Abstract. Twelve perfluoroalkyl substances (PFASs) were investigated in fish
samples collected in West Lake and Yen So Lake. Six PFASs including five
perfluoroalkylcarboxylic acids (PFCAs) and only one perfluoroalkyl sulfonates acids
(PFSAs) compounds were found in fish samples in both lakes. The concentration of
long-chain carbon compounds such as PFNA, PFDA, PFUdA and PFDoA were
predominant in the entire both lakes. The highest PFASs concentration was found in
catfish (1.98 ng.g-1 w.w). The bioconcentration factor (BCF) of PFDoA were the
highest in both lakes (854.48 - 3742.68), whereas PFOA‟s BFC values were the
lowest in both lakes (2.19 - 27.48). In PFCAs group, BFC values increased with the
carbon chain length but with the same carbon chain length PFOS‟s BCF value were
higher than PFOA„s.
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HNUE JOURNAL OF SCIENCE DOI: 10.18173/2354-1059.2017-0052
Chemical and Biological Science 2017, Vol. 62, Issue 10, pp. 36-43
This paper is available online at
SURVEY OF PERFLUOROALKYL SUBSTANCES CONCENTRATION
AND THEIR BIOACCUMULATION IN FISH
FROM TWO URBAN LAKES, HA NOI, VIETNAM
Nguyen Thuy Ngoc, Phan Thi Lan Anh, Phan Dinh Quang, Truong Thi Kim,
Tran Thi Mai, Duong Hong Anh and Pham Hung Viet
VNU Key Laboratory of Analytical Technology for Environmental Quality and Food
Safety Control (KLATEFOS), University of Science, Vietnam National University, Hanoi
Abstract. Twelve perfluoroalkyl substances (PFASs) were investigated in fish
samples collected in West Lake and Yen So Lake. Six PFASs including five
perfluoroalkylcarboxylic acids (PFCAs) and only one perfluoroalkyl sulfonates acids
(PFSAs) compounds were found in fish samples in both lakes. The concentration of
long-chain carbon compounds such as PFNA, PFDA, PFUdA and PFDoA were
predominant in the entire both lakes. The highest PFASs concentration was found in
catfish (1.98 ng.g
-1
w.w). The bioconcentration factor (BCF) of PFDoA were the
highest in both lakes (854.48 - 3742.68), whereas PFOA‟s BFC values were the
lowest in both lakes (2.19 - 27.48). In PFCAs group, BFC values increased with the
carbon chain length but with the same carbon chain length PFOS‟s BCF value were
higher than PFOA„s.
Keywords: PFASs, LC-MS/MS, fish, urban lake, West Lake, Yen So, Hanoi.
1. Introduction
PFASs are a group of anthropogenic compounds that are known as new persistent
organic pollutants (POPs) with special surface-active properties [1]. Their molecular
contains two both lipophilic and hydrophilic groups at both sides. PFASs have been
manufactured since the late 1940s [1, 2]. Then they have been widely applied in industrial
and commercial products such as refrigerants, surfactants, and polymers and as
components of pharmaceuticals, fire retardants, lubricants, adhesives, cosmetics, paper
coatings, and insecticides because of their extremely strong carbon – fluorine bonds [3].
These compounds are now common contaminants in wastewater because of their
widespread occurrence in the environment and their ability to bioaccumulation [4]. They
are toxic and carcinogenic to animals such as rats, fishes, monkeys, and even humans [4-7].
Received November 17, 2017. Revised December 7, 2017. Accepted December 14, 2017.
Contact Pham Hung Viet, e-mail address: phamhungviet@hus.edu.vn
Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish
37
The concern about their presence in the environmental and potential human exposure is
rising all over the world. A great number of studies have been available on the
contaminations of PFASs in rivers, lakes, and ocean waters and even in air [8, 9], dust[10].
