Environ Sci Pollut Res (2010) 17:634–642
DOI 10.1007/s11356-009-0236-z
AREA 6 • ENVIRONMENTAL ANALYSES AND MONITORING • RESEARCH ARTICLE
Polybrominated diphenyl ethers and their methoxylated
metabolites in anchovy (Coilia sp.) from the Yangtze River
Delta, China
Guan-yong Su & Zi-shen Gao & Yijun Yu & Jia-chun Ge &
Si Wei & Jian-fang Feng & Feng-yan Liu & John P. Giesy &
Michael H. W. Lam & Hong-xia Yu
Received: 1 May 2009 / Accepted: 24 August 2009 / Published online: 25 September 2009
# Springer-Verlag 2009
Abstract
Background, aim, and scope Polybrominated diphenyl
ethers (PBDEs) and their metabolites are toxic to animals,
and concentrations of the PBDEs metabolites can exceed
those of the parent materials. But no information was available
on concentrations of PBDEs metabolites in the lower Yangtze
River in the region around Jiangsu Province of China, which
is heavily urbanized and industrialized area. The aims of this
study were to determine whether PBDEs and their methoxylated PBDEs (MeO-PBDEs) were accumulated in Coilia sp.
in this area and to investigate the potential sources for these
two kinds of brominated organic pollutants.
Materials and methods Samples of four species of anchovy
were collected from eight sites in the lower Yangtze River,
Taihu Lake, and Hongzehu Lake. Concentrations of 13
PBDEs congeners and eight methoxylated PBDEs were
determined by use of organic solvent extraction, followed
by gas chromatography and mass spectrometry.
Results and discussion The frequencies of detection for
PBDEs and MeO-PBDEs were 92% and 53%, respectively.
Concentrations of ∑PBDEs ranged from not detected (ND)
to 77 ng/g lipids (ND–3.8 ng/g wet weight). Concentrations
of ∑MeO-PBDEs in anchovy ranged from ND to 48 ng/g
lipids (ND–8.2 ng/g wet weight). The PBDE concentrations
in anchovy from the Yangtze River Delta were similar to or
less than those reported for other species from other
locations around the world, while the concentrations of
MeO-PBDEs were comparable to or slightly less than those
Responsible editor: Alvin L. Young
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-009-0236-z) contains supplementary material,
which is available to authorized users.
G.-y. Su : Z.-s. Gao : Y. Yu : S. Wei : J.-f. Feng : J. P. Giesy :
H.-x. Yu (*)
State Key Laboratory of Pollution Control and Resource Reuse,
School of the Environment, Nanjing University,
Nanjing 210093, China
e-mail: Yuhx@nju.edu.cn
Y. Yu
Changzhou Environmental Monitoring Center,
Changzhou 213001, China
J.-c. Ge : F.-y. Liu
Freshwater Fisheries Research Institute of Jiangsu Province,
Nanjing 210017, China
J. P. Giesy
Department of Veterinary Biomedical Sciences and Toxicology
Centre, University of Saskatchewan,
Saskatoon, SK, Canada
J. P. Giesy
Department of Zoology, Michigan State University,
East Lansing, MI, USA
J. P. Giesy : M. H. W. Lam
Centre for Coastal Pollution and Conservation, Department
of Biology and Chemistry, City University of Hong Kong,
Tat Chee Avenue,
Kowloon, Hong Kong SAR, People’s Republic of China
J. P. Giesy
State Key Laboratory of Marine Environmental Science, College
of Oceanography and Environmental Science, Xiamen University,
Siming Nanlu 422,
Xiamen, Fujian 361005, People’s Republic of China
Environ Sci Pollut Res (2010) 17:634–642
reported in other studies. This is the first report of MeOPBDEs in biota of China.
Conclusions The results of this study as well as those of
other studies suggest that PBDEs in anchovy are primarily
of synthetic origin and released by human activities, while
MeO-PBDEs in anchovy are primarily from nature as
natural products from the sea instead of metabolism of
PBDEs in anchovy.
Keywords GC/MS . Polybrominated diphenyl ethers .
