsequent environmental
PCDD/Fs behavior varied between the congeners. Photo-degradation was the major transformation process as
Photo-degradation
PCDD/Fs were adsorbed onto the pine needle surfaces. Higher chlorinated PCDD/Fs were more recalci-
Stack gas
trant to photo-degradation than those that were less chlorinated, and PCDDs were more resistant to
Dust
photo-degradation than PCDFs. On the other hand, the strong ability of lipid-rich pine needles to
accumulate dioxin compounds indicates they can be used as the absorption sink of PCDD/Fs in heavily
polluted areas because it is easier to dispose of pine needles than it is to clean contaminated air.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction “Stockholm Convention” as early as 2001 and have been studied

Polychlorinated dibenzo-p-dioxins (PCDDs) and poly-
chlorinated dibenzofurans (PCDFs) are well-known persistent
organic pollutants (POPs). These compounds were included in the
* Corresponding author. Guangzhou Institute of Geochemistry, Chinese Academy
of Sciences Wushan, P. O. Box 1131, Guangzhou, GD, 510640, China.
E-mail address: pchen@gig.ac.cn (P. Chen).
for nearly half a century (van Bavel and Abad, 2008). They are
ubiquitous in the environment and with respect to the high
toxicity of some congeners, such as 2,3,7,8-substituted PCDD/Fs,
they are considered to have the highest potential risk to human
health (Boening, 1998). PCDD/Fs are unwanted products of hu-
man activities, such as biomass and fossil fuel combustion, in-
dustrial processes (chemical manufacturing, metal smelting, steel
sintering and paper mills, etc.), medical waste incineration

