Science of the Total Environment 712 (2020) 136540

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Science of the Total Environment

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

Occurrence of pesticides in surface water, pesticides removal efficiency in

drinking water treatment plant and potential health risk to consumers in
Tengi River Basin, Malaysia
Nurulizani Elfikrie a, Yu Bin Ho a,⁎, Siti Zulfa Zaidon a, Hafizan Juahir b, Eugenie Sin Sing Tan c
a
Department of Environmental and Occupational Health, Faculty of Medicine and Health Sciences, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
East Coast Environmental Research Institute (ESERI), Universiti Sultan Zainal Abidin (UniSZA), Gong Badak Campus, 21300 Kuala Terengganu, Malaysia
c
School of Healthy Aging, Medical Aesthetics and Regenerative Medicine, Faculty of Medicine and Health Sciences, UCSI University, 56000 Kuala Lumpur, Malaysia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Eleven pesticides detected in Tengi

River and four in finished water of
DWTP.
• First investigation of six target
pesticides in DWTP
• Removal efficiencies of pesticides in
conventional DWTP ranged from 77 to
100%.
• Maximum concentration quantified
in river water was 4493.1 ng/L
(propiconazole).
• Hazard quotients (HQs) and hazard
index (HI) were less than 1 in finished
water.

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

Article history: Agricultural activities have been arising along with the use of pesticides. The use of pesticides can impact not only
Received 23 August 2019 on vector or other pest but also able to harm human health. Pesticide may leach from the irrigation of plant into
Received in revised form 3 January 2020 the groundwater and in surface water. These waters could be sources of drinking water in a pesticides polluted
Accepted 3 January 2020
area. This study aims to determine the occurrence pesticides in surface water and pesticides removal efficiency
Available online 08 January 2020
in a conventional drinking water treatment plant (DWTP) and the potential health risk to consumers. The
Editor: Yolanda Picó study was conducted in Tanjung Karang, Selangor, Malaysia. Thirty river water samples and eighteen water sam-
ples from DWTP were collected. The water samples were extracted using solid phase extraction (SPE) before
Keywords: injected to the ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS).
UHPLC-MS/MS Five hundreds and ten respondents were interviewed using questionnaires to obtain information for health
Solid phase extraction risk assessments. The results showed that propiconazole had the highest mean concentration (4493.1 ng/L)
Hazard quotient while pymetrozine had the lowest mean concentration (1.3 ng/L) in river water samples. The pesticides removal
Tengi River efficiencies in the conventional DWTP were 77% (imidacloprid), 86% (propiconazole and buprofezin), 88%
Malaysia
(tebuconazole) and 100% (pymetrozine, tricyclazole, chlorantraniliprole, azoxystrobin and trifloxystrobin), re-
spectively. The hazard quotients (HQs) and hazard index (HI) for all target pesticides were b1, indicating there
was no significant chronic non-carcinogenic health risk due to consumption of the drinking water. Conventional

⁎ Corresponding author.
E-mail address: yubin@upm.edu.my (Y.B. Ho).