Methoxylated polybrominated diphenyl ethers . Fish . China
1 Background, aim, and scope
Several species of anchovy (genus Coilia) are economically
important in the Yangtze River Delta, China. There are few
differences in morphology among these species, but they
differ in their life histories, especially in their migratory
patterns. The estuarine tapertail anchovy (Coilia nasus) and
tapertail anchovy (Coilia mystus) are economically important species in the Yangtze River estuary. Recent human
influences, including over-fishing and water pollution, have
resulted in a sharp decrease of the natural population of
these species. The lake anchovy (Coilia nasus taihuensis) is
the primary species in Taihu Lake. The population of this
species is rather robust, and more than 15,000 tons are
harvested every year. The shortjaw tapertail anchovy
(Coilia brachygnathus) is a species in Hongzehu Lake.
Recently, heavy metal pollution and organic pollution have
been reported in the Yangtze River Delta (Mueller et al.
2008; Chen et al. 2004; Yang et al. 2008), but concentrations of inorganic and organic pollutants had not been
previously characterized in anchovies, which are important
components of the diet of the densely populated Yangtze
River Delta.
Polybrominated diphenyl ethers (PBDEs) have been
widely used in many products as flame retardants (Covaci
et al. 2003), which has resulted in their release into the
environment. There have been many reports of concentrations of PBDEs in the environment where they can be
found in wildlife (de Wit 2002; Hale et al. 2001; Pettersson
et al. 2004) and humans (Akutsu et al. 2003; Noren and
Meironyte 2000; Johnson-Restrepo et al. 2005; Bi et al.
2007). In China, PBDEs were detected in many media (Guo
et al. 2008; Bi et al. 2006; Chen et al. 2007; Chen et al.
2006a; Jin et al. 2008; Wurl et al. 2006). PBDEs are even
ubiquitous in aquatic (freshwater fishes, shrimps, and crabs)
from the lower Yangtze River (Gao et al. 2009).
PBDEs can be transformed to various metabolites by
animals (Marsh et al. 2006; Qiu et al. 2007). PBDEs and
their metabolites are toxic to animals (Darnerud et al. 2001;
McDonald 2002), and concentrations of the PBDEs
635
metabolites can exceed those of the parent materials
(Pettersson et al. 2004). These metabolites such as some
hydroxylated PBDEs (OH-PBDEs) and methoxylated
PBDEs (MeO-PBDEs) can even cause endocrine disrupting
effects (Canton et al. 2005; Canton et al. 2006). These facts
make scientists pay increasing attention to PBDEs and their
metabolites.
The Yangtze River Delta, located in East China, is a
major production center for chemicals, textiles, and
electronics, some of which use large amounts of flame
retardants such as PBDEs. The annual production and
consumption of PBDEs in this area have led to PBDE
contamination of sediments (Chen et al. 2006b; Shen et al.
2006) and aquatic biota (Xian et al. 2008).
No information was available on concentrations of
PBDE metabolites in the lower Yangtze River in the region
around Jiangsu Province, which is a heavily urbanized and
industrialized area. In this study, different species of
anchovies (Coilia sp.) were collected from the Yangtze
River Delta, and concentrations of 13 major PBDEs
congeners and eight MeO-PBDEs metabolites were measured. Structures of 21 target compounds were given in the
Electronic supplementary material (Figure S1). The main
objectives of this study were to (1) determine whether
PBDEs and their MeO-PBDEs were accumulated in Coilia
sp. in this area, (2) to determine profiles of relative
concentrations of PBDEs and MeO-PBDEs in Coilia sp.,
and (3) to investigate the potential sources for these two
kinds of brominated organic pollutants.
2 Materials and methods
Sampling Specific sampling locations included Haimen
(L-1), Nanjing (L-2), Jingjiang (L-3), and Taicang (L-4) from
the lower Yangtze River; Sanshanhu (L-5), Pingtaishan (L-6)
and Jiaoshan (L-7) from Taihu Lake; and Hongzehu Lake
(L-8). Samples of four species of anchovy, including estuarine
tapertail anchovy (sampling location: L-1, L-2, and L-3),
tapertail anchovy (sampling location: L-4), lake anchovy
(sampling location: L-5, L-6, and L-7), and shortjaw tapertail
anchovy (sampling location: L-8), were collected from April
to August 2007, from eight sites in the lower Yangtze River,
Taihu Lake, and Hongzehu Lake (Fig. 1). Anchovies were
transported to the lab in frozen condition and were
maintained intact at −20°C until dissected for subsequent
identification and quantification of PBDEs and MeOPBDEs. Details of the samples are given in the Electronic
supplementary material (Table S1).
