Occurrence of perfluorinated chemicals (PFCs) in leachate, surface water and sediment collected from Tay Mo landfill and surrounding areas
Cite this paper: Vietnam J. Chem., 2021, 59(2), 239-246
DOI: 10.1002/vjch.202000157
Article
Occurrence of perfluorinated chemicals (PFCs)
in leachate, surface water and sediment collected from Tay Mo landfill
and surrounding areas
Nguyen Thuy Ngoc, Phung Thi Vi, Pham Hung Viet, Duong Hong Anh*
Research Centre for Environmental Technology and Sustainable Development (CETASD),
VNU University of Science, Vietnam National University, Hanoi 10000, Viet Nam
Key Laboratory of Analytical Technology for Environmental Quality and Food Safety Control (KLATEFOS),
VNU University of Science, Vietnam National University, Hanoi 10000, Viet Nam
Submitted September 11, 2020; Accepted February 19, 2021
Abstract
The municipal landfill is considered to be a potential source of different environmental contaminants derived from
consumer goods, including perfluorinated chemicals (PFCs). Twenty-four leachate, surface water samples and twenty-
four sediment samples collected at Tay Mo landfill (Hanoi, Vietnam) and surrounding areas were analysed for sixteen
PFCs. Total concentrations of PFCs in leachate and surface water ranged from 103 to 328 ng/L (mean: 161 ng/L) at Tay
Mo landfill, 19.1-22.4 ng/L (mean: 20.7 ng/L) in ponds nearby the landfill, 5.19-6.96 ng/L (mean: 5.96 ng/L) in Nhue
River around the landfill, 5.57-12.7 ng/L (mean: 9.00 ng/L) in the upstream and 3.81-11.5 ng/L (mean: 7.14 ng/L) in the
downstream. The total concentrations of PFCs in landfill sediment which ranged from 3.52 to 6.70 ng/g (mean: 5 ng/g)
was 3-4 times higher than those in sediment taken from Nhue River and the ponds around the landfill. The dominating
detected compounds were short-chain perfluorinated alkyl substances like PFOA, PFHxA, PFHpA in water, and PFOS,
PFBS in sediment.
Keywords. PFCs, leachate, Tay Mo municipal landfill.
1. INTRODUCTION
upholstery, garments, leather products, wrapping
paper, etc. The landfill technology, which is widely
In 2009, a number of perfluorinated chemicals applied in Vietnam, is the decomposition method of
(PFCs) were included in the list of persistent organic waste material with the least energy consumption.
pollutants (POPs) that need to be monitored, During the decomposition process, consequently
restricted, and even banned under the Stockholm undesirable pollutants such as PFCs can be released
Convention. Due to their both lipophilic and into leachate owning the risk of contamination for
hydrophilic properties, PFCs have been used since the surrounding environment, especially surface
the 1950s[1,2] for the surface treatment of furniture. water and groundwater.[6] While a considerable
There are numerous applications of PFCs in number of studies on the occurrence of PFCs have
domestic and industrial activities such as been conducted in landfills in many countries[7],
impregnation or coating agents on the surface of investigations in Vietnam are still minimal. Joo Woo
carpets, leather, being used in textile and garment Kim et al. reported the occurrence of PFCs in one
products, paper and wrapping paper, metal surface, leachate and nine river water samples around Nam
cleaning products, and some types of plastic, Son landfill since 2011[8] and N.H. Lam investigated
insecticides, etc.[3] After being used, along with levels of PFCs in samples around landfills in Ho Chi
waste, the PFCs will be discharged into the Minh City (HCMC) in 2017.[4] Studies on municipal
surrounding environment and found in most dumping sites in the USA, Europe indicated that
environmental objects like water, soil, biota and the PFCs were detected in the leachate at concentrations
food chain.[1,2,4] To date, the data on PFCs in ranging from hundreds to thousands of ng/L at sites
Vietnam environment is still limited, focusing on where have been closed for 2-4 decades.[7] The Tay
surface water, sediment and freshwater fish, etc.[1,4,5]
Mo landfill has been one of domestic waste sites in
The municipal dumping site is a waste collection Hanoi operating for 3 years from 1997 to 2000. At
site of consumer goods being potential that time, the leachate treatment system was not
contamination sources of PFCs such as carpets, worked effectively, even not used. At present,
239 Wiley Online Library © 2021 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH
Vietnam Journal of Chemistry
Duong Hong Anh et al.
residual household waste has been still piled up to and inefficient technologies. Because leachate from
become open-air huge garbage piles in few areas. the landfill can be washed away with rainwater, it is
Accordingly, this site can be a potential source unavoidable that a lot of toxic substances from
which releases pollutants into the surrounding leachate can be dispersed into the surrounding
environment. In this study, leachate, surface water environment. Currently, the Tay Mo landfill has
and sediment samples were collected at the Tay Mo stopped working, but the amount of garbage in the
landfill, nearby ponds, Nhue River at the positions in past is still piled up. At present, next to this closed
the front, near and the back of the site to elucidate landfill, the Phu Dien composting plant, which
the occurrence and level contamination of PFCs in specializes in the treatment of faecal sludge from
the environment around this garbage dump that has toilets, is managed by the Hanoi Urban
closed for 20 years.