PFASs have been investigated widely in fish of Europe and Asia, such as: Spain [11]
Norway [12], Greece [13], Italy[14], Korea [15], and China[16]. However, there is a lack
of data of these chemical in fish and the potential exposure to humans in Vietnam. The
widespread distribution of PFASs in other environment samples in Hanoi, Vietnam that is
still limited investigation. This research investigates the occurrence of 12 PFASs in
freshwater cultured fish from two large lakes in Hanoi, Vietnam. The fish samples had
been sampling in the interval time of two seasons in the Northern of Vietnam. For fish
sampling, the three to four special fresh water species was collected which have been
cultivating in these lakes. The PFASs in pretreated samples were analyzed using high
performance liquid chromatography-tandem mass spectrometry (LC/MS-MS). The
obtained results showed a sufficient picture of the distribution and accumulation of PFASs
in fish, the bioaccumulation of PFASs from water to fish and presented the initial health
risk assessment for inhabitants using these fishes for meal, correspondingly.
2. Content
2.1. Materials and methods
2.1.1. Chemicals
Table 1. List of target PFAS compounds
PFACMXB0614 MPFACMXA0714
Compound Abbreviation Compound Abbreviation
Perfluorohexansunfonate -
13
C,
18
O MPFHxS Perfluorobutanoic acid PFBA
Perfluorooctansunfonate -
13
C,
18
O MPFOS Perfluoropentanoic acid PFPeA
Perfluorobutanoic acid -
13
C MPFBA Perfluorohexanoic acid PFHxA
Perfluorohexanoic acid -
13
C MPFHxA Perfluoroheptanoic acid PFHpA
Perfluorooctanoic acid -
13
C MPFOA Perfluorooctanoic acid PFOA
Perfluorononanoic acid -
13
C MPFNA Perfluorononanoic acid PFNA
Perfluorodecanoic acid -
13
C MPFDA Perfluorodecanoic acid PFDA
Perfluoroundecanoic acid -
13
C MPFUdA Perfluoroundecanoic acid PFUdA
Perfluorododecanoic acid -
13
C MPFDoA Perfluorododecanoic acid PFDoA
Perfluorobutansunfonate L-PFBS
Perfluorohexansunfonate L-PFHxS
Perfluorooctansunfonate L-PFOS
N. T. Ngoc, P. T. L. Anh, P. D. Quang, T. T. Kim, T. T. Mai, D. H. Anh and P. H. Viet
38
The mixture of PFCAs and PFSAs (PFACMXB0614) and the mixture of Mass-
Labeled PFCAs and PFSAs (MPFACMXA0714) were obtained from Wellington
Laboratories, Canada. All analyzed PFASs compounds and their abbreviations are showed
in table 1. All solvents used in this study were of LC-MS grade. Ammonium acetate was
obtained from Wako Chemicals, Japan. Ultrapure water was delivered by a Direct-Q
water purification system (Millipore, Japan). HPLC-grade methanol was purchased from
Merck, Germany and other chemicals were of analytical reagent grade.
2.1.2. Sampling site
Figure 1 shows the location of sampling
sites. Two biggest reservoirs, West Lake and
Yen So lake, are representative of other
freshwater reservoirs in Hanoi. West lake is
the largest freshwater lake in the Northeastern
of Hanoi city with a shore length of 17km
and an area of 530 hectares. This lake is a
famous place for recreation with many
surrounding gardens, pagodas, hotels, villas
and other entertainment places. Yen So lake
is a complex of small and big reservoirs that
is lying in the Southern of Hanoi with a water
area of 70 hectares. This lake is the largest
reservoir collecting all municipal wastewater
of Hanoi city.
Figure 1. Sampling site in Hanoi
2.1.3. Sample collection and preparation
The targeted fish species in lakes are carp, mud carp, catfish and hypophtalmichthys
that are popular freshwater fishes in Northern of Vietnam. In West Lake, three fish
samples for one species were collected in each season. In Yen So Lake, only carp, mud
carp, and hypophtalmichthys were collected rainy season; mud carp and
hypophtalmichthys were collected in the dry season. In both seasons, twenty-four and
fifteen fish samples were collected in West Lake and Yen So Lake, respectively. The
bodyweights of fish samples were range from 0.6 to 2.6 kg.
The collected fish samples were washed then cut into thin slice and ground well.
Each 5g of fish sample was processed based on the UNU project document [17]. PFSAs
were extracted, purified and concentrated using solid phase extraction techniques using
weak anion exchange columns (WAX, Oasis). The final elution was filtered via 0.2 µm
syringe filter before kept into a 1ml injection vial.