https://doi.org/10.1016/j.scitotenv.2020.136540
0048-9697/© 2020 Elsevier B.V. All rights reserved.
2 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540
DWTP was not able to completely remove four pesticide; thus, advanced treatment systems need to be consid-
ered to safeguard the health of the community in future.
1. Introduction
Rice is a staple food for most countries in Asia, the region consumes
N80% of the world's rice. While there is dietary diversification, an aver-
age person still consumes rice as the main source of caloric intake in
Malaysia (Khazanah Research Institute, 2019). Rice is a crucial part of
everyday Malaysian meals; consuming about 82.3 kg per annum on
the average (Shamshiri et al., 2018). In 2016, Malaysia produced about
1.8 million metric tons of rice (Khazanah Research Institute, 2019). In-
evitably, pesticides are rampantly applied as they help to increase land
productivity, reduce crop damages and improve rice production. They
enter the environment during spraying activities, soil seepage and con-
tamination of surface as well as ground water (Herrero-Hernández
et al., 2013).
Exposure of pesticides to human can occur via ingestion, dermal and
inhalation; more prominently is daily exposure via food and drinking
water. Pesticides enter the human body, distributed via bloodstream
and excreted via urine, skin and exhaled air (Damalas and Koutroubas,
2016). Pesticides are known to cause various health effects such as der-
matological, gastrointestinal, neurological, carcinogenic, respiratory, re-
productive and endocrine disrupting particularly among vulnerable
population such as children, pregnant women and aging population
(Kim et al., 2017; Nicolopoulou-Stamati et al., 2016).
Surface and ground water surrounding agricultural areas are often
contaminated; its use for human consumption elicits deleterious health
effects (Herrero-Hernández et al., 2013). To date, there had been several
studies reporting presence of pesticides in surface water (Climent et al.,
2019; Derbalah et al., 2019; Herrero-Hernández et al., 2013; Montiel-
León et al., 2019; Papadakis et al., 2018). However, reported pesticides
differ from this study. Strobin, thiadiazin, anthranilic diamide, azole,
pyrazole, neonicotinoid, dithiolane, chloroacetanilide and triazine
were selected based on its rampant use in study area (Hamsan et al.,
2017).
Previous studies had reported coagulation–sedimentation to be inef-
fective for removal of pesticides and pesticide transformation products
during conventional drinking water treatment process (Benner et al.,
2013; Li et al., 2016). Occurrence of pesticides in drinking water had
been discussed by different authors in Canada, Ethiopia, Brazil and mid-
western United States (Caldas et al., 2019; Klarich et al., 2017; Mekonen
et al., 2016; Sultana et al., 2018). Klarich Wong et al. (2019) reported
concentrations of neonicotinoid metabolites (desnitro-imidacloprid
and imidacloprid-urea) in Midwestern United States; they were present
at lower concentrations than parent compound but exhibited higher
mammalian toxicity. Six pesticides investigated in this study have
never been previously reported in finished water.
Studies on health risk due to consumption of pesticide contaminated
drinking water remain scanty. Pesticides had been found in Ethiopia's
drinking water sources and affecting human health despite its concen-
trations being lower than acute reference dose; which was deemed
safe. However, due to the cumulative effect of pesticides, they may
cause harm to human health through chronic exposure (Mekonen
et al., 2016). Chronic exposure to pesticides has been associated with
health effects such as hormone disturbance, reproductive aberrance,
cancer, neurological disorders and cardiorespiratory symptoms
(Hamid et al., 2016).
Tanjung Karang in Kuala Selangor is a famous rice granary area and
is the fourth largest area of land rice cultivation in Malaysia (Rasit
et al., 2016). Tengi River is the main water supply for paddy irrigation
and serves a conventional drinking water treatment plant (DWTP).
Community in Tanjung Karang is at risk to pesticides contamination in
© 2020 Elsevier B.V. All rights reserved.
finished water from DWTP. As such, this study aims to determine
(i) occurrence of pesticides in Tengi River; (ii) pesticides removal effi-
ciency in a conventional DWTP and (iii) potential health risk to con-
sumers from ingestion. Target compounds were azoxystrobin,
buprofezin, chlorantraniliprole, difenoconazole, fipronil, imidacloprid,
isoprothiolane, pretilachlor, propiconazole, pymetrozine, tebuconazole,
tricyclazole and trifloxystrobin. Detailed information on the individual
target compounds including ISO common name, class, type, CAS-No,
molecular formula, molecular structure, and molecular weight, Log
Kow and cancer classification are available in Supplementary material
at the Elsevier publisher website (Table S1).
2. Materials and methods
2.1. Chemicals and standards
Reagent-grade acetone, reagent-grade dichloromethane (DCM) and
HPLC-grade methanol (MeOH) were purchased from Fisher Scientific
(New Hampshire, USA). Reagent-grade MeOH and hydrochloric acid
(HCl) 37% were sourced from Merck (Darmstadt, Germany). Formic
acid 98% and sodium thiosulphate (Na2O3.5H2O) 99% were purchased
from R&M Chemicals (Malaysia). Ammonium formate 10 M in water
and reference standards of azoxystrobin (98.5%), buprofezin (99.0%),
chlorantraniliprole (99.0%), difenoconazole (98.7%), fipronil (99.0%),
imidacloprid (99.0%), isoprothiolane (97.8%), propiconazole (99.0%),
pymetrozine (99.0%), tricyclazole (99.0%), trifloxystrobin (99.0%) were
supplied by Dr. Ehrenstorfer (Germany). Pretilachlor (98.7%),
tebuconazole (99.3%) and surrogate standard imidacloprid-d4 (99.0%)
were purchased from Sigma-Aldrich (MO, USA). Ultrapure water was
generated using a Milli-Q Advantage A10 (France). A solid-phase ex-
traction (SPE) 12-position vacuum manifold set was purchased from
Phenomenex (CA, USA), an Oasis® hydrophilic-lipophilic balance
(HLB) SPE cartridge 3 mL of 60 mg was obtained from Waters (MA,
USA). Nylon membrane filter papers (0.45 μm) were purchased from
Membrane Solutions (Texas, USA).
2.2. Sampling and site characterization
Study was conducted at Tengi River and a conventional DWTP in
Tanjung Karang, Selangor, Malaysia as shown in Fig. 1. Tengi River has
two tributaries; of which one irrigates paddy farms and serves the
DWTP while another is a fishing region and irrigates remaining paddy
farms. The main canal is used to irrigate the Sawah Sempadan paddy
field. Upon completion of harvest, remaining water in the farming
area will be discharged via three outlet sluices into the Tengi River.
Vice versa, river water will be supplied to paddy farms for new season
via the main inlet sluice. Outlet sluices will be opened during heavy
downpour to allow adjustment of water level. The three outlet sluices
are used to (i) discharge irrigation water from paddy farming; (ii) dis-
charge irrigation water from paddy farming and permanent crop plan-
tation; and (iii) discharge irrigation water from permanent crop
plantation only. Opening of these outlet sluices contaminates Tengi
River with pesticides residue from surrounding paddy and farming
area. Pesticide contamination may also occur due to overflow during
rainy season. Besides, these sluices are worn out due to prolong use
and poor maintenance.
A conventional DWTP is located along the main canal of Tengi River
as depicted in Fig. 1. It is operating since 1988; supplying six million gal-
lons of clean water to population of Tanjung Karang and Sekinchan,
Malaysia. Water treatment process begins with river water uptake at
 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540 3

Fig. 1. Sampling locations along Tengi River and DWTP.

