Science of the Total Environment 640–641 (2018) 671–677

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Science of the Total Environment

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

Removal of selected pharmaceuticals and personal care products in

reclaimed water during simulated managed aquifer recharge
Soohyung Park, Wontae Lee ⁎
Department of Environmental Engineering, Kumoh National Institute of Technology, Gumi, South Korea

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

• Per monitoring of 22 PPCPs at a WRF in

Korea, 15 substances were detected.
• Atenolol, propranolol and trimethoprim
were removed N80% through MAR.
• Atrazine, carbamazepine, lincomycin
and primidone were not readily
removed.

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

Article history: This study investigated the removal of selected pharmaceuticals and personal care products (PPCPs) in a simu-
Received 27 February 2018 lated managed aquifer recharge (MAR) system. The PPCPs included antibiotic, antiepileptic, antihypertensive,
Received in revised form 28 April 2018 anti-inflammatory, and antilipidemic drugs, contrast media, herbicides, and stimulants. We first monitored the
Accepted 18 May 2018
occurrence and fate of 22 PPCPs at a water reclamation facility (WRF) in Korea, and found carbamazepine and
Available online xxxx
primidone were not readily removed (below 25% removal in average) by the WRF. This reclaimed water passed
Keywords:
through a laboratory-scale soil column set-up at 0.5 m/d over one year, simulating MAR system. Atenolol, pro-
Pharmaceuticals pranolol, and trimethoprim exhibited higher removal rates (N80%) than other PPCPs through the simulated
Personal care products MAR, while atrazine, carbamazepine, lincomycin, primidone, and sulfamethazine were not readily removed,
Water reclamation exhibiting removal rates below 20%. It can be efficient to monitor and manage these recalcitrant compounds at
Water reuse MAR systems to improve water quality.
Managed aquifer recharge © 2018 Elsevier B.V. All rights reserved.

1. Introduction
Approximately 12,000 pharmaceuticals and personal care products
(PPCPs) have been distributed for human use worldwide. PPCPs include
a variety of chemical substances, including human and veterinary drugs,
disinfectants or fragrances in personal care products such as lotions, lip-
sticks, hair sprays/dyes, body cleaning products, and sun-screens
(Balmer et al., 2005; Gago-Ferrero et al., 2011), and household
chemicals (Boxall et al., 2012; Bu et al., 2013; Lin et al., 2016). After
their use in hospitals, households, and industries, residual PPCPs can
enter the aquatic environment via wastewater treatment systems
⁎ Corresponding author.
E-mail address: wtlee@kumoh.ac.kr (W. Lee).
and/or water reclamation facilities (WRFs) (Tran et al., 2014a, 2018).
PPCPs have been detected in waste and reclaimed waters at ng/L to
μg/L levels (Pedrouzo et al., 2007; Tran and Gin, 2017; Yang et al., 2011).
The presence of PPCPs in reclaimed water has received great atten-
tion owing to their potentially adverse influences on human health
and ecosystems (Tran et al., 2014a; Tran and Gin, 2017; Yang et al.,
2011). PPCPs are potentially hazardous to the aquatic ecosystem, and
can cause endocrine disruption and other severe side effects resulting
from the specific biological effects they were developed to induce
(Clara et al., 2005; Nakada et al., 2007; Tran and Gin, 2017; Tran et al.,
2014b; Vulliet et al., 2011). Wastewater can be reclaimed and reused
through various engineering techniques and natural or passive treat-
ment processes. Most WRFs employ multiple barrier approaches, in-
cluding activated sludge processes, media and/or membrane filtration,