Environmental Company (URENCO).
Leachates, surface water and sediment samples
were collected at the following locations: (i) At the
landfill: 04 points (TM1, TM2, TM3, TM4) -
drainage from the landfill; (ii) ponds next to landfill:
02 points (TM5, TM6); (iii) Nhue River around the
landfill (NS01, NS02, NS03, NS04); (iv) the
upstream of Nhue River (NU01, NU02, NU03,
NU04); (v) the downstream of Nhue River (ND01 to
ND10). Sampling locations are shown in figure 1.
Total collected samples were 24 water samples and
24 sediment samples.
2. MATERIALS AND METHODS
2.1. Studied area and sampling location
The Tay Mo landfill with an area of 4.9 ha which
located about 10 km west of the center of Hanoi was
operated from 1997 to 2000 and received about
1,400 tons of waste per day.[9] In the 1990s, the
primary treatment and disposal method for the city's
domestic waste was landfills. At those landfills,
leachate was hardly treated or only treated by old
Figure 1: Sampling areas: Tay Mo landfill and
surrounding area, Nhue River upstream, Nhue
River downstream
Figure 2: Sampling locations: Tay Mo landfill
(TM1 to TM4) and surrounding area (the pond:
TM5, TM6; Nhue River: NS01 to NS04)
sample was filtered through a glass filter GF/F
(Whatman) to remove suspended solids, then spiked
2.2. Analysis
The analytical procedure of PFCs in water and with the surrogate solution containing MPFAC -
sediment was optimized by the laboratory[10] based MXA (Wellington, Canada). An Oasis-WAX
on the method provided in ISO 25101:2009.[11] The cartridge (225 mg, Water, USA) was conditioned
steps of sample preparation and analysis of PFCs by before the sample was passed through the cartridge.
liquid chromatography-tandem mass spectrometry The extraction column was eluted with 4 mL of
(LC-MS/MS) are briefly summarized below.
methanol and 4 mL of 0.1 % ammonium acetate
Preparation of surface water samples: The water solution in methanol (m/v). The eluate was
Vietnam Journal of Chemistry
Occurrence of perfluorinated chemicals…
concentrated to 1 mL under a gentle nitrogen stream, samples and sediment samples ranged from 67 to 114
filtered through a 0.2 µm nylon filter and put into an % and from 60 to 116 %, respectively. The limit of
injection vial.
detection (LOD) and limit of quantitation (LOQ) was
calculated as the concentrations that had signal-to-
Preparation of sediment samples: Approximately noise (S/N) ratios of 3 and 10, respectively. LOQ of
5.0 g of the wet sample was weighed and stored in a PFCs in water samples ranged from 0.1-0.4 ng/L, and
50 mL PP tube, then spiked with the surrogate LOQ in sediment samples was in the range of 0.1-0.2
standards containing MPFAC - MXA (Wellington, ng/g.
Canada). The sample was added with 20 mL of
methanol, vortexed and subjected to an ultrasonic 3. RESULTS AND DISCUSSION
extraction for 15 minutes. Next, the mixture was
centrifuged to collect the extract. This procedure
was repeated three times, and all supernatant was
combined and concentrated to 5 mL in a rotary
3.1. Total concentration of PFCs in leachate and
sediment from Tay Mo landfill
evaporator. The final 5 mL was mixed with distilled At studied sites in Tay Mo landfill, the total
water to obtain a solution containing 20 % (v/v) concentrations of 16 PFCs ranged from 103-328
methanol. The SPE procedure for the solution of ng/L in leachate and 3.52-6.70 ng/g d.w in dry
sediment extract was the same as that described for sediment. Total concentrations of PFCs in sampling
the water sample.