Tengi River and undergoes initial screening process. Two types of filters
are used for screening; coarse and fine filter. They remove and separate
coarse and fine particles from the water. Thereafter, water will flow into
raw water tank via gravity. Aluminium sulphate and Superfloc C591 will
be added to raw water for coagulation and to produce flocs. Water will
be pumped using the submersible pump for mixing. During sedimenta-
tion, flocs will form sludge blanket trapping and preventing flocs from
surfacing. Once again, water will be filtered via gravity to remove parti-
cles; then chlorinated, adjusted for pH and fluoridated. Finally, finished
water is stored in clean water tank and pump house for distribution to
population of Tanjung Karang and Sekinchan, Malaysia.
Forty-eight (48) composite water samples were collected from
Tengi River and DWTP. Thirty (30) water samples were collected from
10 sampling points along the Tengi River (Fig. 1) and 18 water samples
were collected from 6 points in DWTP (Fig. 2). Samples were kept in 1 L
amber glass bottles. Sodium thiosulphate (80 mg) was used to dechlori-
nate collected water samples according to USEPA method 1699 (USEPA,
2007). Bottles were labelled, wrapped with aluminium foil, stored in ice

Fig. 2. Process flow of water treatment plant and the sampling points in DWTP.
4 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540
box at 0–4 °C and transported to the laboratory on the same day. Water
samples from DWTP were collected on 27 February 2017; while river
water samples were collected on 5 March 2017. During our sampling,
most rice plantations were cultivating; while some began harvesting.
During sampling, in-situ water quality parameters such as pH, tem-
perature, electrical conductivity, dissolved oxygen and turbidity of the
water were measured. Turbidity was measured using HACH 2100P
Turbiditimeter (USA). pH was measured using Milwaukee Portable pH
meter (USA) while dissolved oxygen was measured using Eutech In-
strument Cyberscan DO110 Dissolved Oxygen Portable meter (Thermo
Fisher Scientific Inc., USA). Next, electrical conductivity and tempera-
ture was measured using Waterproof Portable Meter (CyberScan Series
600, USA); both parameters were measured simultaneously.
2.3. Extraction of water samples
The extraction was modified according to De Gerónimo et al. (2014).
Water samples were filtered through 0.45-μm nylon membrane filter
removing particles that may interfere with analysis. Prior to solid
phase extraction, 30-μL of 1 mg/L surrogate standard (imidacloprid-
d4) was added to 60 mL of filtered samples. Then, samples were diluted
with 60 mL of ultrapure water to decrease their organic matter content,
viscosity and minimize matrix effects. The OASIS HLB 3 mL 60 mg solid
phase extraction cartridges were conditioned using 5 mL of methanol
and 5 mL of ultrapure water. Then, 120 mL of diluted samples were
loaded using a vacuum system. Cartridges were washed with 3 mL of ul-
trapure water and dried under vacuum for 20 min. After that, cartridges
were eluted using 4 mL of methanol. Extracts obtained were evaporated
using a gentle stream of nitrogen gas in a water bath (40 °C) and
reconstituted with 0.6 mL of methanol-water (50:50, v/v). Analysis
was performed using UHPLC-MS/MS system with injection volume of
2 μL.
2.4. UHPLC-MS/MS analysis
The UHPLC-MS/MS profile was based on Zaidon et al. (2019). The
UHPLC-MS/MS (Agilent, USA) was equipped with Zorbax Eclipse Plus
C18 column (2.1 mm × 50 mm I.D., 1.8 μm particle size) (Agilent,
USA). The composition of the mobile phase was as follows: Mobile
phase A composed of 0.1% formic acid and 5 mM ammonium formate
in ultrapure water; mobile phase B composed of 0.1% formic acid and
5 mM ammonium formate in methanol. Flow rate of mobile phase
was 0.5 mL/min with total run time of 20 min. Gradient of mobile
phase was as follows: 0 min: 94% A, 6% B; 15 min: 2% A, 98% B;
18 min: 2% A, 98% B; 18.01 min: 94% A, 6% B; and 20 min: 94% A, 6% B.
Column temperature was set at 40 °C. All target analytes were quanti-
fied using positive electrospray ionization (ESI) mode except fipronil
which was quantified using negative ESI mode. Information of multiple
reaction monitoring (MRM) conditions in UHPLC-MS/MS analysis are
summarized in Table S2 (Supplementary Material).
2.5. Pesticides removal efficiency in DWTP
Pesticides removal efficiencies at each water-treatment process
were calculated using Eq. (1).
Pesticides removal efficiency
concentration of pesticide in
the raw water−concentration of pesticide under
treatment X
¼  100%
Concentration of pesticide in the raw water
where X is treatment process in DWTP (screening, mixing, sedimenta-
tion, filtration, finished water).
2.6. Quality control (QC)
All glassware were washed with acid and solvents to remove con-
taminants based on US EPA method 1699 (2007). Standard mixtures
were injected to UHPLC-MS/MS to obtain calibration curve for each an-
alyte; its concentrations ranged from 0.01 ng/L to 500 ng/mL. Linearity
of calibration curve was validated using coefficient of determination
(R2). Method detection limits (MDL) and method quantification limits
(MQL) were determined by its S/N value of 3 and 10 respectively
(Casado et al., 2018). All MDL and MQL were validated to have accept-
able accuracy (70%–120%) and precision (RSD ≤ 20%) according to
SANTE/11813/2017 (European Commisison, 2018).
Recovery was determined by comparing quantified concentrations
of target analyte in blank samples to spiked concentrations
(100 ng/mL) as depicted in Eq. (1) (Magnusson and Örnemark, 2014).
Cspiked −Cunspiked
Recovery ð%Þ ¼  100 ð1Þ
Cadd
where Cspiked is the concentration or target analyte measured in a spiked
sample, Cunspiked is the concentration of target analyte measured in a
blank sample, and Cadded is the known concentration added to the sam-
ple (Magnusson and Örnemark, 2014).
Matrix effects (ME) were determined by comparing response
analytes' peak area in samples to that in solvent at the same concentra-
tion (100 ng/mL) (Bordin et al., 2017). The ME was determined using
Eq. (2).
Rmatrix
Matrix effect ð%Þ ¼  100 ð2Þ
Rsolvent
Quality control parameters are summarized in Table S3 (Supple-
mentary material). MRM chromatograms of native standards
(100 ng/mL) and surrogate standard (50 ng/mL) spiked in sample
blanks are shown in Fig. S1 in Supplementary materials.
2.7. Health risk assessment
Respondents sample size for this study was calculated using formula
from Naing et al. (2016). Sample size was calculated to involve at least
380 respondents. Additional 30% were added considering non-
response and missing data. Five hundreds and ten respondents were re-
cruited for cross sectional questionnaire survey consisting of two sec-
tions; section A (socio-demographics) and section B (information of
water intake). All respondents consume finished water supplied by
DWTP as their only source of drinking water. Information gathered
was subsequently used to calculate ingestion risk of pesticides contam-
inated drinking water by population around Tengi River. Questionnaires
were distributed from 16th to 19th January 2017.
Non-carcinogenic risks were calculated using hazard quotient (HQ);
ratio of exposure dose to compound-specific reference dose (RfD). The
HQ was used to determine non-carcinogenic health risks; which
HQ b 1 no significant risk and HQ N 1 indicates significant non-
carcinogenic health risk. The ingestion HQ was defined based on
USEPA, 2004 (Eq. (3)):
ADD
HQ ¼ ð3Þ
RfD
where ADD is the average daily dose (mg/kg/day), and RfD is the refer-
ence dose (mg/kg/day). RfD values for the targeted compound are
ð1Þ
shown in Table S4 as attached in Supplementary Material.
ADD is defined by Eq. (4) based on USEPA, 2004:
C  IR  EF  ED
ADD ¼ ð4Þ
BW  AT
 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540 5