http://dx.doi.org/10.1016/j.chemosphere.2017.04.098
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
 P. Chen et al. / Chemosphere 181 (2017) 360e367
(MWI), and municipal solid waste incineration (MSWI) (Kulkarni
et al., 2008). Once emitted from pollution sources, these types of
POPs were primarily into the ambient air directly, and were then
transported to other parts of biosphere, such as land and
vegetation.
Because of the hydrophobic outer surfaces that can absorb
lipophilic organic compounds, mainly from atmosphere, vegetation
has been used as a passive air sampler to indicate atmospheric
pollution (Ok et al., 2002; Chen et al., 2006, 2012; Bochentin et al.,
2007). Among evergreen species, pines are widely distributed, and
their needles have high lipid contents. Consequently, pine needles
are considered as suitable and useful long-term biomonitors for
atmospheric POP pollution at global and regional scales. Pine
needles have been used for atmospheric PCDD/F contaminant
monitoring in many countries (Holoubek et al., 2000; Kim et al.,
2005; Chen et al., 2006; Ok et al., 2002; Safe et al., 1992).
Pollutant uptake by vegetation occurs mainly through gas-phase
partitioning or particle-phase deposition from the atmosphere
adsorbing onto the surface and subsequently diffuses into the waxy
cuticle of the leaves or through stomata followed by phloem
translocation.
In the current study, pine needle samples were collected from
the vicinity of an MSWI. In addition, stack gas and dust samples
from the MSWI were simultaneously collected to further investi-
gate the PCDD/F accumulation status in pine needles, expanding on
our previous research (Chen et al., 2012). MSWIs, which have been
identified as significant contributors to the environmental levels of
PCDD/Fs in many countries, serve as stationary dioxin emission
sources. Pine needles in the vicinity of MSWIs have being exposed
to a relatively steadily contaminated atmosphere, which may allow
us to explore variations in the concentrations of PCDD/Fs in pine
needles of different growing years and in different sampling loca-
tions relative to the contaminant source. The main aims of this
study are to examine the PCDD/F accumulation rate in pine needles
and try to found out the details of congener behavior during the
accumulation.
2. Materials and methods
2.1. Basic information on the MSWI
The investigation was conducted in an MSWI plant located in
Pearl River Delta, southern China. More than 1000 tons of munic-
ipal solid wastes are treated daily, and the MSWI has been oper-
ating for more than ten years. The MSWI power plant consists of
four fluidized bed incinerators, each with its own air pollutant
control devices (APCDs) which are composed of a semi-dry
scrubber and bag filter.
2.2. Sampling
One- and two-year-old pine (Pinus massoniana) needle samples
were collected near the MSWI in March 2013. The sampling sites
were located to the north and south of the MSWI. All 12 pine needle
samples were collected from a similar height of approximately
1.5e2.0 m above the ground. Several sub-samples from three to six
trees were pooled to yield a representative sample. Three dust
samples were collected from the MSWI workshop. A total of nine
stack gas samples from the MSWI were collected at the stack
sampling point with a sampling time of 120 min for each sample,
following the Standard EPA Method 23A (US EPA, 1996). All the
three types of samples were transported to the laboratory and
stored in aluminum foil at 20  C until analysis.
361
2.3. Chemicals and standards
All solvents, including toluene, hexane, dichloromethane
(DCM), methanol and acetone, were of HPLC/American chemical
society (ACS) certified grade and were obtained from Honeywell
and J.T. Baker (USA). Silica gel (70e230 mesh) and Florisil used in
the clean-up procedures were purchased from Merck (Germany). In
addition, 13C12-labeled PCDD/F standards were obtained from
Cambridge Isotope Laboratories (CIL, USA).
2.4. Cleanup and instrumental analysis
The sample preparation procedures were reported in our pre-
vious work (Chen et al., 2012). In brief, pine needle samples were
sequentially washed, three times, using distilled water. The sam-
ples were then freeze-dried, pulverized to a size less than 80 mesh,
and homogenized. The pine needle, stack gas and dust samples
were then analyzed following the USEPA Method 1613B (US EPA,
1994) by isotope dilution high resolution gas chromatography-
high resolution mass spectrometry (HRGC-HRMS, Trace GC 2000
and Finnigan MAT 95 XP, Thermo). Firstly, the powdered pine
needles, glass fiber filters and XAD-2 resin and dust samples were
Soxhlet-extracted with toluene for 24 h after being spiked with a
mixture of 15 13C-labeled internal standards (CIL, EDF-8999). The
extracts were rotary evaporated to 1e2 ml and were sequentially
cleaned using an acid silica gel bed, a multilayer silica gel column
and a Florisil column. The final eluate was concentrated to 20 mL
under gentle nitrogen gas flow and spiked with injection standards
(CIL, EDF-5999). The details of the cleanup procedures, HRGC-
HRMS conditions and quality assurance/quality control (QA/QC)
measures are described in the Supporting Information (SI).
3. Results and discussion
3.1. The concentrations of 2,3,7,8-PCDD/Fs in stack gas and dust
The concentrations of seventeen 2,3,7,8-chlorine-substituted
congeners and the total PCDD/Fs were presented in Table 1. PCDD/
Fs were identified in all three sample types, and the levels indicated
considerable differences between pine needles collected from
different geographical locations and with different growth years.
The toxicity equivalencies (TEQs) of the 2,3,7,8-PCDD/Fs were
calculated based on World Health Organization (WHO) toxicity
equivalency factors (W-TEFs) (Van den Berg et al., 2006) and in-
ternational TEFs (I-TEFs) recommended by the North Atlantic
Treaty Organization (Kutz et al., 1990), respectively.
The total concentration of seventeen 2,3,7,8-PCDD/Fs in nine
stack gas samples ranged from 1.9 to 14.8 ng/Nm3, with TEQs of
0.16e0.79 ng WHO-TEQ/Nm3 and 0.17e0.84 ng I-TEQ/Nm3
respectively. The values were lower than the regulation level (1.0 ng
TEQ/Nm3) set by the Ministry of Environmental Protection of the
People's Republic of China (MEP) in 2001 (China MEP, 2001).
However, the values were higher than the newly modified limit and
European Union directive value, both of which are 0.1 ng TEQ/Nm3
(China MEP, 2014; European Union, 2000). A study carried out in
2006 investigated 19 waste incineration plants in China and found
that the emission levels of PCDD/Fs ranged from 0.042 to 2.5 ng
TEQ/Nm3 (average value of 0.42 ng TEQ/Nm3) (Ni et al., 2009); 84%
of the results met the MEP regulation level at that time (1.0 ng TEQ/
Nm3). Compared to other studies around the world (Table 2), the
levels in this study are higher than those of developed countries
with the emission levels less than 0.1 ng TEQ/Nm3 (Quass et al.,
2004). Studies in Korea are the exception: the PCDD/F emission
level of MSWIs reached a value of 36.3 ng TEQ/Nm3 (Oh et al., 1999).
Incinerators operating over long-term periods may contribute to a
362 P. Chen et al. / Chemosphere 181 (2017) 360e367