https://doi.org/10.1016/j.scitotenv.2018.05.221
0048-9697/© 2018 Elsevier B.V. All rights reserved.
672 S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677
and disinfection (Page et al., 2010a, 2010b). However, the removal of
PPCPs by WRFs is reportedly inefficient (Nakada et al., 2006; Santos et
al., 2007; Tran et al., 2018) and depends on compound-specific proper-
ties as well as factors related to WRFs, such as the types of treatment
processes or age of sludge (Tran et al., 2013, 2018).
Water reuse can be facilitated by purposefully recharging reclaimed
water into aquifers for natural treatment prior to recovery and reuse.
This artificial recharge is called “managed aquifer recharge (MAR)”,
and is a natural water treatment process that induces the flow of
water the soil. MAR provides a natural buffer, provides a residence
time that can facilitate the removal of biodegradable organic matters
and pathogens, improves the quality of the treated wastewater, includ-
ing PPCPs, and reduces the cost of seasonal peak demands (Dillon et al.,
2008; Levantesi et al., 2010; Page et al., 2010a, 2010b).
MAR has not yet been applied for water reuse in Korea, although
this technology has been studied and applied in other countries, such
as the United States and Australia. PPCPs are an ideal group of com-
pounds for assessing the removal mechanisms of emerging contami-
nants by MAR owing to their varied chemical properties. The
occurrence of PPCPs in wastewater can be related to local production,
and the fate of these compounds in WRF and MAR can differ from that
observed in other countries. Though previous studies have elucidated
the removal characteristics of several PPCPs in MAR, few have system-
atically evaluated the relationship between the removals of PPCPs and
operational conditions with respect to the PPCPs' properties. This
study addresses these questions by monitoring the removals of 22
PPCPs in a full-scale water reclamation facility in Korea and a labora-
tory-scale MAR.
2. Materials and methods
2.1. Laboratory-scale soil column set-up and operation
MAR was simulated using a laboratory-scale soil column set-up,
which consisted of four 1000-mm acrylic glass columns in series with
an inner diameter of 150 mm. The columns were filled with native allu-
vial material (diameter b 2 mm). The porosity was 0.4, and the perme-
ability coefficient was 0.013 cm/s. The system was positioned in a
temperature-controlled room at 20 °C, and feed water was injected
into the soil column system by a peristaltic pump at 0.5 m/day (volu-
metric flow rate of 6.13 mL/min) upward flow, considering the typical
residence time of water in MAR systems (Racz et al., 2012). To eliminate
the effect of varying hydraulic recharge conditions, the experiment ran
at a fixed flow rate over the whole experimental period (from Septem-
ber 2016 through August 2017). The columns were initially saturated
with ambient groundwater and subsequently rinsed with the final efflu-
ent. The initial increase in electrical conductivity was used as a tracer for
determining the hydromechanical properties of the columns. The soil
columns were kept saturated at all times.
2.2. WRF and feed water to MAR
The simulated MAR system was fed with the final effluent of a WRF
in an industrial complex in Gumi, Korea, which had a capacity of
50,000 m3/d and received wastewater from the surrounding industrial
complex. The WRF consisted of primary treatment followed by a biolog-
ical process, coagulation/filtration, and UV disinfection. Prior to MAR
test, concentrations of target PPCPs in the influent, biological process,
coagulation/filtration process, and effluent were monitored for the 12-
month period (sampled every other month) from January to December
2015. The final effluent of the facility was collected and used as the feed
water for the laboratory-scale MAR from September 2016 through Au-