where C is concentration of pesticides (mg/L), IR is ingestion rate (L/
day), EF is exposure frequency (days/year), ED is exposure duration
(years), BW is body weight (kg) and AT is averaging time (days).
Table S5 in Supplementary material summarized all value of the param-
eters stated in the equation above.
2.8. Statistical analysis
Statistical Package for the Social Sciences (SPSS) version 22 was used
to perform the statistical analysis. A pre-test was conducted to ensure
the reliability and validity of the questionnaire used in this study. Rela-
tionships between concentrations of pesticides in water samples with
in-situ water quality parameters were determined by using Spearman's
rank correlation coefficient (Spearman's rho).
Principal Component Analysis (PCA) assumes a bilinear model to ex-
plain variance in observed data using a reduced of orthogonal variables
known as principal component (PCs; Pekey et al., 2004). Once Kaiser's
VARIMAX rotation is performed, factor loadings remain orthogonal
and are no longer directed toward maximum explained variance, and
scores are not orthogonal (Peré-trepat et al., 2006). Using PCA, we
could identify unobservable and latent pollution sources (Helena et al.,
2000; Juahir et al., 2011). Fig. S2 shows the application process of PCA
techniques in this study. The PCA were carried out using XLSTAT in
Excel for Window.
3. Results and discussion
3.1. Concentration of pesticides in water samples collected from Tengi River
Concentration of pesticides in Tengi River is tabulated in Table 1.
Eleven out of thirteen compounds were detected in water samples.
Among 13 compounds, the maximum mean concentration was
propiconazole (4493.1 ng/L); ranged from 17.6 ng/L to 4493.1 ng/L.
Meanwhile, the minimum mean concentration was pymetrozine
(1.3 ng/L); ranged from ND to 260.8 ng/L. Multiple pesticides were de-
tected in water samples due to varying paddy cultivation period within
the study area as well as diversity of pesticides used by farmers.
The maximum concentration of propiconazole (4493.1 ng/L) quanti-
fied in this study was higher than previous studies. Propiconazole was
detected in several samples at a maximum concentration of 83 ng/L at
Llobregat River basin, Barcelona (Quintana et al., 2019). In Northern
Greece, Papadakis et al. (2018) reported a lower maximum concentra-
tion of propiconazole (0.307 μg/L) in Strymonas basin. Propiconazole
dissolves due to its water solubility, rarely volatilize, undergoes slow
degradation and not likely to partition to sediment (Battaglin et al.,
2011). To date, no study had reported occurrence of similar target pes-
ticides in Malaysia's water samples; either in surface water or drinking
water samples. Nevertheless, Wee et al. (2016) had reported the
occurrence of organophosphorus pesticides (chlorpyrifos, quinalphos
and diazinon) in Langat River, Malaysia and concentrations ranged
from 0.0094 to 0.0202 μg/L.
Results in this study reported point 10 to be most polluted with pes-
ticides and is located downstream of Tengi river. The highest mean con-
centration in point 10 was pymetrozine (260.81 ng/L) and the lowest
mean concentration was azoxystrobin (4.92 ng/L). All outlet sluices re-
leased irrigation water from paddy farms as well as adjacent agricultural
plantations such as oil palms. Therefore, most pesticides were quanti-
fied at this point.
Imidacloprid and tebuconazole were detected at highest frequency
in water samples from Tengi River. Most paddy blocks were in cultiva-
tion phase during sampling. At this juncture, use of insecticides such
as imidacloprid was preferred by farmers to avoid pest invasion. Insec-
ticide was frequently detected because it should be applied every
15 days after cultivation (Ali et al., 2017). Tebuconazole is a fungicide.
According to Battaglin et al. (2011), fungicide are often used as protec-
tive measure and commonly applied to prevent infections.
In this study, 2 out of 13 pesticides were not detected in river water
samples; they were fipronil and pretilachlor. Concurrent use of both in-
secticides (imidacloprid and fipronil) was not practiced; as informed by
paddy farmers during our survey. Pretilachlor was not detected in river
water samples as it is an herbicide and its application is typically during
early cultivation phase (1–2 days after seeding) (Chauhan et al., 2014).
In addition, pretilachlor is non-persistent in nature with short half-life
of 3.0 to 3.6 days in paddy water. Its continuous use will not lead to res-
idue built up over time (Fajardo et al., 2000).
3.2. Concentration and removal efficiency of pesticides in DWTP
Table 2 illustrates concentration of pesticides found in DWTP and re-
moval efficiencies for each treatment process. Nine pesticides were de-
tected in water samples collected from the intake point of DWTP; they
are pymetrozine, imidacloprid, tricyclazole, chlorantraniliprole,
azoxystrobin, tebuconazole, propiconazole, trifloxystrobin and
buprofezin. Results showed that combined water treatment processes
were effective for removing five pesticides completely; 100% removal
efficiency. However, four target compounds were inadequately re-
moved with removal efficiencies of 77% (imidacloprid), 86%
(propiconazole and buprofezin) and 88% (tebuconazole) and were
quantified in finished water.
The maximum concentration of pesticide detected in finished water
was 56.6 ng/L (buprofezin). Its concentration was lower compared to a
study in Ethiopia; which had maximum concentration of 11.948 μg/L
(Malathion) in drinking water (Mekonen et al., 2016). All target com-
pounds in this study were less than European Health-Based Chemical
Standards of 0.1 μg/L for pesticides other than organochlorine com-
pounds (Northern Ireland Environment Agency, 2016). To the author's