2.1.4. PFASs analysis
PFASs were analyzed by LC-MS/MS 8040, Shimadzu, Japan. The LC system was
equipped with a column (Poroshell 120, EC.C18 (2.1 mm I.D. × 150 mm L, 2.7 μm) and
guard column EC-C18, Agilent, USA. The mobile phase consisted of a binary mixture of
A (2 mM.L
-1
ammonium acetate in water with methanol in a ratio of volume is 9 and 1)
and solvent B (methanol) at flow rate of 0.25 ml.min
-1
. The gradient, the start with 50% B
in 2 min increased to 95% B for 18 min and linearly at 95% B for 4 min then ramped to
Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish
39
50%A for 5 min. Total running time was 29 min. The inject volume was 2μL. The MS
system was running with an electrospray ionization source in negative mode (ESI)
at 3.5kV.
2.1.5. Quality Assurance and Quality Control
Mass-labeled
13
C of 7 pefluoroalkyl carboxylic acid compounds (including C4, C6,
C8, C9, C10, C11, and C12) and marked
18
O,
13
C of 2 Perfluoroalkylsulfonate compounds
(including C6 and C8) were used as internal standards for PFASs, being added to fish
homogenates before digestion to minimize analytical bias. Procedural blanks were tested
every 5 - 10 samples to check for possible laboratory contaminations and interferences.
Matrix spike recovery was determined by spiking mixed target standards into the fish
muscle samples, followed by the extraction and analysis. In a batch of samples on LC-
MS/MS, the standard solution was checked for 10 replications. Quantitative limits for 12
PFASs ranged from 0.01 to 0.06 ng.g
-1
for fish homogenates samples. The recovery of 12
PFASs ranged from 81% to 125% (CV 3-12%) for fish matrix.
2.2. Result and discussion
2.2.1. PFASs concentrations in fish samples
The total of PFASs concentrations in the fish samples are presented in figure 2 for
two lakes. PFASs were detected in all four fish species (catfish, mud carp,
hypophtalmichthys, and carp) in both lakes. The PFASs concentration in fish muscle in
Yen So lake tends to be higher than those in West Lake. In comparison with previous
reports, the total concentration of PFASs in fish blood samples in Yen So lake was higher
than those in West Lake [18]. This is explained by the fact that Yen So lake contains
wastewater of Hanoi city from To Lich, Kim Nguu, Set and Lu rivers while the West
Lake only contains domestic waste water from residential areas along the lake and
rainwater from the surrounding area.
Figure 2. PFASs concentrations in fish samples in West lake and Yen So lake
The PFASs concentrations are different in four fish species and decrease from catfish,
mud card, hypophtalmichthys to carp in West Lake. The PFASs concentration average
was in range from 1.98 ng.g
-1
w.w. in catfish to 0.44 ng.g
-1
w.w in carp. The catfish
N. T. Ngoc, P. T. L. Anh, P. D. Quang, T. T. Kim, T. T. Mai, D. H. Anh and P. H. Viet
40
samples have higher PFASs concentration because they live in the bottom water layer and
sediment of the lake. Other while, their average body weight is the highest among other
fish samples species. Although we only study the PFASs contamination on three fish
species in Yen So Lake, but the PFASs contamination concentration are higher than those
in West Lake. The PFASs concentrations decrease from hypophtalmichthys to carp, and
mud card.
2.2.2. Composition profiles of various PFASs in fish samples
Figure 3. Distribution of 12 analysed PFASs in fish muscle samples:
(a) in West lake and (b) in Yen So lake
The composition profiles of PFASs are presented in figure 3. Five
perfluoroalkylcarboxylic acids (PFOA, PFNA, PFDA, PFUdA, and PFDoA) and only one
perfloankylsulfonates compound (PFOS) were found in fish samples in both lakes. The
concentrations were different in various compounds. Such as in catfish sample in West
Lake, the concentrations were: PFOA (0.005 ng.g
-1
w.w), PFNA (0.054 ng.g
-1
w.w),
PFDA (0.81 ng.g
-1
w.w), PFUdA (0.66 ng.g
-1
w.w), and PFDoA (0.33 ng.g
-1
w.w). The
PFASs with long-chain carbon compounds such as PFNA, PFDA, PFUdA and PFDoA
were predominant in the entire both lakes. This may be explained by a more extensive use
in consumer products in the country and/or by their relatively higher solubility and thus
higher mobility in water [19]. The bioaccumulative of PFASs should be studied to find
out the different concentration in various compounds.