gust 2017. The feed water was filtered through glass fiber filters with
a pore size of 0.7 μm after collection.
2.3. Target PPCPs
Among the diverse array of PPCPs, we selected 22 compounds that
are common in aquatic systems, and the physical and chemical proper-
ties of these target compounds are presented in the supplementary ma-
terial (Table A.1). The compounds were selected to represent different
antibiotics, such as chlortetracycline, lincomycin, oxytetracycline,
sulfachloropyridazine, sulfamethazine, sulfamethoxazole, sulfathiazole,
tetracycline, and trimethoprim; antiepileptics, such as carbamazepine
and primidone; antihypertensive drugs, such as atenolol, metoprolol,
and propranolol; anti-inflammatory drugs, such as acetaminophen,
diclofenac, ibuprofen, and naproxen; antilipidemics, such as gemfibro-
zil; contrast media, such as iopromide; herbicides, such as atrazine;
and stimulants, such as caffeine. These compounds were listed among
the 30 most frequently detected organic wastewater contaminants re-
ported by the United States Geological Survey (Kolpin et al., 2002).
Atenolol, carbamazepine, gemfibrozil, ibuprofen, and sulfamethoxazole
were among the top ten high-priority pharmaceuticals identified in a
European PPCP assessment (Global Water Research Coalition, 2008).
2.4. Determination of water quality parameters and target PPCPs
All samples were filtered through membrane filters (0.4 μm,
Whatman, USA) to remove any particulate materials, and stored at 4 °C
in the dark. All water samples were extracted within one week for fur-
ther analysis if necessary. DOC was measured by a TOC analyzer (TOC-
VCPH, Shimadzu, Japan) using the non-purgeable organic carbon
method. Ultraviolet absorbance at 254 nm (UVA254) was measure at
254 nm wavelength by a UV spectrophotometer (Hach, USA). Electrical
conductivity (EC) was measured using a conductivity meter
(ThermoFisher, USA).
A highly sensitive analytical method was developed and validated
for determining the levels of PPCPs in wastewater. The PPCPs were sep-
arated and detected using LC-MS/MS methods based on the direct injec-
tion of a sample into the chromatograph (Tran et al., 2016; Tran and Gin,
2017; Vymazal et al., 2017). A 1290 High-Performance Liquid Chro-
matograph tandem with a 6490 Triple Quad Mass Spectrophotometer
(LC/MS-MS) (Agilent 1200 series rapid-resolution liquid chromato-
graph (Waldbronn, Germany), triple quadrupole 6490 Mass) was used
in the electrospray ionization (ESI; positive/negative) mode. ESI separa-
tion was conducted on an Eclipse C18 analytical column (100 × 2.1 mm,
3.5 μm particle size, Agilent). The mobile phase for material separation
contained de-ionized water (solvent a) and acetonitrile/methanol
(4:1, V/V) (solvent b). Both solvents A and B were added with 0.1%
formic acid, and the fractions of solvents A and B were changed over
time to efficiently separate the target material. Analytical conditions
for the LC/MS-MS are summarized in the supplementary material
(Table A.2). Limit of quantification (LOQ) for PPCPs was 1 ng/L, except
naproxen (20 ng/L). All standards were of high purity grade (N99%)
and purchased from Sigma-Aldrich (USA).
3. Results and discussion
3.1. Removal of target PPCPs by the WRF
The target compounds were selected to represent different PPCPs,
such as antihypertensive drugs (such as atenolol), stimulants (such as
caffeine), antilipidemics (such as gemfibrozil), antibiotics (such as sulfa-
methoxazole), and antiepileptics (such as carbamazepine and
primidone). Seven of the twenty-two target compounds were detected
at every sampling campaign of the WRF for the 12-month period from
January to December 2015, and they were listed in Table 1. Table 1 sum-
marizes the average, minimum, and maximum concentrations of the
target PPCPs in the influent and biological process, coagulation/filtra-
tion, and UV disinfection effluents.
 S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677 673