Identification and quantification of PBDEs and MeOPBDEs Concentrations of individual PBDEs and
MeO-PBDEs were determined by use of organic solvent
636
Environ Sci Pollut Res (2010) 17:634–642
Fig. 1 Collection locations of
anchovy
119° 07’ E
Sample locations
Cities
L-8
N
Yangtze
River
Hongzehu
Lake
32° 20’ N
L-2
L-3
L-4
Nanjing
Changzhou
L-7
L-5
L-6
L-1
Wuxi
Suzhou
Shanghai
Taihu Lake
extraction, followed by gas chromatography and mass
spectrometry (GC/MS). After measuring the length and
weight of individual fish, the edible fillet was taken out of
the fish. The fillet was freeze-dried and homogenized.
Approximately 2.0 g of dry sample, to which surrogate
standard— 13 C-BDE-139 (Wellington Laboratories,
Canada) was added—was Soxhlet-extracted with a mixture
of dichloromethane and hexane (V/V=1:1) for 24 h. The
extract was concentrated by rotary evaporation and lipid
content was determined gravimetrically. The extract was
dissolved in dichloromethane and hexane (V/V=1:1) and
acidified with 5 mL H2SO4 to remove the fat. PBDEs and
MeO-PBDEs were back-extracted with a total of 30 mL
dichloromethane and hexane (V/V=1:1) in three separate
10 mL extractions. The organic solvent containing PBDEs
and MeO-PBDEs was concentrated and passed through a
silica gel column for further clean up. The silica gel column
was packed with glass-wool, activated silica gel (0.25 g),
44% (w/w) acid silica gel (1.0 g), silica gel (0.25 g), and
anhydrous sodium sulfate (0.30 g) from bottom to top in a
disposable Pasteur pipette. The fraction containing PBDEs
and MeO-PBDEs was eluted with 13 mL hexane followed
by 10 mL dichloromethane. The eluate was concentrated by
rotary evaporation and further concentrated to near dryness
under a gentle nitrogen flow. A known amount of 13C-PCB178 (Cambridge Isotope Laboratories, USA) was added as
the internal injection standard and made up to 100 μL with
hexane prior to GC/MS analysis. Concentrations of 13
PBDEs and eight MeO-PBDEs were determined by use of a
GC/MS (Thermo Finnigan Polaris Q, USA) coupled with
an Agilent DB-XLB column (15 m×0.25 mm×0.25 μm,
USA) in two separate runs. The mass spectrometer detector
was operated in electron impact ionization (EI) mode.
Samples and standards were analyzed in both SIM and
MS/MS mode. Quantification and qualification were
processed by SIM and MS/MS modes in a single analysis.
The selected ions (m/z) in SIM mode, precursor ion, and
product ions selected in MS/MS mode for each chemical
were based on the mass spectrum of the standard solution.
Detailed information about the SIM ion, precursor ion, and
product ions were given in the Electronic supplementary
material (Table S2). The individual PBDEs, in order of
retention times, included BDE-17, 28, 71, 47, 66, 100, 99,
85, 154, 153, 138, 183, and 190, The eight target MeOPBDEs included 2′-MeO-BDE-28, 2′-MeO-BDE-68,
6-MeO-BDE-47, 4′-MeO-BDE-49, 2′-MeO-6′-Cl-BDE-68,
6-MeO-BDE-90, 6-MeO-BDE-85, and 6-MeO-BDE-137,
in order of retention times. Identification of specific PBDEs
and MeO-PBDEs was performed by comparing relative
retention times versus internal standard and product ions in
MS/MS mode with the standard chemicals. The limit of
detection (LOD) was defined as the concentration that
would result in a signal-to-noise ratio of 3. LOD based on
2.0 g of dry sample and instrument sensitivity, varied from
Environ Sci Pollut Res (2010) 17:634–642
637
congener to congener, from 0.011 to 0.11 ng/g dry weight.
Concentrations less than the LOD were assumed to be not
detected in calculating summary statistics.
Quality assurance/quality control One procedural blank
was run with every batch of six to ten samples to assess
potential sample contamination. The laboratory blanks
demonstrated that the sample analysis was free from
background contamination. Therefore, concentrations
were not corrected for background. Recoveries of
13
C12-BDE-139 surrogate standard in blanks and samples
ranged from 100.2% to 136.3% and from 65.6% to
122.7%, respectively. Recoveries of the 13 PBDEs and
eight MeO-PBDEs in initial and ongoing recovery
samples ranged from 74.4% to 94.5%. Method performance in spiked samples was listed in the Electronic
supplementary material (Table S3), and reported results
were not corrected for surrogate recovery. To facilitate
comparison with the results of other studies, concentrations of PBDEs and MeO-PBDEs are given normalized to
both wet weight and lipid weight (Tables 1 and 2).