Table 1
Concentrations of 2,3,7,8-substituted PCDDs/Fs in stack gas, dust and pine needle samples.

Stack Gas (n ¼ 9) ng/Nm3 average (range) Dust (n ¼ 3) ng/kg, average Pine needle (1 year) ng/kg Pine needle (2 years) ng/kg
dw average dw average

S-1 (n ¼ 3) N-1 (n ¼ 3) S-2 (n ¼ 3) N-2(n ¼ 3)

2,3,7,8-TCDF 0.089 (0.018e0.17) 40.2 8.8 28.9 17.4 53.1

1,2,3,7,8-PeCDF 0.18 (0.053e0.31) 63.6 9.2 25.6 17.4 48.4
2,3,4,7,8-PeCDF 0.35 (0.16e0.63) 106 8.6 27.8 18.0 51.1
1,2,3,4,7,8-HxCDF 0.32 (0.12e0.60) 222 6.8 19.9 16.5 49.0
1,2,3,6,7,8-HxCDF 0.34 (0.12e0.61) 183 6.4 19.6 15.9 46.8
2,3,4,6,7,8-HxCDF 0.48 (0.15e0.92) 198 5.7 18.3 15.7 35.8
1,2,3,7,8,9-HxCDF 0.032 (0.0069e0.072) 12.6 1.1 3.7 2.9 6.9
1,2,3,4,6,7,8-HpCDF 1.1 (0.35e1.9) 1147 50.0 32.2 78.3 65.9
1,2,3,4,7,8,9-HpCDF 0.19 (0.044e0.44) 97.6 1.3 2.5 4.1 5.3
OCDF 0.73 (0.26e1.9) 460 5.4 8.9 18.9 17.3
2,3,7,8-TCDD 0.016 (0e0.029) 5.6 1.2 3.6 2.3 7.9
1,2,3,7,8-PeCDD 0.079 (0.031e0.16) 17.7 2.5 9.5 8.3 18.1
1,2,3,4,7,8-HxCDD 0.10 (0.030e0.23) 29.0 5.1 5.4 11.2 10.9
1,2,3,6,7,8-HxCDD 0.19 (0.057e0.48) 55.4 4.7 10.4 7.3 22.5
1,2,3,7,8,9-HxCDD 0.16 (0.042e0.41) 43.5 11.4 23.5 31.3 47.3
1,2,3,4,6,7,8-HpCDD 0.90 (0.21e2.4) 654 7.8 16.0 20.0 44.6
OCDD 1.0 (0.34e3.0) 1483 12.7 34.8 36.3 59.2
P
2,3,7,8-PCDD/Fs 6.3 (1.9e14.8) 4819 149 291 321.7 590
WHO-TEQ 0.40 (0.16e0.79) 155 12.1 35.7 29.3 71.2
I-TEQ 0.44 (0.17e0.84) 170 12.8 37.1 29.2 73.4

Nm3: m3 at 0  C and 1 atm.

Table 2
Comparison of 2,3,7,8-substituted PCDD/Fs in stack gas from other studies.