Table 1
Concentrations of PPCPs in influent and biological process, coagulation/filtration, and UV disinfection effluents of WRF (the value in parentheses is average; n = 6, sampled every other
month from January to December 2015).

Compound Concentration (ng/L)

Influent Biological process treated water Coagulation/filtration treated water UV disinfection (final effluent)

Atenolol 44–85 (71) 18–49 (44) 16–49 (34) 15–47 (32)

Caffeine 873–2104 (1336) 106–456 (256) 71–248 (158) 35–329 (103)
Carbamazepine 42–148 (90) 39–99 (70) 43–95 (71) 35–92 (68)
Gemfibrozil 58–394 (209) 25–161 (116) 24–145 (84) 27–148 (82)
Ibuprofen 641–1768 (1077) 76–203 (157) 34–127 (95) 24–104 (84)
Sulfamethoxazole 55–395 (182) 23–220 (127) 24–193 (104) 16–115 (72)
Primidone 3–11 (8) 3–10 (8) 3–10 (7) 3–11 (7)

Caffeine and ibuprofen were found at the highest levels of one μg/L
(Table 1). These compounds are steroid and analgesic, and they are
among the most widely used PPCPs in Korea. The caffeine concentra-
tions of the influents varied from approximately 873 to 2104 ng/L,
with an average concentration of 1336 ng/L. Caffeine is a stimulant
that is also commonly used in beverages and foods. Similar levels of
these compounds have been observed in the raw wastewater of other
municipal wastewater treatment plants in other countries (Benotti
and Brownawell, 2007; Tran et al., 2018; Vieno et al., 2005). For exam-
ple, caffeine in abundant in the influents of WRFs in other countries, at
concentrations ranging from below the method quantification limit to
120,000 ng/L (Tran et al., 2018). Yang et al. (2011) reported caffeine
concentrations ranging from 54,000–120,000 ng/L in the USA; Behera
and Kim (2011) reported caffeine concentrations ranging from 1608
to 3217 ng/L in wastewater in Korea; Tran et al. (2014b) reported con-
centrations ranging from below the detection limit to 16,249 ng/L in an
urban catchment area in Singapore; and Li et al. (2013) measured caf-
feine concentrations of 51,300–57,700 ng/L in a wastewater treatment
plant in Illinois, USA.
In this study, the ibuprofen concentrations of the influents varied
from approximately 641 to 1768 ng/L, with an average concentration
of 1077 ng/L. This pharmaceutical is widely used to relieve pain or sup-
press inflammation, and often detected in the influents of WRFs at con-
centrations reaching several hundreds of micrograms per liter (Miége et
al., 2009). Similarly, the concentrations of ibuprofen in the influents of
WRFs in previous studies varied from below the method quantification
limit to a few micrograms per liter (Kasprzyk-Hordern et al., 2009;
Kosma et al., 2010, 2014; Miége et al., 2009; Papageorgiou et al., 2016;
Tran et al., 2018). Ferrari et al. (2003) reported an ibuprofen concentra-
tion range of 3900–15,000 ng/L in the USA; Santos et al. (2007) reported
an average concentration of 93,925 ng/L in Seville, Spain; and Carballa et
al. (2004, 2008) reported an ibuprofen concentration range of 3697–
19,000 ng/L in Galicia, Spain.
PPCP removal by WRFs is a complicated process and depends on the
chemical and biological properties of the pollutants, such as their hydro-
philicity, solubility (Evgenidou et al., 2015), volatility, and biodegrad-
ability (Jones et al., 2005), and the adsorption capability of the
sludge process through biodegradation. The presence of electron donat-
ing groups (\\CH3) in caffeine molecules tends to increase the electron
density in the regions where these groups are attached. This causes caf-
feine to experience a large imbalance in its electrostatic distribution.
Therefore, it is assumed that the biodegradation of caffeine tends to be
initiated at the electron donating groups (\\CH3). Previous studies
demonstrated that N-demethylation is one of the main pathways for
the biodegradation of caffeine (Summers et al., 2015; Yu et al., 2015).
Additionally, caffeine is readily biodegradable (Okuda et al., 2008;
Thomas and Foster, 2005; Valsero et al., 2016).
The removal rate of ibuprofen (analgesic drug) was also high (~80%)
in previous studies (Ferrari et al., 2003; Nakada et al., 2007; Yu et al.,
2006). The excellent elimination rates of ibuprofen by biological waste-
water treatment processes could also be caused by the higher strength
of electron donation groups, such as alkyl groups (\\CH2\\CH[CH3]2),
than the electron withdrawing groups (\\CH[CH3]\\COOH) in these
molecules. Similar to caffeine, the biotransformation of ibuprofen
often takes place at the electron donating group (\\CH2\\CH[CH3]2)
on the aromatic ring via the hydroxylation or demethylation pathways
(Tran and Gin, 2017).
The carbamazepine and primidone removal levels achieved by the
WRF were below 20% in average. Several PPCPs with low removal effi-
ciencies, such as carbamazepine and primidone, are hardly biodegraded
or removed by treatment processes, regardless of the type of system
used (Behera and Kim, 2011; Clara et al., 2004; Joss et al., 2005; Miao
et al., 2005; Wang et al., 2014). The ineffective removal of PPCPs creates
by-products or metabolites and the causes the target PPCPs to conjugate
(Miao et al., 2005). The absence of electron donating group in carbamaz-
epine could be the reason resulting in poor removal in biological waste-
water treatment processes (Tran and Gin, 2017). Also, the results for
primidone indicate that it is resistant to activated sludge, coagulation,
100
January
March
80
May
July
September
Removal efficiency (%)