Statistical analysis Statistical analysis was performed with
the SPSS 13.0 for Windows. Spearman rank correlation
was used to examine the strength of associations between
different datum (including weight and length of individual
Table 1 PBDEs and MeO-PBDE concentrations in anchovy (pg/g ww)
Lipid (%)
BDE-17
BDE-28
BDE-71
BDE-47
BDE-66
BDE-100
BDE-99
BDE-154
BDE-153
∑PBDEs
2′-MeOBDE-68
6-MeOBDE-47
∑MeOPBDEs
Coilia nasus
(L-1)
Coilia
nasus
(L-2)
Coilia
nasus
(L-3)
Coilia
mystus
(L-4)
Coilia nasus
taihuensis
(L-5)
Coilia nasus
taihuensis
(L-6)
Coilia nasus
taihuensis
(L-7)
Coilia
brachygnathus
(L-8)
11–17
14
ND
–
ND–270
8.7–20
13
ND
–
ND–74
5.0–23
12
ND
–
ND–240
2.4–5.6
3.7
ND
–
ND
4.9–8.2
7.0
ND–140
79
160–540
3.1–5.8
4.2
ND
–
67–140
3.8–5.5
4.4
ND
–
ND
0.60–1.2
0.80
ND
–
ND
62
ND–330
190
300–650
25
ND–85
54
ND–390
–
ND
–
ND–220
300
580–1.1×103
720
760–1.5×103
88
450–790
590
590–1.3×103
–
250–430
340
440–720
–
ND–110
30
ND–230
540
ND–60
32
ND–140
88
ND–25
1.2×102
200
ND
–
ND–67
23
ND–59
20
87
ND–320
160
150–1.7×
103
690
ND
–
38–130
82
ND–95
41
87
ND
–
ND
–
ND
–
1.0×103
ND–150
40
53–140
110
70–130
110
950
ND–170
41
80–310
200
18–190
120
620
ND
–
ND–83
53
ND
–
62
ND
–
ND
–
ND
–
ND–440
150
ND–190
37
650–2.0×103
ND
–
ND
–
ND–600
ND
–
ND
–
ND–220
320
ND–160
81
ND–2.6×
103
1.2×103
ND–2.7×
103
1.3×103
ND–190
67
ND–39
14
1.7×103–
3.8×103
2.5×103
ND
–
ND–38
ND
–
ND
–
1.2×103–
2.8×103
2.0×103
ND
–
ND–160
ND
–
ND
–
780–1.2×
103
1.0×103
ND
–
ND
ND
–
ND
–
ND–340
1.2×103
ND–270
180
2.3×103–
7.9×103
4.3×103
2.4×103–
8.2×103
4.5×103
ND–340
100
ND–46
15
210–2.5×
103
1.2×103
ND–450
200
ND–2.5×
103
1.1×103
ND–2.9×
103
1.3×103
8.0
ND–38
40
ND–160
–
ND
–
ND
8.0
40
–
–
87
ND
–
120–1.5×
103
520
120–1.5×
103
520
Only chemicals with concentrations greater than the LOD are listed
ND not detected, the concentration was less than the LOD
92
ND
–
ND
638
Environ Sci Pollut Res (2010) 17:634–642
Table 2 PBDEs and MeO-PBDEs concentrations in anchovy (ng/g lip)
Lipid (%)
BDE-17
BDE-28
BDE-71
BDE-47
BDE-66
BDE-100
BDE-99
BDE-154
BDE-153
∑PBDEs
2′-MeOBDE-68
6-MeO-BDE47
∑MeOPBDEs
Coilia
nasus
(L-1)
Coilia
nasus
(L-2)
Coilia
nasus
(L-3)
Coilia
mystus
(L-4)
Coilia nasus
taihuensis
(L-5)
Coilia nasus
taihuensis
(L-6)
Coilia nasus
taihuensis
(L-7)
Coilia
brachygnathus
(L-8)
11–17
14
ND
–
ND–1.9
0.45
ND–2.4
1.4
2.5–4.7
3.8
ND–0.43
0.23
ND–1.1
0.65
ND–1.5
0.84
ND–2.6
1.0
8.7–20
13
ND
–
ND–0.73
0.24
ND–0.98
0.57
ND–4.5
2.2
ND
–
ND–0.78
0.26
ND–0.68
0.23
ND
–
5.0–23
12
ND
–
ND–4.8