Country Concentration (ng/Nm3) I-TEQ (ng TEQ/Nm3) Reference

China 0.13e32.4 0.0054e0.19 Yan et al., 2006

0.042e2.5 Ni et al., 2009
1.9e14.8 0.15e0.84 This study
Korea 4.7e2100 0.07e36.5 Oh et al., 1999
36.3 1.9 Kim et al., 2005
Spain <0.1 ng (except two case of 0.7 and 1.08) Fabrellas et al., 2001
France 0.017 ng (Larger MSWIs) Nzihou et al., 2012
0.003 ng (Smaller MSWIs)
Taiwan 0.14 ng (average) Chang et al., 2004
0.17 ng (average) Chi and Chang, 2005

higher level of PCDD/Fs in stack gas; thus, proper maintenance of
the incinerator, improved APCDs, and advanced incineration con-
trol technologies are urgently needed in China.
2,3,7,8-PCDD/Fs in the dust samples collected from the MSWI
workshop in this study were at a high level (average value of 4.8 ng/
g and 0.17 ng I-TEQ/g). However, these values are much lower than
those measured in dust from an industrial waste incinerator (IWI)
in Korea (61.2 ng/g and 1.8 ng I-TEQ/g) (Kim et al., 2005) and
comparable to family-based workshop dust (average: 3.4 ng/g and
0.38 ng WHO-TEQ/g) collected from intensive electronic waste (e-
waste) recycling sites in southern China (Ma et al., 2008; Hu et al.,
2013) and Vietnam (Tue et al., 2010). With respect to general indoor
house dust, the PCDD/Fs in the MSWI workshop dust were
approximately 1e3 orders of magnitude higher than those in house
dust reported in several countries (United States, Korea, Japan)
(Wenning et al., 2006; Deziel et al., 2012; Kim and Moon, 2013;
Takigami et al., 2009; Suzuki et al., 2010). This finding indicates
that MSWI workers are more readily exposed to dioxins via dust
ingestion through inhalation/dermal absorption than other resi-
dents. In addition, these workers might be subjected to a higher risk
of cancer compared with other residents, according to an epide-
miological study on PCDD/F exposure and cancer mortality among
industrial workers (Wang et al., 2013).
3.2. 2,3,7,8-PCDD/Fs levels in pine needles
The concentrations of PCDD/Fs in pine needles near the MSWI
ranged from 137 to 306 ng/kg dw in the one-year-old samples and
285e625 ng/kg dw in the two-year-old samples, with mean values
of 220 ng/kg dw (I-TEQ: 24.9 ng/kg) and 456 ng/kg dw (I-TEQ:
51.3 ng/kg), respectively. The PCDD/F concentration measured in
the two-year-old pine needles is the highest level ever reported in
China and is also higher than some developed countries such as
Japan (27e110 ng/kg dw), Korea (0.62e26.9 ng TEQ/kg dw), Ger-
many (2.5e11.5 ng/kg dw) and Poland (0.01e3.2 ng TEQ/kg dw)
(Hanari et al., 2004; Ok et al., 2002; Rappolder et al., 2007;
Bochentin et al., 2007). In our previous study, we monitored
PCDD/Fs in pine needles in 38 cities across China, and the con-
centrations ranged from 5.4 to 330 pg/g dw (Chen et al., 2012). The
pine needle samples from these 38 cities were mainly collected far
enough from industrial plants or major traffic roads and repre-
sented the general PCDD/F contamination extent of urban areas.
Therefore, it is logical that these results are much lower than those
of needles exposed to a stationary emission source in the current
study. The PCDD/F concentrations in pine needles around other
intensive point sources, such as pulp/paper mills, penta-
chlorophenol (PCP) wood-preserving sites and IWIs, were lower
than 144 ng/kg dw (Sinkkonen et al., 1997), 7.7 ng TEQ/kg dw (Safe
et al., 1992) and 16.4 ng TEQ/kg dw (7.4 ng TEQ/kg ww, at a water
content of 55%) (Kim et al., 2005), respectively, which were much
lower than the PCDD/F concentrations of pine needles from the
MSWI in this study. Therefore, the elevated data from the present
study indicates the MSWI is an important emission source of
environmental PCDD/Fs.
 P. Chen et al. / Chemosphere 181 (2017) 360e367
The pine needles were further discussed in two groups, the
southern and northern groups, in order to better understand the
factors that affect PCDD/F accumulation in pine needles. The results
showed that samples collected from the north of the MSWI had
obviously higher dioxin levels (Table 1 & Fig. 1). As the pine needles
in the present case were exposed to the only stationary emission
source, the main reason for that disparity may be the typical sub-
tropical monsoon climate and the prevailing wind from the
southeast. In addition, the PCDD/F contents of the northern
(downwind) group were almost 2e3 times as the southern (up-