activated sludge (Liu and Wong, 2013). Secondary treatment manly re- November
fers to biological processes (i.e., activated sludge process) and enables 60
the removal of PPCPs through partition, adsorption, biotransformation,
and biodegradation (McClellan and Halden, 2010; Miao et al., 2005).
The removal efficiency of PPCPs by biological processes is highly depen- 40
dent on their nature, the hydraulic retention time (HRT), sludge age, ad-
sorption capacity on sludge, and reactor design (Bulloch et al., 2015;
Evgenidou et al., 2015; Lin et al., 2009). 20
The WRF consisted of screening, primary sedimentation, secondary
treatment, coagulation, and UV disinfection. The PPCP removal efficien-
cies by the WRF processes are presented in Fig. 1. In this study, caffeine 0
removal ranged from 89% to 95%, with an average value of 92%, and ibu- e n l le il e
ein ofe o lo o oz pin ne
ff pr en az ibr ze ido
profen removal ranged from 90% to 96%, with an average value of 92%. Ca Ibu At ox mf im
eth Ge ma Pr
m rba
The removal rates of caffeine and ibuprofen in our study are similar to lfa Ca
those observed in previous work. Federle et al. (2002) reported that
over 80% of caffeine and ibuprofen were removed by the activated Fig. 1. Removal efficiencies of seven PPCPs by treatment processes in the WRF.
674 S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677

100
and UV disinfection as it was frequently detected in the final effluent of
Travel time 2 days
the treatment facility. Although corresponding properties for primidone Travel time 8 days
were not found in the literature, these results indicate that primidone is
80
recalcitrant to water reclamation processes.

Removal efficiency (%)

3.2. Removal of PPCPs by the simulated MAR
60

Of the 22 monitored PPCPs, 15 (acetaminophen, atenolol, atrazine,

caffeine, carbamazepine, diclofenac, ibuprofen, iopromide, lincomycin,
primidone, propranolol, sulfamethazine, sulfamethoxazole, sulfathia-
zole, and trimethoprim) were detected in all samples from the WRF
effluent which was feed water to the MAR system. The levels of
chlorotetracycline, ibuprofen, metoprolol, naproxen, oxytetracycline,
sulfachloropyridazine, and tetracycline were below the LOQ in the sam-
ples. Table 2 presents concentrations of 15 PPCPs in feed water to the
MAR system. PPCP levels of the samples varied over the duration of
the experiment. However, no statistical trends was observed between
PPCP levels and the four seasons. Overall, caffeine was found at the
highest level of 328 ng/L in average, followed by iopromide (76 ng/L)
and carbamazepine (74 ng/L). General water quality parameters such
as DOC, UVA254, EC, and pH were also monitored and no substantial dif-
ference was observed between water quality levels and any of the four
seasons.
Removal efficiencies of PPCPs by the simulated MAR was assessed by
measuring concentrations of PPCPs in outflows from columns #1 (travel
time of 2 days), #2 (travel time of 4 days), #3 (travel time of 6 days),
and #4 (travel time of 8 days). The results of PPCP removals from the
soil column experiments in travel time 2 and 8 days were presented
in Fig. 2. Overall, removal rates of most compounds were higher after
8 days of traveling in the soil columns than 2 days of traveling. Both bio-
degradation and sorption could be major removal mechanisms for the
compounds, but we could not differentiate each mechanism in this
study because we did not inject biocide to the system. DOC and its hy-
drophobic portions, represented by UVA254, were removed during the
soil column experiment, indicating both biodegradation and sorption
occurred. As the travel time increased in the MAR system, both DOC
and UVA254 decreased (Table 3). Removal of UVA254 was higher than
that of DOC, which resulted in lowering specific ultraviolet absorbance
(SUVA) values. SUVA is a calculated parameter by dividing a sample's
UVA254 by the DOC concentration, and then multiplying by 100. SUVA
values indicate the degree of hydrophobicity or aromaticity of dissolved
organics (Chin et al., 1994). The removal of UVA254 by biodegradation
and adsorption occurred throughout the column experiments as pre-
sented in Fig. 3. The average UVA254 removal efficiencies of outflows
40
20
0
lol im lol en zil de ne ac le le ne ne in ne ne
no opr no ph ibro mi ffei fen azo azo azi epi myc ido azi
Ate eth ropra mino emf Iopro Ca iclo lfathi thox Atr maz inco Prim eth
im P a G D u e a L m
T r et S fam rb lfa
Ac l Ca Su
Su
Fig. 2. Removal efficiencies of PPCPs by the simulated MAR (n = 37; box plot: average; ⌶:
standard deviation).
from column #1 (travel time 2 days), column #2 (travel time 4 days),
column #3 (travel time 6 days), and column #4 (travel time 8 days)
were 24.5%, 29.8%, 35.1%, and 42.6%, respectively, during the steady pro-
cess period, excluding those during day 1 to day 30.
Based upon the simulated MAR test results over one year, the re-
moval efficiencies of atenolol, propranolol, and trimethoprim were
higher (N80%) than other PPCPs (Fig. 2). Propranolol has a high bioaccu-
mulation potential as indicated by its high lipophilicity (log Kow =
3.48), and the removal rate of propranolol (average 88% removal) in
this study is a good agreement with this. Both the chemical structures
and physicochemical properties of PPCPs significantly influence the de-
gree of biodegradation (Maeng et al., 2010). Trimethoprim has an affin-
ity for sorption to the sediment, and our result (89% removal) is in
agreement with previous study (WateReuse Foundation, 2007). The re-
movals of propranolol and trimethoprim fluctuated very little between
sampling dates from beginning to day ~150, suggesting that the biodeg-
radation and adsorption reached a pseudo-steady state (Fig. 4). During
this period, atenolol, propranolol, and trimethoprim were suitably
removed by passage through the soil columns. The analysis of later
210-day period from days 151 to 360 demonstrated that propranolol
and trimethoprim removal fluctuated slightly between sampling
dates, suggesting that the biodegradation and adsorption decreased.