1.2
ND–1.9
1.1
2.5–33
9.7
ND
–
0.22–2.5
1.1
ND–1.9
0.66
ND–6.8
1.6
2.4–5.6
3.7
ND
–
ND
–
ND
–
ND–4.9
2.4
ND
–
ND
–
ND
–
ND
–
4.9–8.2
7.0
ND–2.4
1.2
2.4–11
4.8
7.9–21
11
10–29
16
ND–3.0
0.74
0.78–2.9
1.6
1.0–2.6
1.6
ND–3.8
1.1
3.1–5.8
4.2
ND
–
1.2–3.6
2.2
9.8–20
15
19–31
23
ND–4.1
1.0
2.6–7.7
4.7
0.60–4.8
2.8
ND
–
3.8–5.5
4.4
ND
–
ND
–
4.6–11
8.0
8.0–18
15
ND
–
ND–2.0
1.2
ND
–
ND
–
0.60–1.2
0.80
ND
–
ND
–
ND–13
3.6
ND–28
7.5
ND
–
ND
–
ND
–
ND
–
ND–1.1
0.22
3.9–14
8.6
ND–2.4
1.4
19–47
ND
–
ND–6.9
3.5
ND–1.9
0.89
ND–29
ND–0.24
0.090
4.4–50
15
ND–2.0
1.1
ND–12
ND
–
ND–4.9
2.4
ND
–
ND–0.79
0.23
24–77
38
ND
–
ND
–
36–69
48
ND
–
ND
–
14–31
24
ND
–
ND
–
ND–41
11
ND
–
29
20–48
31
13
ND–31
14
8.0
ND–13
9.1
3.5–27
13
3.5–27
13
ND–0.55
0.11
ND–0.55
0.11
ND–4.0
1.0
ND–4.0
1.0
ND
–
ND
–
ND
–
ND
–
Only chemicals with concentrations greater than the LOD are listed
ND not detected, the concentration was less than the LOD
fish, concentrations of individual target compounds,
∑PBDEs, and ∑MeO-PBDEs), though the relativity was
very low between the shape of individual fish and
concentrations of target compounds. Mann–Whitney U
nonparametric tests were used to compare the difference
between/among groups. The meaning of group was shown
in the last part of the discussion.
3 Results and discussion
3.1 PBDEs and MeO-PBDEs concentrations
In the present study, nine out of 13 targeted PBDEs were
detected and two out of eight MeO-PBDEs were detected.
Four PBDEs, including BDE-85, BDE-138, BDE-183, and
BDE-190, were not detected in anchovy. Similarly, six
MeO-PBDEs, including 2′-MeO-BDE-28, 4′-MeO-BDE49, 2′-MeO-6′-Cl-BDE-68, 6-MeO-BDE-90, 6-MeO-BDE85, and 6-MeO-BDE-137, were not detected either.
The MeO-PBDEs detected in anchovy were 2′-MeOBDE-68 and 6-MeO-BDE-47. These MeO-PBDEs have
been detected in previous studies. This is the first report of
MeO-PBDEs in the biota in China. The mass spectra
showed that the precursor ions of 2′-MeO-BDE-68 and
6-MeO-BDE-47, which were also their molecular ions, had
a loss of BrCH3 (M-94+) in the EI-MS/MS mode. These
fragmentations were in agreement with the previous
observations of ortho-MeO-PBDEs (Athanasiadou et al.
2006). The fragmentation of 2′-MeO-BDE-68 and 6-MeOBDE-47 in EI-MS/MS mode also showed similar ion
Environ Sci Pollut Res (2010) 17:634–642
clusters compared with the synthesized MeO-PBDEs
standard (see Figure S2). Thus, it was confirmed that the
above MeO-PBDEs were detected in anchovy from the
Yangtze River Delta.