2.2.3. Bio-Accumulation of fish
The water environment can be significantly effective to aquatic biota. Fish is one of
specific bio-indicators shows for water contamination level. Mean bioconcentration
factors (BCF) were calculated based on PFASs concentration measured in water and biota
collected from the same area, followed in equation 1.
w
f
C
C
BCF
(1)
where Cf is the PFASs concentration in fish (ng.g
-1
w.w) and Cw is the PFASs
concentration in water (ng.mL
-1
).
Twenty surface water samples were collected in each study lake to calculate BCF.
BCF values of fish samples are presented in the table 2. PFNA, PFDA, PFDoA and PFOS
(a) (b)
Survey of perfluoroalkyl substances concentration and their bioaccumulation in fish
41
were the main PFASs components bioaccumulated in fish samples in both lakes. The
PFDoA‟s BCF values were the highest (854 - 3743), whereas PFOA‟s BFC values were
the lowest in both lakes (2.19 - 27.5). In perfluoroalkylcarboxylic acids group, BFC
values increase with the carbon chain length. This tendency is similar to other PFASs
bioaccumulation studies [20, 21]. A. Hagenaars et al., found that PFASs with longer chain
lengths are more toxic than PFASs with shorter chain lengths [22]. Comparison based on
the functional groups of compounds with the same chain length indicates that PFASs with
a sulfonate group have a larger toxic potential than the ones with a carboxyl group. In this
study results, PFOS‟s BCF value was higher than PFOA‟s. Depend on individual living
environment and fish species, PFOS‟s BFC values are 10 to 135 times more than PFOA‟s.
Lam et al. also reported the BCF values for the longer carbon chain PFASs were higher
than those for the shorter carbon chain PFASs in tilapia liver. The PFOA concentrations
in water were relatively higher than those of PFOS, but the BCFs of PFOA in biota were
less than those of PFOS [23].
Table 2. BCFs for individual PFASs
P
F
B
A
P
F
P
eA
P
F
H
x
A
P
F
H
p
A
P
F
O
A
P
F
N
A
P
F
D
A
P
F
U
d
A
P
F
D
o
A
P
F
B
S
P
F
H
x
S
P
F
O
S
West
lake
Catfish - - - - 2.19 132 1654 - 3044 - - 298
Mud carp - - - - 27.4 90.4 656 - 1943 - - 260
Hypo. - - - - - 18.6 543 - 1287 - - 269
Carp - - - - 5.78 92.4 172 - 854 - - 541
Yen So
lake
Mud carp - - - - 27.5 46.7 600 - 2515 - - 145
Hypo. - - - - - 37.2 1066 - 3367 - - 472
Carp - - - - - 20.6 659 - 3743 - - 671
“-“ non- detectable data
3. Conclusion
The research results provide the valuable information of PFASs contamination in
freshwater fish species of two urban lakes in Hanoi. The source of PFASs contamination
in these lakes related to the wastewater from municipal discharge. Yen So lake reserves
the municipal wastewater of Hanoi therefore the PFASs contamination concentrations are
higher than those in West lake.
Five PFCAs including PFOA, PFNA, PFDA, PFUdA, and PFDoA were found in fish
muscle samples in both West Lake and Yen So Lake. Only PFOS dominated PFSAs
N. T. Ngoc, P. T. L. Anh, P. D. Quang, T. T. Kim, T. T. Mai, D. H. Anh and P. H. Viet
42
compound was found. The BCF of PFDoA was the highest in both study lakes (854.48 -
3742.68), whereas PFOA‟s BFC values were the lowest in both lakes (2.19 - 27.48).
In PFCAs acids group, BFC values increased with the carbon chain length but with the
same carbon chain length, BCF value for PFOS were higher than for PFOA.
PFASs are concerned contaminants in recently because of their bioaccumulation,
toxicity, and availability. The further studies with greater numbers of water, sediments,
and fish are needed for accurate assessment of sources and pathways of exposures, and
bioaccumulation of PFASs in aquatic environment in other locations in Vietnam.
Acknowledgements. The research was conducted in the frame of the project
“Monitoring and Management of POPs in Asia” co-ordinate by the United Nation
University and supported a part finance from Shimadzu Co., Japan.
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