Table 2
Concentrations of PPCPs in feed water (final effluent of the WRF) to the simulated MAR system.

Compound Concentration (ng/L)

September to November December 2016 to March to May 2017 June to August 2017
2016 (n = 13) February 2017 (n = 12) (n = 6) (n = 6)

Avg. Std. Avg. Std. Avg. Std. Avg. Std.

Acetaminophen 114.17 168.46 78.77 51.21 29.16 36.99 40.55 10.73

Atenolol 16.94 15.68 25.53 17.04 55.92 9.17 22.52 8.66
Atrazine 26.60 23.11 1.85 0.49 0.94 0.46 1.70 0.87
Caffeine 137.95 31.18 492.08 132.20 471.64 287.08 209.55 212.92
Carbamazepine 52.32 32.35 67.16 6.86 87.09 14.43 90.97 7.24
Diclofenac 21.21 7.24 35.95 2.31 28.96 4.47 21.89 4.78
Gemfibrozil – – – – 2.56 0.04 16.29 23.39
Iopromide 13.77 14.83 63.73 90.06 167.45 179.86 59.60 65.37
Lincomycin 32.06 12.73 46.53 9.39 57.22 10.88 47.48 4.82
Primidone 5.50 0.71 6.33 1.53 – – 5.56 1.05
Propranolol 10.54 4.81 17.18 1.74 17.68 2.30 25.72 19.63
Sulfamethazine 3.65 1.20 3.51 2.03 4.41 1.81 4.03 1.00
Sulfamethoxazole 25.16 9.77 35.63 7.03 38.37 11.53 36.77 5.46
Sulfathiazole 18.00 4.24 21.67 3.51 – – 3.35 0.92
Trimethoprim 11.68 4.72 22.27 7.88 34.68 7.02 9.42 6.26
 S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677 675

Table 3 80
Water quality parameters of feed and treated waters by the simulated MAR (average
values of one-year operation).

Atenolol (ng/L)
60

Travel time (days) Water quality parameter

after injection 40
DOC (mg/L) UVA254 SUVA (L/mg·m)

0 (feed water) 5.24 0.094 1.79

2 3.92 0.071 1.81 20
4 3.81 0.066 1.73
6 3.74 0.061 1.63 0
8 3.71 0.054 1.46 80
Feed water

Propranolol (ng/L)
Travel time 2 days
60 Travel time 4 days
Travel time 6 days
As presented in Fig. 2, atenolol was also readily removed (99%) Travel time 8 days
40
during the MAR although it shows a low bioaccumulation potential as
indicated by its low lipophilicity (log Kow = 0.16). The monitoring re-
sults of the WRF showed moderate removal of atenolol (~60% in aver- 20

age) (Fig. 1). Atenolol is not readily biodegradable and is not expected
to significantly adsorb to sludge solids and sediments. However, oxida- 0
80
tion–coagulation can increase the ready biodegradability of atenolol

Trimethoprim (ng/L)
(Wilde et al., 2013). This could explain why the column test could
60
achieve the high removal rate of atenolol; the feed water to the column
was final effluent from the WRF with coagulation and UV processes. As
presented in Fig. 4, the removal efficiency of atenolol by the soil column 40

was high (N99%) at all times.