wind) group (for similar-aged samples), suggesting that in addition
to the point emission source, the wind orientation also played an
important role in rising topical atmospheric pollution level,
resulting in a relatively higher accumulation in the pine needles
nearby. In addition, the concentration of PCDD/Fs was approxi-
mately doubled in the two-year-old pine needle samples compared
with the one-year-old samples (Table 1 & Fig. 1). It was inferred that
pine needles have a considerable ability to serve as a dioxin sink to
record and indicate the local pollution situation over a long-time
period. The contents in pine needles of different ages may help to
reconstruct the historical variation tendency of PCDD/F contami-
nation. However, there is no information on the saturation level of
this species for these types of compounds, which requires further
investigation. In conclusion, the important finding was that PCDD/F
accumulation in pine needles depends mainly on the atmospheric
concentration and exposure time.
3.3. Congener and homologue profiles of PCDD/Fs in pine needles
The congener and homologue profiles of 2,3,7,8-PCDD/Fs in pine
needles are shown in Fig. 2(c, d, e, f) and Fig. 3. The predominant
congener was 1,2,3,4,6,7,8- HpCDF, which accounted for 29.0%
(mean value) in the southern samples and 11.1% (mean value) in the
northern samples, followed by OCDD. An interesting result was that
both the northern and southern samples exhibited a little differ-
ence with respect to the homologue profiles. Samples from the
south of the MSWI were dominated by hepta-PCDFs (mean 30.1%),
whereas hexa-PCDFs were dominant in the northern samples, i.e.,
22.3% (mean value). All samples showed a similar distribution
pattern with respect to the PCDDs, i.e., hexa- > octa- > hepta-
> penta- and tetra-PCDD.
The ratio of PCDFs to PCDDs is a useful source and degradation
indicator. Fresh emitted PCDD/Fs from combustion processes usu-
ally showed a typical congener pattern in which PCDFs was equal to
or greater than the PCDDs (Reischl et al., 1989), while aged PCDD/Fs
Fig. 1. 2,3,7,8-PCDD/F concentrations in pine needles.
363
or those from sources other than combustion are abundant in
PCDDs. Therefore, high PCDFs/PCDDs ratios (ranged from 1.75 to
2.33) found in pine needle samples of the current study indicating
the PCDD/Fs in the pine needles were freshly produced and mainly
derived from a combustion source.
The PCDD/F distribution patterns of pine needles in our study
were in accord with those of pine needles from areas with intensive
industrial activities in China (Chen et al., 2012) and from the vi-
cinity of an IWI in Korea (Kim et al., 2005), but quite differed from
those collected from unindustrialized cities (such as Laizhou,
Sanming, Nanping, Kunming, Conghua) or from areas that far away
from point emission sources (such as parks, residential areas and
botanical garden), in which OCDD or OCDF was the dominant
congener (Chen et al., 2006, 2012; Bochentin et al., 2007; Mei et al.,
2016). That disparity mainly ascribed to the environmental be-
haviors of PCDD/Fs during their transport process from “source” to
“sink”. MSWIs are usually considered to be an important source of
chlorinated dioxins and furans in some countries because these
types of compounds were first detected in flue gas (Olie et al., 1977).
According to Hites (1990), once dioxins are emitted from MSWIs
and reach the atmosphere, the air becomes uniformly mixed, then
go through a series of reactions (including photo/chemical degra-
dation, volatilization, gas-particle partitioning and deposition),
changing gradually from “fresh” to “aged” as the air mass moves
away from the primary source diluted with cleaner air. Highly
chlorinated dioxins and furans exhibit greater persistence than less
chlorinated forms. Therefore, variations in the types of and dis-
tances from the emission sources to which pine needles are
exposed lead to different dioxin distribution patterns in different
studies.
3.4. Comparison of 2,3,7,8-PCDD/Fs in pine needle, dust and stack
gas samples
The comprehensive patterns of 2,3,7,8-chlorinated congeners
were plotted for all pine needle, dust and stack gas samples (Fig. 2).
The congener percentages were normalized to the total concen-
tration of the 2,3,7,8-PCDD/Fs. As shown in Fig. 2, all sample types
had a similar distribution trend of seventeen 2,3,7,8-PCDD/F con-