The frequencies of detection for PBDEs and MeOPBDEs were 92% and 53%, respectively. PBDEs and
MeO-PBDEs were not detectable in one anchovy sample
(C. brachygnathus) from L-8. PBDEs were not detected in
one anchovy sample (C. mystus) from L-4. MeO-PBDEs
were also not detected in most individuals of C. nasus
taihuensis. The detection rates of PBDEs and MeO-PBDEs
were as follows: 11% (BDE-17), 42% (BDE-28), 72%
(BDE-71), 94% (BDE-47), 17% (BDE-66), 58% (BDE100), 50% (BDE-99), 31% (BDE-154), 14% (BDE-153),
25% (2′-MeO-BDE-68), and 53% (6-MeO-BDE-47).
In anchovy, concentration of ∑PBDEs ranged from not
detected (ND) to 77 ng/g lip (ND–38 ng/g ww) with mean and
median values of 18 ng/g lip (1.0 ng/g ww) and 8.6 ng/g lip
(0.81 ng/g ww), respectively (Tables 1 and 2). By comparison, concentrations of ∑PBDEs in anchovy from the
Yangtze River Delta were generally less than those in biota
from other locations around the world (Gao et al. 2009).
Concentrations of ∑MeO-PBDEs in anchovy ranged
from ND to 48 ng/g lip (ND–8.2 ng/g ww) with the mean
and median values of 9.1 ng/g lip (1.0 ng/g ww) and
2.0 ng/g lip (0.078 ng/g ww), respectively (Tables 1 and 2).
Concentrations of PBDEs in anchovy were less than those
reported in biota from other locations, while the concentrations of MeO-PBDEs were comparable to or slightly less
than those reported from other locations, especially when
compared with the wet weight concentration (see Table S3).
The highest concentration was observed for 6-MeO-BDE47 (0.92 ng/g ww, mean values). The relatively high concentrations of the 6-MeO-BDE-47 congener in anchovy
may be due to the relatively high lipid content in anchovy
Fig. 2 Profiles of PBDEs and
MeO-PBDEs in anchovy from
the Yangtze River Delta
639
(Verreault et al. 2005a, b; Stapleton et al. 2006). However,
the MeO-PBDEs concentrations were definitely less than
concentrations of MeO-PBDEs that have been reported for
some marine mammals, which can reach micrograms per
gram, lipid levels (Teuten et al. 2005).
3.2 Profiles of PBDEs and MeO-PBDEs
The PBDEs that were most frequently detected also
contributed the highest proportion to the ∑PBDEs. For
example, BDE-47 and BDE-71 contributed more than 70%
of the ∑PBDEs. Besides these two tetra-BDEs, BDE-28,
BDE-100, BDE-99, and BDE-154 also were predominant
congeners. After BDE-47, BDE-71 was the second most
predominant PBDEs congener in anchovy. This result is
different from the PBDE profiles reported for other aquatic
species from other locations. The different patter observed
in anchovy may be due to species-specific metabolism of
anchovy. BDE-183 and BDE-190 were not detected in
anchovy, which indicates that more-brominated PBDEs
congeners were not readily accumulated by anchovy. Lack
of heavier PBDEs might be related to the source profile or
the fact that they were less soluble in water. Congeners
2′-MeO-BDE-68 and 6-MeO-BDE-47 were detected in
some anchovy with concentrations of 2′-MeO-BDE-68 less
than those of 6-MeO-BDE-47. The concentration of
6-MeO-BDE-47 was relatively high in anchovy from
locations L-1, L-2, L-3, and L-4, in which concentrations
of 6-MeO-BDE-47 were comparable or even higher than
that of BDE-47 (Fig. 2).
Concentrations of PBDEs congeners and MeO-PBDEs
were inter-correlated. Concentrations of most PBDEs
congeners were positively correlated with each other, and
concentrations of the 2 detected MeO-PBDEs were also
positively correlated with each other. However, concen-
640
trations of the two detected MeO-PBDEs were negatively
correlated with concentrations of BDE-47. Concentration of
6-MeO-BDE-47 was also significantly negatively correlated with the concentration of ∑PBDEs. This may be due to
the lack of a metabolic origin of MeO-PBDEs from PBDEs.
This fact is also supported by Vetter et al. (2001) who did
not detect significant amounts of parent compounds
(PBDEs) in marine mammals from northeastern Australia
despite the high levels found of 6′-MeO-BDE47. Previous
research has shown that there is a wide variety of naturally
occurring organobromine compounds, which are produced
by bacteria, fungi, plants, and animals (Gribble 2000). Both
OH-PBDEs and MeO-PBDEs have been found in marine
sponges and freshwater species (Kierkegaard et al. 2004).