Atrazine, carbamazepine, lincomycin, primidone, and sulfametha- 20

zine were not readily removed by the simulated MAR system. The aver-
age removal efficiencies of atrazine, carbamazepine, lincomycin, 0
0 60 120 180 240 300 360
primidone, and sulfamethazine were 18.1%, 11.2%, 10.3%, 5.1%, and
1.0% during the steady process period, respectively (Fig. 2). Moreover, Duration (days since injection)
the removal efficiencies of these compounds were consistently low.
The removal rates of atrazine, carbamazepine, lincomycin, primidone, Fig. 4. Evolution of atenolol, propranolol, and trimethoprim remaining in the outflow from
columns #1 (travel time 2 days), #2 (travel time 4 days), #3 (travel time 6 days), and #4
and sulfamethazine by the soil column was below 40% at all times. (travel time 8 days).
(Fig. 5). This is in general agreement with previous studies (Clara et
al., 2004; Drewes et al., 2003; Huntcha et al., 2013; Nakada et al.,
4. Conclusions
2007; WateReuse Foundation, 2007; Yu et al., 2006). Atrazine, carba-
mazepine, primidone, and sulfamethazole were not well removed
The removal of selected PPCPs in reclaimed water was investigated
under either oxic or anoxic conditions (WateReuse Foundation, 2007)
using a laboratory-scale MAR system. The PPCPs included antibiotic, an-
as these compounds could be resistant to biodegradation (Nakada et
tiepileptic, antihypertensive, anti-inflammatory, and antilipidemic
al., 2007; Yu et al., 2006). Due to their persistent characteristics, these
drugs, contrast media, herbicides, and stimulants. First, PPCP removal
compounds (atrazine, carbamazepine, lincomycin, primidone, and sul-
by water reclamation processes was assessed at a WRF in Korea over
famethazine) can be anthropogenic markers and/or tracers, and used
one year, which consisted of screening, primary sedimentation, second-
to determine dilution of recharge water (reclaimed water) with native
ary treatment, coagulation, and UV disinfection. The sampling cam-
groundwater in MAR systems.
paigns at the WRF revealed that carbamazepine and primidone were
recalcitrant (below 25% removal in average). These compounds were

1.0
1.0

0.8
0.8
UVA254 (C/C0)

0.6
0.6
Atrazine
C/C0

Carbamazepine
Lincomycin
0.4 0.4 Sulfamethazine
C1/C0 Primidone
C2/C0
0.2 C3/C0 0.2
C4/C0

0.0 0.0
0 60 120 180 240 300 360 0 60 120 180 240 300 360

Duration (days since injection) Duration (days since injection)