sites TM2, TM3, and TM4 locating on the water
runoff from the landfill to the surrounding area were
Instrumental analysis of PFCs by LC-MS/MS: detected at similar levels in both leachate and
Sixteen PFCs including 12 perfluoroalkyl carboxylic sediment samples. The point TM1 which was
acids (PFCAs, C5-14, C16 and C18),
4
collected at open-air waste piles, reached a very high
perfluoroalkyl sulfonates (PFASs, C4, C6, C8 and level of total PFCs in leachate (328 ng/L). There is a
C10), and 9 isotope-labelled surrogate standards of similarity in the total PFCs concentration of leachate
PFCAs and PFASs were analyzed on LC-MS/MS samples between Tay Mo closed landfill (in this
8040 (Shimadzu, Japan). The chromatographic study) and Nam Son active landfill (363 ng/L in the
separation was achieved with a Poroshell 120 EC- study of J. W. Kim[8]). By contrast, the total
concentrations of PFCs in the sediment at TM1 were
lower than other points. At present, information on
the occurrence of PFCs in sediment samples in
landfills has been limited in Vietnam. N. H. Lam
reported that concentrations of the target PFCs in
sediments obtained from the discharge drain at a
landfill in HCMC ranged from 1.31 to 1.75 ng/g
d.w,[4] only equal to one-third of these levels found
in this study.
In leachate, perfluoroalkyl carboxylic acids
(PFCAs) were found at higher concentrations than
perfluoroalkyl sulfonates (PFCASs) (p < 0.05) due
to the better solubility in water of the former. Short-
chain PFCAs (C5-C8) were detected at much higher
frequencies than long-chain PFCAs (p < 0.05), and
long-chain PFAAs with more than 11 carbon atoms
were hardly found. Among sixteen PFCs, PFOA,
PFHxA, and PFHpA were the most common
compounds, with the contribution to total PFCs in
the leachate of 31.7 %, 28.2 % and 16.3 %,
respectively. PFOA which had concentrations in the
range of 28.9 and 110 ng/L in wastewater at Tay Mo
landfill were significantly higher than other PFCs, it
is notable that this compound was always detected in
surface water in Vietnam.[4,12] The most significant
predominance of PFOA in leachate in this work is
consistent with other studies in the world.[6] Of the
C18 analytical column (150 mm 2.1 mm 2.7
µm) with the mobile phase A containing 2 mM
ammonium acetate and methanol (9:1, v/v) and
methanol as solvent B. Solvent gradient program
was set up as following steps. The mobile phase was
initially 30 % B and 70 % A for 2 min and then
changed to 95 % B and 5 % A in 16 min and held
for 4 min. At the end of the analysis, the mobile
phase was changed to the initial composition (30 %
B) for 3 min; flow rate was 0.3 mL/min. The PFCs
were quantified and qualified using tandem mass
spectrometry where the precursor ions were
fragmented into product ions. The target compounds
were ionized by the Electrospray Ionization (ESI)
o
technique with DL temperature of 250 C and the
nitrogen and dry air at the flow rate of 3 and 15
L/min, respectively. The calibration curve for each
congener was constructed at concentrations of 0.1;
0.5; 2.0; 5.0; 10; 20 ppb. The correlation coefficient
of the calibration curve (R2) was over 0.997.
QA/QC: The mixture of surrogate standards was
added to each sample prior to sample pre-treatment
for the purpose of determining the recovery efficiency
of PFCs in each run. A blank- and a matrix-spiked
samples were always analysed performed in the same
batch. The recovery efficiency of PFCs in water
Vietnam Journal of Chemistry
Duong Hong Anh et al.
PFASs, PFOS was found at the highest ng/L. The obtained results were similar to various
concentration in a range of 6.66-45.9 ng/L, studies, suggesting that PFAAs are the most
accounting for 11.9 % of total PFCs. In comparison dominant components of PFCs, and mainly short-
with other congeners, long-chain PFASs like PFDS chain substances were released from domestic
had the lowest concentration, approximately 0.2 waste.[7]
Table 1: Concentrations of PFCs in leachate and sediment collected from Tay Mo landfill, Hanoi
Concentrations in leachate
(ng/L)
Concentrations in sediment
(ng/g d.w)
Compounds
TM1
TM2
TM3
TM4
TM1
TM2
TM3 TM4
Perfluorooctanonic acid
(PFOA)
110.8
33.53
28.90
31.29
0.39
0.34
0.51
0.48
Perfluorooctansulfonate
(PFOS)
45.91
12.38
6.66
11.58
0.94
2.08
0.26
2.54
Total 16 PFCs
328
103
104
108
3.52
5.74
4.06
6.70
Average concentration of
total PFCs
161
5.00
chain PFASs like PFDS was detected. For the
PFAAs group, the short-chain acids such as PFHxA,
PFHpA and PFOA were observed in all samples
3.2. Composition of PFCs in leachate and
sediment at Tay Mo landfill
The composition of all target PFCs in leachate and where PFOA was still the most dominant
sediment samples at Tay Mo landfill is shown in component. Compared with the results in leachate,
figures 3 and 4.
the detection frequencies of long-chain acids with
Unlike the trend of leachate samples, in more than 11 carbon atoms in sediment samples
sediments, PFASs were major congeners were higher than those in leachate samples. The
contributing to the total content of PFCs. For PFOS and PFOA concentrations found in sediment
instance, PFOS and PFBS were found with the samples ranged from 0.26-2.54 and from 0.34-0.51
highest proportion in all samples, accounting for ng/g, respectively.