These facts suggest that MeO-PBDEs in anchovy from the
Yangtze River Delta may also result from their food web in
which MeO-PBDEs may be also naturally produced.
Environ Sci Pollut Res (2010) 17:634–642
synthetic PBDEs (Teuten et al. 2005). (2) C. nasus and
C. mystus from the lower Yangtze River are migratory
fishes, residing in the Yangtze River estuary and migrating
back to the Yangtze River to spawn. Since they do not feed
during the migration and spawning, most of their food come
from the estuary and are of marine origin, rather in the river.
(3) Concentrations of ∑MeO-PBDEs in anchovy from
Yangtze River (L-1, L-2, L-3, and L-4) were obviously higher
than those in anchovy from Taihu Lake and Hongzehu Lake
(L-5, L-6, L-7, and L-8). This result suggests that the source
of MeO-PBDEs in anchovy may be from the sea. (4) C.
nasus taihuensis and C. brachygnathus are non-migratory
fishes which reside in Taihu and Hongzehu Lakes. Concentrations of PBDEs in C. nasus taihuensis from Taihu Lake
are higher than that of other anchovies. This is in agreement
with the fact that artificial pollution is, in general, higher in
Taihu Lake than in other areas of the Yangtze River Delta.
3.3 Potential source of PBDEs and MeO-PBDEs
4 Conclusions
In order to investigate potential sources of PBDEs and
MeO-PBDEs in anchovy, samples were divided into three
groups based on their location and natural history characteristics. The first group (G1) consists of C. nasus and
C. mystus samples from the lower Yangtze River (sampling
locations: L-1, L-2, L-3, and L-4). Both of these species
reside in the coastal area and migrate back to the Yangtze
River to spawn. The second group (G2) consists of
C. nasus taihuensis from Taihu Lake (sampling locations:
L-5, L-6, and L-7), while the third group (G3) consists of
C. brachygnathus from Hongzehu Lake (sampling location:
L-8). The difference among G1, G2, and G3 is that these
latter two spices reside in the lake for all their lifetime.
Concentrations of ∑PBDEs in anchovy of G2 were
significantly higher than concentrations of ∑PBDEs in
anchovy classified as G1 or G3 (Mann–Whitney U test;
p<0.01). Concentrations of ∑MeO-PBDEs in G1 anchovy
were significantly higher than those classified as G2 or G3
(p<0.01). In general concentrations of PBDEs were higher
in anchovy from Taihu Lake than those from other two
regions. But concentrations of MeO-PBDEs in anchovy
from the lower Yangtze River were higher than those in the
other two regions.
Based on this observation, it is postulated that PBDEs
in anchovy from Taihu Lake are primarily from human
activities around the highly populated area (such as city of
Suzhou, Wuxi, and Changzhou), while MeO-PBDEs are
primarily derived from natural sources in the sea instead
of the metabolism of synthetic PBDEs. This hypothesis is
supported by the following observations: (1) The two
detected MeO-PBDEs, 2′-MeO-BDE-68 and 6-MeOBDE-47, have both been shown to be natural products
produced by marine organisms instead of by metabolism
PBDEs and MeO-PBDEs were detected in anchovy from
the Yangtze River Delta. This is the first report of MeOPBDEs in biota of China. The PBDE concentrations in
anchovy from the Yangtze River Delta was similar to or
less than those reported for other species from other
locations around the world, while the concentrations of
MeO-PBDEs were comparable to or slightly less than those
reported in other studies. The results of this study as well as
those of other studies suggest that PBDEs in anchovy are
primarily of synthetic origin and released by human
activities around the highly populated Taihu Lake area,
while MeO-PBDEs in anchovy are primarily from nature as
natural products from the sea instead of metabolism of
PBDEs in anchovy.
Acknowledgments We are grateful to the financial supports of the
National Basic Research Program of China (973 program) (No.
2008CB418102), National Natural Science Foundation of China (No.
20737001), NSFC/RGC Joint Research Grant (No. 20518002 and
N_CityU110/05), Jiangsu Science and Technology Department
(BM2006503), Jiangsu Ocean and Fishery Department (K2006-3)
and Department of Personnel Jiangsu (07-G-028) China. Prof. Giesy
was supported by the Canada Research Chair program and an at large
Chair Professorship at the Department of Biology and Chemistry and
Research Centre for Coastal Pollution and Conservation, City
University of Hong Kong.
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