Table 1
Target compound concentrations in Tengi River (ng/L) (n = 3).

Target compound Mean ± SD

Point 1 Point 2 Point 3 Point 4 Point 5 Point 6 Point 7 Point 8 Point 9 Point 10

Pymetrozine ND ND ND 4.8 ± 2.4 2.7 ± 0.6 ND 1.3 ± 0.3 4.6 ± 0.8 7.9 ± 6.0 260.8 ± 284.4
Imidacloprid 19.5 ± 8.9 4.6 ± 2.5 8.5 ± 2.0 9.8 ± 5.7 7.2 ± 4.4 15.3 ± 11.9 20.6 ± 14.2 23.2 ± 5.9 57.7 ± 37.5 38.8 ± 21.4
Tricyclazole ND ND ND ND ND 4.44 ± 0.42 ND 8.72 ± 1.1 14.90 ± 1.1 20.92 ± 10.9
Chlorantraniliprole 24.9 ± 6.0 ND ND ND ND 56.9 ± 63.5 ND ND 19.2 ± 2.8 25.4 ± 16.0
Azoxystrobin ND ND ND ND ND 10.9 ± 14.1 ND ND ND 4.9 ± 0.5
Isoprothiolane ND ND ND ND ND 34.9 ± 60.3 ND 5.1 ± 2.5 16.2 ± 2.3 32.7 ± 18.0
Fipronil ND ND ND ND ND ND ND ND ND ND
Tebuconazole 17.4 ± 4.5 5.1 ± 1.6 4.0 ± 1.7 6.9 ± 4.6 5.5 ± 4.4 512.1 ± 149.8 17.7 ± 3.2 23.2 ± 7.4 43.3 ± 8.1 48.5 ± 27.7
Propiconazole 22.5 ± 8.0 28.2 ± 8.3 23.5 ± 7.3 48.9 ± 18.1 23.7 ± 13.0 4493.1 ± 1093.4 ND 17.6 ± 8.0 34.3 ± 9.3 49.1 ± 41.8
Difenoconazole 48.7 ± 12.6 ND ND ND ND 1620.3 ± 417.8 14.5 ± 3.5 16.8 ± 3.7 52.6 ± 10.5 67.1 ± 50.9
Pretilachlor ND ND ND ND ND ND ND ND ND ND
Trifloxystrobin 33.3 ± 9.9 ND ND ND ND 607.8 ± 153.6 9.3 ± 2.7 13.8 ± 3.3 47.7 ± 9.6 62.9 ± 43.0
Buprofezin 42.2 ± 11.3 ND ND 4.2 ± 2.2 6.8 ± 2.3 729.1 ± 184.3 15.7 ± 4.0 19.6 ± 3.6 53.7 ± 7.0 64.5 ± 40.1

ND – not detected.
6 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540

Table 2
Concentrations of target compounds in DWTP (ng/L) (n = 3) and removal efficiency in each treatment process.