geners, which were characterized as being rich in furans, and
1,2,3,4,6,7,8-HpCDF was the dominant congener, followed by OCDD.
These results indicate that this type of POP can directly influence
the ambient environment.
Further investigation of the stack gas, dust and pine needle
samples was conducted using principal component analysis (PCA).
The first two principal components (PCs) extracted by the PCA
explained 75.1% (PC1) and 13.9% (PC2) of the total variance,
respectively. PC1 was affected by higher chlorinated (hepta-, octa-)
PCDD/Fs, while PC2 was mainly influenced by lower chlorinated
(tetra-, penta-) PCDD/Fs. Fig. 4 indicates two distinct clusters of
samples were generally identified by PCA. The workshop dust
samples were obviously separated from the other two sample
types. In addition, there was a relatively higher proportion of
HpCDD/Fs and OCDD/Fs, especially for OCDD (up to 31%), due to
their lower vapor pressure and greater tendency to condense onto
the particles. The pine needles were located much closer to the
stack gas samples than the workshop dust samples. This suggests
that gas-phase partitioning of compounds in the atmosphere,
resulting from stack gas emissions, was the dominant process
through which PCDD/Fs adsorbed onto the surface of the pine
needles, in contrast to particle-phase deposition. However, pine
needles of different ages and from different locations showed
different relationships with the stack gas samples. The southern
group was located much closer to the stack gas samples than the
northern group, and one-year-old pine needles displayed a much
364 P. Chen et al. / Chemosphere 181 (2017) 360e367
Fig. 2. 2,3,7,8-PCDD/F congener profiles of the stack gas, workshop dust and pine needle samples.
closer relationship with the stack gas samples than the two-year-
old needles. These results imply a variation in subsequent envi-
ronmental processes such as evaporation, photo-degradation or
chemical/biological degradation of PCDD/F congeners after being
adsorbed onto the pine needle surfaces.
To explore additional details pertaining to the behavioral dis-
parities of each monomer, differences in the relative concentration
percentages of seventeen 2,3,7,8-chlorinated congeners between
one- and two-year-old needles were calculated and are presented
in Fig. 5. A positive value represents an increasing trend in the
relative concentration of the PCDD/Fs, and vice versa. As mentioned
above, the concentrations of the PCDD/Fs were approximately
doubled in the two- than in the one-year-old pine needle samples,
seeming all 2,3,7,8-chlorinated congeners of PCDD/Fs were accu-
mulated and degraded at a steady rate. However, tetra-PCDF, penta-
PCDF, 1,2,3,6,7,8-HxCDD and 1,2,3,4,6,7,8-HpCDF were obviously
reduced in the two-year-old pine needles compared with the one-
year-old samples, while hexa-PCDF increased by approximately 3%
relative to the total 2,3,7,8-PCDD/F concentration. These responses
may be ascribed mainly to photolysis by sunlight rather than
evaporation or chemical/biological degradation (McCrady and
Maggard, 1993; Welschpausch et al., 1995; Schuler et al., 1998).
Photo-degradation reactions can occur in various media, such as
surface waters, soil, solvents, vegetation and atmosphere, and are
consistently the dominant processes through which chemical
transformations occur in the environment (Crosby et al., 1971;
Crosby and Wong, 1977; McCrady and Maggard, 1993; Mill, 1999;
Larson and Weber, 1994). Niu et al. (2003) studied the fate of
PCDD/Fs after they were adsorbed on spruce needles and exposed
to sunlight irradiation. The photo-degradation rate constants (kp)
and the decrease rate constants of PCDD/Fs without sunlight irra-
diation (kE) were determined simultaneously. The results indicated
that kp was far higher than kE, suggesting that under field condi-
tions, photo-degradation is the major process when PCDD/Fs are
adsorbed onto the pine needle surfaces. Moreover, in the current
study, the relative concentrations of highly chlorinated PCDD/Fs
(except 1,2,3,4,6,7,8-HpCDF) showed an increasing trend. By
contrast, the relative concentrations of the less chlorinated PCDD/
Fs tended to decrease for the southern pine needles, whereas the
trends for the northern group were not that clear, and the variation
 P. Chen et al. / Chemosphere 181 (2017) 360e367 365