28.3 and 14.6 % of total PFCs; meanwhile, no long-
Figure 3: PFC composition profiles in leachate
Figure 4: PFC composition profiles in sediment
from Tay Mo landfill
from Tay Mo landfill
to the Tay Mo landfill, water and sediment samples
from the surrounding areas were collected, including
two ponds next to the landfill, the Nhue River (the
3.3. Occurrence of PFCs in Nhue river and
surrounding area
As described in the sampling locations, in addition upstream (n = 4), downstream (n = 10), and the part
Vietnam Journal of Chemistry
Occurrence of perfluorinated chemicals…
flowing through the landfill (n = 4)). Total river. Therefore, the influence of the leachate in Tay
concentrations of PFCs and two considerable Mo landfill on the presence of PFCs in water
substances, including PFOS and PFOA in water and samples taken in Nhue River at the time of sampling
sediment, are listed in table 2.
(dry season) was not observed. At the landfill and
The total concentrations PFCs which varied from two ponds next to there, PFOA and PFOS were
19.1-328 ng/L (n = 6) in water samples at the Tay detected with the detection frequency of 100 %. For
Mo landfill and two ponds next to the landfill were surface water samples collected from Nhue River,
much higher than those in Nhue River (n = 18, the while PFOS was found at a lower frequency (61 %),
concentration range of 12.7-3.81 ng/L). Besides, PFOA was observed in all samples and had the
there was no difference (p > 0.05) in the total highest concentration among PFCs. The PFCs
concentration of PFCs in surface water samples from concentrations in Nhue River water were similar to
the different parts of the Nhue River. These the results obtained in our previous studies on the
phenomena may be due to different effects caused wastewater in the drainage system in central Hanoi
by the water flowing from the PFCs source (leachate (Kim Nguu River, To Lich River, Yen So Lake)
in the landfill) to the receiving water bodies (the two with the total concentration of PFCs ranging from 4
ponds and Nhue River). The small ponds are closed to 10 ng/L in the dry season and there was no
water bodies which only receive rainwater and difference between upstream and downstream.[13]
leachate from the landfill; consequently, the effect of Although there are seven municipal wastewater
substances in the leachate is significant. For the treatment plants which have currently worked in
Nhue River, although the leachate from the landfill Hanoi, it is the fact that approximately three fourth
had high concentrations of PFCs, the flow of the of wastewater amount from domestic activities and
drainage from this closed landfill was negligible production has been discharged directly into this
compared to the large and continuous flow of the river and lake systems without sufficient treatment.
Figure 5: Total concentration of PFCs in leachate, surface water and sediment
at Tay Mo landfill compared to other investigated areas
At the Tay Mo landfill, the average total
concentrations of PFCs found in sediment (5 ng/g)
were three- to four-fold greater than those in Nhue
river (1.57 ng/g) and the ponds surrounding the
landfill (1.34 ng/g), respectively. However, the
comparison within result sets showed no statistically
meaningful difference between samples collected at
the landfill and other investigation areas.
3.4. Comparison of PFCs concentrations in
wastewater and sediment from different dumping
sites
A variety of data on PFCs at landfill obtained in this
study and other publications are summarized in table
2. The presence of PFCs in the wastewater and
leachate is of great concern in many countries
around the world, but in Vietnam, the data of PFCs
in wastewater and leachate is still limited. The first
literature published by J. W. Kim et al. in 2012[8]
Analysis results indicated that, despite being
closed, the Tay Mo landfill might be a potential
source of PFCs that pre-existed or emerged by the showed that the total concentration of PFCs, PFOA
and PFOS in leachate in Nam Son landfill in Hanoi
were 360, 100 and 11 ng/L, respectively. The Nam
Son landfill was put into operation after the Tay Mo
decomposition of residual waste, probably affecting
closed water bodies (like ponds) next to there.