Target compound Drinking water treatment process

Intake Screening Mixing Sedimentation Filtration Clean Water

point

Mean Mean Removal Mean Removal Mean Removal Mean Removal Mean Removal
± SD ± SD efficiency ± SD efficiency ± SD efficiency ± SD efficiency ± SD efficiency
(ng/L) (ng/L) (%) (ng/L) (%) (ng/L) (%) (ng/L) (%) (ng/L) (%)

Pymetrozine 4.2 ± 0.6 3.0 ± 1.4 29 2.8 ± 1.2 33 2.3 ± 1.5 45 2.1 ± 0.1 50 ND 100
Imidacloprid 115.3 ± 15.7 105.4 9 177.7 −54 116.1 −1 88.7 ± 39.9 23 26.3 77
± 29.5 ± 58.5 ± 23.5 ± 11.2
Tricyclazole 12.2 ± 2.4 7.2 ± 4.7 41 10.2 ± 1.6 16 6.0 ± 3.7 51 5.4 ± 1.8 56 ND 100
Chlorantraniliprole 54.7 ± 10.1 31.57 ± 4.5 42 29.0 ± 3.6 47 27.9 ± 5.5 49 25.4 ± 3.0 54 ND 100
Azoxystrobin 17.9 ± 7.3 7.0 ± 1.8 61 7.0 ± 1.1 61 6.7 ± 4.0 63 6.5 ± 2.1 64 ND 100
Isoprothiolane ND ND – ND – ND – ND – ND –
Fipronil ND ND – -ND – ND – ND – ND –
Tebuconazole 42.3 ± 10.7 24.4 ± 9.2 42 20.8 ± 6.0 51 18.8 ± 3.6 55 14.5 ± 9.2 66 5.2 ± 5.2 88
Propiconazole 265.1 ± 75.4 169.0 36 161.5 39 158.6 40 115.1 57 37.7 86
± 28.3 ± 45.3 ± 25.4 ± 62.5 ± 31.3
Difenoconazole ND ND – ND – ND – ND – ND –
Pretilachlor ND ND – ND – ND – ND – ND –
Trifloxystrobin 52.6 ± 18.5 47.3 ± 7.8 10 45.6 ± 12.6 13 38.5 ± 6.4 27 21.0 ± 2.1 60 ND 100
Buprofezin 392.8 234.7 40 272.9 31 227.6 42 191.7 51 56.6 86
± 147.6 ± 20.8 ± 39.2 ± 47.5 ± 81.5 ± 29.7

ND – not detected.