Fig. 3. 2,3,7,8-PCDD/F homologue profiles of the pine needle samples.

Fig. 4. PCA score plot of the first two principal components.

ranges scarcely exceeded by 2%. These results can probably be
attributed to the highly chlorinated PCDD/Fs being more resistant
to photo-degradation compared with less chlorinated PCDD/Fs, as
the photolysis half-lives of the former are longer than their less
chlorinated counterparts (Niu et al., 2003); this has been confirmed
in other studies (Crosby et al., 1971; Choi et al., 2000). In addition,
the downstream pine needles (northern group) were influenced by
a continuous supply of fresh PCDD/Fs emitted from the MSWI,
which may cover up the actual photolysis information that was
displayed by the southern pine needles. Furthermore, the PCDDs
showed minor differences in relative concentration changing than
compared with the PCDFs. This supports the higher photolysis rate
constants for PCDFs compared with PCDD homologues, as reported
by Niu et al. (2003), implying that PCDDs are more resistant to
photo-degradation than PCDFs.
4. Conclusion
MSWIs have been identified as an important emission source of
environmental PCDD/Fs, and MSWI workers might be subjected to
a higher risk of cancer than other residents due to a more severe
exposure to dioxins. Accumulation of PCDD/Fs in the pine needles
mainly depended on the atmospheric concentration, exposure
time, as well as the atmospheric conditions (wind direction). Var-
iations in the type of and distance from the emission sources to
which the pine needles were exposed could lead to different dioxin
distribution patterns. Gas-phase partitioning of compounds in the
atmosphere was the dominant process through which PCDD/Fs
366 P. Chen et al. / Chemosphere 181 (2017) 360e367
Fig. 5. Differences in the relative concentration percentage between one- and two-year-old pine needle samples.
were adsorbed onto the pine needle surfaces, in contrast with
particle-phase deposition, and subsequent environmental pro-
cesses varied between the congeners. The total PCDD/F concen-
tration in the pine needles cover up the actual photolysis
information. Generally speaking, photo-degradation was the major
transformation process that occurred after the PCDD/Fs were
adsorbed onto the pine needle surfaces. Highly chlorinated PCDD/
Fs are more recalcitrant to photo-degradation than less chlorinated
PCDD/Fs, and PCDDs are more resistant to photo-degradation than
PCDFs. Lipid-rich pine needles have a strong ability to accumulate
dioxin compounds tells it can be used as absorption sinks of PCDD/
Fs in heavily polluted areas, for it is easier to dispose of pine needles
than it is to clean contaminated air.
Acknowledgments
We are grateful to the National Natural Science Foundation of
China for financial support (No. 41390242) and we also thank four
anonymous reviewers for their critical comments that greatly
improved the quality of this manuscript.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.chemosphere.2017.04.098.
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