Vietnam Journal of Chemistry
Duong Hong Anh et al.
landfill was full and had to stop working. Despite However, the Tay Mo landfill remains a potential
being closed for nearly 20 years, total concentrations source of POPs contamination like PFCs to nearby
of PFCs, PFOA and PFOS in leachate at Tay Mo water bodies especially during the rainy season.
landfill were similar to those at the operating Nam
Son landfill. In the study reported by N. H. Lam in Acknowledgement. This study was financially
2017, in wastewater drainage canal of two domestic supported by the National Foundation for Science
landfills in HCMC, PFCs were found at and Technology Development according to the
concentrations (3.19-3.33 ng/L) much lower than project grant No. 104.04-2017.346. The authors
that observed at Nam Son and Tay Mo. would like to thank the project ''Monitoring and
Additionally, the total concentrations of PFCs and management of POPs compounds in Asia''
PFOA from the drainage canals of the domestic coordinated by United Nations University of Japan
wastewater treatment plant in HCMC are about two- (UNU-IAS) for providing guidance on basic
to three times lower than that at the Nam Son and analytical techniques.
Tay Mo landfills. Through occurrence data of PFCs
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Corresponding author: Duong Hong Anh
Research Centre for Environmental Technology and Sustainable Development
(CETASD), VNU University of Science, Vietnam National University
334 Nguyen Trai, Thanh Xuan, Hanoi 10000, Viet Nam
Tel: +84- 91-238-0373, E-mail: duonghonganh@hus.edu.vn.
Table 2: Concentrations of PFCs in leachate and sediment from other landfills in the world
Country
Vietnam
Type of leachate (number of landfills)
PFOA (ng/L)
PFOS (ng/L)
PFCs (ng/L)
References
In this study
In this study
Tay Mo, Hanoi
Tay Mo, Hanoi
Nam Son, Hanoi
Nam Son, Hanoi
Hochiminh City
Hochiminh City
Spain
Leachate (n = 4)
51.0 (29.9-110)
6.11 (5.85-6.37)
100
19.1 (6.66-45.9)
1.49 (1.43-1.54)
11
161 (103-328)
Surface water from ponds next to landfill (n = 2)
Leachate (n = 1)
20.7 (19.1-22.4)
360 Joon-Woo Kim (2012) [8]
Surface water around the landfill (n = 9)
Drainage canals - landfill (n = 2)
Drainage canals - WWTP (n = 6)
Leachate (n = 4)
1.2 (< 1.4-11)
1.39 (1.38-1.39)
17.1 (0.84-53.5)
461 (387-584)
145 (< 0.4-926)
23.2-115.6
0.28 (0.8-2.5)
0.42 (0.26-0.59)
9.26 (<0.03-40.2)
11 (nd - 43)
8.4 (nd-15) Joon-Woo Kim (2012) [8]
3.26 (3.19-3.33)
N.H.Lam (2017) [4]
N.H.Lam (2017) [4]
I. Fuertes (2017) [6]
J. Busch (2010) [14]
Field et al. (2005) [19]
H. Yan (2015) [17]
36.2 (1.30-107)
1082 (639-1379)
1174
Germany
Leachate (treated and untreated) (n = 20)
Leachate (untreated) (n = 6)
Leachate (untreated) (n = 5)
Leachate (treated) (n = 5)
30.9 (0.01-235)
4.2-24.2
Norway
62-251
China
281-214000
1150-6020
7280-292000
98.4-286000
4960 (2515-8589)
2219
H. Yan (2015) [17]
China, Beijing
Australia
Leachate (untreated) (n = 3)
Leachate (closed landfills) (n = 7)
Leachate (n = 12)
2627 (1211-4658)
390±170
32 (<15-76)
180±250
C. Zhang (2014) [18]
C. Gallen (2017) [15]
C. Gallen (2017) [15]
B.O. Clarke (2015) [16]
510±410
300±330
3466
United States
Leachate (n = 5)
820 (177-2500)
52 (26-92)
Country
Vietnam
Sediment (number of landfills)
PFOA (ng/g d.w)
PFOS (ng/g d.w)
PFCs (ng/g d.w)
References
In this study
Tay Mo, Hanoi
Hochiminh City
Hochiminh City
China
Drainage canals - landfill (n = 4)
Drainage canals - landfill (n = 2)
Drainage canals - WWTP (n = 4)
Sludge from WWTP (n = 28)
Landfill ( n = 6)
0.29 (0.34-0.51)
< 0.2
0.97 (0.26-2.54)
< 0.08
5.00 (3.52-6.70)
1.31-1.75
0.18-23.4
1-23
N.H. Lam (2017) [4]
N.H. Lam (2017) [4]
Wei. Zhang (2013) [20]
Field et al. (2005) [19]
< 0.2
< 0.08
Norway
<LOD - 7.862
0.216-10.02
2.78-23.54
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