best knowledge, six target pesticides (pymetrozine, tricyclazole, (DO) and imidacloprid, (iii) imidacloprid and tricyclazole, (iv)
chlorantraniliprole, isoprothiolane, pretilachlor and buprofezin) were imidacloprid and tricyclazole, chlorantraniliprole and azoxystrobin,
reported for the first time in drinking water samples. (v) tricyclazole and isoprothiolane, tebuconazole, trifloxystrobin and
All target compounds in raw water were not removed by coagula- buprofezin, (vi) chlorantraniliprole and azoxystrobin, tebuconazole,
tion and sedimentation. Thereafter, five target compounds were 100% propiconazole, trifloxystrobin and buprofezin, (vii) azoxystrobin and
removed by filtration. The result was supported by Matsushita et al. propiconazole, trifloxystrobin and buprofezin, (viii) isoprothiolane
(2018), concentrations of their target compounds did not differ and tebuconazole, difenoconazole and trifloxystrobin, (ix) tebuconazole
after coagulation-sedimentation. They suggested that soluble and difenoconazole, trifloxystrobin and buprofezin, (x) propiconazole
micropollutants such as pesticides and their transformation products and trifloxystrobin and buprofezin, (xi) difenoconazole and
were not associated with suspended and colloidal particulate matter. trifloxystrobin, (xii) trifloxystrobin and buprofezin (p b 0.01) were re-
Results showed that conventional drinking water treatment process ported. Negative correlations were reported between (i) pH and dis-
such as coagulation and sedimentation to be incapable for removing solved oxygen (DO), (ii) pH and azoxystrobin and (iii) pH and
pesticides. This result is consistent with previous reports that most tebuconazole (p b 0.01).
micropollutants were difficult to be removed by coagulation–
sedimentation (Benner et al., 2013). Granulated activated carbon
(GAC) filter bed in DWTP had been reported to remove 94% of 3.4. Principal component analysis (PCA)
imidacloprid; meanwhile, laboratory batch kinetic tests reported rapid
removal N80% with 1 h contract with GAC (Klarich et al., 2017). Addition PCA was employed to the data set comparing compositional spatial
of powdered activated carbon in DWTP also improved removals of variation between quantified pesticide compounds in surface river
imidacloprid resulting in its non-detection in finished water samples water quality. Two Principal Components (PCs) were obtained with ei-
(Klarich Wong et al., 2019). genvalues larger than one; summing almost 91.7% of total variance in
Frequency of detection and concentration of compounds in the data set. All values of PCs after varimax rotation, variable loadings, and
water depended on their relative log Kow and water solubility variance are explicitly explained in Table 3 and Fig. 3.
(Stackelberg et al., 2007). Imidacloprid (log Kow = 0.57), tebuconazole
(log Kow = 3.7), trifloxystrobin (log Kow = 4.5) and buprofezin (log Table 3
Kow = 4.30) have higher log Kow compared to other target compounds Loadings of pesticide compounds on the varimax-rotated PCs for water quality data col-
lected at Tengi River.
in this study (Table S1 in Supplementary Material). According to
Stackelberg et al. (2007), incomplete removal of pesticides by existing Pesticide PC1 PC2
water treatment process resulted in their occurrence in drinking Pymetrozine −0.017 0.751
water; thus drinking water is a potential pesticide source to human. Imidacloprid −0.019 0.876
Tricyclazole 0.933 0.317
3.3. Correlation between the concentration of pesticides in water samples Chlorantraniliprole 0.943 0.261
Azoxystrobin 0.998 0.001
with the in-situ water quality parameters Isoprothiolane 0.795 0.553
Fipronil 0.000 0.000
During samples collection, in-situ water quality parameters such as Tebuconazole 0.998 −0.003
temperature, pH, electrical conductivity, dissolved oxygen and turbidity Propiconazole 0.995 −0.093
Difenoconazole 0.189 0.949
were measured. Results were tabulated in Table S6. According to Spear-
Pretilachlor 0.000 0.000
man correlation tests on pesticides and in-situ water quality parameters Trifloxystrobin 0.224 0.971
(Table S7), there was no significant correlation between temperature Buprofezin 0.069 0.982
with other in-situ water quality parameters as well as with pesticides. Eigenvalue 6.432 3.656
However, significant positive correlations between (i) electrical con- Variability (%) 49.690 42.017
Cumulative % 49.690 91.707
ductivity and isoprothiolane and difenoconazole, (ii) dissolved oxygen
 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540
2.5
Point 10
2 Imidacloprid
Pymetrozine
1.5 Point 9
PC2 (42.02 %)
Point 1
0.5
0
Point 8
-0.5 Point 7
Point 3 Point 4
Point 5
-1
Point 2
-1.5
-1 -0.5
Fig. 3. Factor loading PC1 vs PC2 after varimax rotation for pesticide compounds sampled from upstream and downstream of Tengi River.
Based on the analysis, PC1 accounted for 49.7% of the total variance,
reporting strong positive loadings (factor loading N0.6) of pesticides
compounds consisting of tricyclazole (0.933), chlorantraniliprole
(0.943), azoxystrobin (0.998), isoprothiolane (0.795), tebuconazole
(0.0.998), and propiconazole (0.995). While, PC2 responsible for 42.0%
of the total variance and reported strong factor loadings of chemicals
in pesticides, they are; pymetrozine (0.751), imidacloprid (0.876),
difenoconazole (0.949), trifloxystrobin (0.971) and buprofezin (0.982).
The highest concentration of pesticide compounds were detected at
sampling points number 10 and 6 (Fig. 1). Evidently, six sampling points
(out of 11) exhibited (PC1); these sampling stations were quantified
with the highest concentration of pesticide compounds namely;
tricyclazole (5.19 ng/L), chlorantraniliprole (8.87 ng/L), azoxystrobin
(1.2 ng/L), isoprothiolane (4.12 ng/L), tebuconazole (51.21 ng/L), and
propiconazole (299.54 ng/L). Furthermore, the highest concentration
of pesticide compounds was also recorded for PC2. Five out of 11 sam-
pling stations were also quantified with the highest pesticides com-
pounds; pymetrozine (17.39 ng/L), imidacloprid (3.878 ng/L),
difenoconazole (6.712 ng/L), trifloxystrobin (6.293 ng/L) and
buprofezin (6.454 ng/L). Sampling points number 1 and 9 were catego-
rized as moderate risk, while remaining six (6) sampling points were
categorized as low risk of pesticide contamination. Based on PCA results,
downstream areas of Tengi River basin were reported to be ‘high risk’ as
alarming concentrations of pesticides were quantified compared to up-
stream areas. There are several possibilities for these pattern of occur-
rence; (i) pesticides were used excessively upstream and contributed
to surface runoffs into Tengi river, (ii) physical-chemical properties of
pesticides causing cumulative effects at downstream areas, (iii) farmers
applying higher concentration of pesticides upstream than permitted
limits by relevant authorities and (iii) larger paddy areas downstream
compared to upstream leading to higher volume of pesticide use.
7
Biplot (axes PC1 and PC2: 91.71 %)
aer Varimax rotaon
Buprofezin
Trifloxystrobin
Difenconazole
Isoprothiolane
Tricyclazole
Chlorantraniliprole
Fipronil Azoxystrobin
Prelachlor Tebuconazole
Propiconazole
Point 6
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
PC1 (49.69 %)
3.5. Health risk assessment
This study focused on chronic exposure to target compounds via in-
gestion of finished water from DWTP. The chronic non-carcinogenic
health risk of consuming pesticides contaminated drinking water was
estimated based on information gathered from 510 respondents in
Tanjung Karang, Malaysia. Health risk assessments were focused on
four compounds detected in the final stage of treatment plant or in fin-
ished water; they are imidacloprid, tebuconazole, propiconazole and
buprofezin.
The HQ and HI for non-carcinogenic health risks are summarized in
Table 4. Among target compounds, buprofezin showed the highest HQ
(1.85 × 10−4) among kindergarten children while tebuconazole
showed lowest HQ (5.09 × 10−6) among elderly group. All HQ values
of these four target compounds were b1 which indicates that no signif-
icant chronic health risk due to daily ingestion of finished waster from
DWTP. To date, there is no publication on non-carcinogenic health risk
due to ingestion of target pesticides finished water of DWTP. However,
Mekonen et al. (2016) had reported chronic risks to human health for
exposure to diazinon and fenpropimorph in drinking water sources
from streams and ponds in Ethiopia; their estimated daily intake (EDI)
was greater than the acceptable daily intake (ADI). Zheng et al. (2016)
had reported risk quotient for human consumption of river water (Jiu-
long River and estuary in South China) to be b0.01 in respect to
imidacloprid, propiconazole, tebuconazole and buprofezin; thus postu-
lating pesticides to pose low risk to human health.
All HI values for this study were b1 which indicate non-significant
risk of exposure to mixture of four target pesticides found in finished
water. Kindergarten children recorded the highest HI value
(2.94 × 10−4) while the elderly group showed the lowest HI value
(7.72 × 10−5). Children and toddlers have the highest exposure because
8 N. Elfikrie et al. / Science of the Total Environment 712 (2020) 136540

Table 4
Hazard quotient (HQ) and hazard index (HI) values for non-carcinogenic health risk.

Compound Non-carcinogenic health risk

Kindergarten Primary school Secondary school Adult Elder

(age b 6) (age 7–12) (age 13–18) (age 19–60) (age N 61)

HQ HI HQ HI HQ HI HQ HI HQ HI

Imidacloprid 4.96 × 10−5 2.41 × 10−5 1.51 × 10−5 1.39 × 10−5 1.30 × 10−5
Tebuconazole 1.94 × 10−5 9.45 × 10−6 5.92 × 10−6 5.45 × 10−6 5.09 × 10−6
Propiconazole 4.05 × 10−5 1.97 × 10−5 1.24 × 10−5 1.14 × 10−5 1.06 × 10−5
Buprofezin 1.85 × 10−4 8.99 × 10−5 5.64 × 10−5 5.18 × 10−5 4.84 × 10−5
2.94 × 10−4 1.43 × 10−4 8.98 × 10−5 8.25 × 10−5 7.72 × 10−5

they consume more water per kg bodyweight compared to adult References

Lozowicka (2015). Lifetime cancer risk (LCR) for carcinogen
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samples.
4. Conclusion
This study showed that selected pesticides were detected in Tengi
River and a conventional DWTP. Most pesticides detected in the con-
ventional DWTP were efficiently removed except for imidacloprid,
buprofezin, tebuconazole and propiconazole. Pesticides removal effi-
ciency in DWTP should be improved to reduce risk for communities in
Tanjung Karang and Sekinchan. Hazard quotient showed that respon-
dents were unlikely to be effected by adverse non-cancer effect due to
consumption of finished water from the DWTP. The HI was less than
one indicating that the risk of exposure to mixture of pesticides was
not significant. This conclusion was made based on our quantified con-
centration and sampling duration. Researchers had identified several
influencing factors; they are plantation phases, government's pesticide
subsidy which affect farmers' selection of pesticides and maintenance
of DWTP. Since there was pesticide contamination, consistent water
quality monitoring was recommended for drinking water treatment
plant and its processes. Application of pesticides varies and is influenced
by paddy farming season. Likewise, concentration of pesticides in the
environment varies accordingly. It is suggested that addition of some
advanced water treatment processes such as activated carbon can in-
crease pesticide removal efficiencies in drinking water treatment plant.
Ethical considerations
All respondents were briefed and had given their informed consent
prior to participation. Ethical approval for this study was granted by
the University Research Ethics Committee of Universiti Putra Malaysia,
Selangor Malaysia ((JKEUPM) [Ref: FPSK (EXP15) P019]).
Declaration of competing interest
The authors declare that there is no conflict of interest.
Acknowledgments
This work was financially supported by the fund of the Ministry of
Education, Malaysia under the Fundamental Research Grant Scheme
(FRGS) under project number 5540106. We would like to thank the
Salak Tinggi Veterinary Public Health Laboratory, Department of Veter-
inary Services, Malaysia, for the use of their UHPLC-MS/MS. Special
thanks to the Department of Irrigation and Drainage, Tanjung Karang,
Malaysia for providing information for this study.
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