Fig. 3. Evolution of UVA254 remaining in the outflow from columns #1 (C1/C0), #2 (C2/C0), Fig. 5. Evolution of atrazine, carbamazepine, lincomycin, sulfamethazine and primidone
#3 (C3/C0), and #4 (C4/C0). remaining in the outflow (travel time = 8 days) of the soil columns.
676 S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677
not readily removed by coagulation and ultraviolet disinfection pro-
cesses, which were followed by biological processes.
This reclaimed water passed through a laboratory-scale soil column
set-up at 0.5 m/d over one year, simulating MAR system. Overall, re-
moval rates of most compounds increased as traveling time in the soil
columns increased. Both biodegradation and sorption could be major
removal mechanisms for the compounds, considering removals of
both DOC and UVA254. The removal rates of atenolol, propranolol, and
trimethoprim by the simulated MAR were high (N80%), and that of
atenolol exhibited was particularly high (N99%). However, atrazine, car-
bamazepine, lincomycin, primidone, and sulfamethazine were not read-
ily removed by the soil column (removal rates below 20%). Therefore, it
may be more efficient to monitor and manage these persistent com-
pounds at the WRF, rather than establishing effluent limits for all
PPCPs. Also, these persistent compounds can be anthropogenic markers
and can be used to determine dilution of recharge water (reclaimed
water) with native groundwater in MAR systems.
Acknowledgements
This research was supported by the Korea Ministry of Environment
(MOE) as “Geo-Advanced Innovative Action” Program (Project No.
2015000560002) and by the National Research Foundation of Korea
(NRF) grant funded by the Korea government (No. NRF-
2017R1A2B4009908).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2018.05.221.
References
Balmer, M.E., Buser, H.-R., Müller, M.D., Poiger, T., 2005. Occurrence of some organic UV
filters in wastewater, in surface waters, and in fish from Swiss Lakes. Environ. Sci.
Technol. 39 (4), 953–962.
Behera, S.K., Kim, H.W., Oh, J.E., Park, H.S., 2011. Occurrence and removal of antibiotics,
hormones and several other pharmaceuticals in wastewater treatment plants of the
largest industrial city of Korea. Sci. Total Environ. 409, 4351–4360.
Benotti, M.J., Brownawell, B.H., 2007. Distributions of Pharmaceuticals in an Urban Estu-
ary During Both Dry- and Wet-weather Conditions. pp. 5795–5802.
Boxall, A.B.A., Rudd, M.A., Brooks, B.W., Caldwell, D.J., 2012. Pharmaceuticals and personal
care products in the environment: what are the big questions? Environ. Health
Perspect. 120, 1221–1229.
Bu, Q., Wang, B., Huang, J., Deng, S., Yu, G., 2013. Pharmaceuticals and personal care prod-
ucts in the aquatic environment in China: a review. J. Hazard. Mater. 262, 189–211.
Bulloch, D.N., Nelson, E.D., Carr, S.A., Wissman, C.R., Armstrong, J.L., Schlenk, D., Larive, C.
K., 2015. Occurrence of halogenated transformation products of selected pharmaceu-
ticals and personal care products in secondary and tertiary treated wastewaters from
Southern California. Environ. Sci. Technol. 49 (4), 2044–2051.
Carballa, M., Omil, F., Lema, J.M., Llompart, M., Jares, C.G., Rodriguez, I., Gomez, M., Ternes,
T., 2004. Behavior of pharmaceuticals cosmetics and hormones in a sewage treatment
plant. Water Res. 38, 2918–2926.
Carballa, M., Omil, F., Lema, J.M., 2008. Comparison of predicted and measured concentra-
tions of selected pharmaceuticals, fragrances and hormones in Spanish sewage.
Chemistry 72, 1118–1123.
Chin, Y.P., Aiken, G., O'Loughlin, E., 1994. Molecular weight, polydispersity, and spectro-
scopic properties of aquatic humic substances. Environ. Sci. Technol. 28, 1853–1858.
Clara, M., Strenn, B., Kreuzinger, N., 2004. Carbamazepine as a possible anthropogenic
marker in the aquatic environment: investigations on the behavior of carbamazepine
in wastewater treatment and during groundwater infiltration. Water Res. 38 (4),
947–954.
Clara, M., Strenn, B., Gans, O., Martinez, E., Kreuzinger, N., Kroiss, H., 2005. Removal of se-
lected pharmaceuticals, fragrances and endocrine disrupting compounds in a mem-
brane bioreactor and conventional wastewater treatment plants. Water Res. 39
(19), 4797–4807.
Dillon, P., Page, D., Vanderzalm, J., Pavelic, P., Toze, S., Bekele, E., Sidhu, J., Prommer, H.,
Higginson, S., Regel, R., Rinck-Pfeiffer, S., Purdie, M., Wintgens, T., 2008. A critical eval-
uation of combined engineered and aquifer treatment systems in water recycling.
Water Sci. Technol. 57 (5), 753–762.
Drewes, J.E., Heberer, T., Rauch, T., Reddersen, K., 2003. Fate of pharmaceuticals during
ground water recharge. Groundw. Monit. Remediat. 23 (3), 64–72.
Evgenidou, E.N., Konstantinou, I.K., Lambropoulou, D.A., 2015. Occurrence and removal of
transformation products of PPCPs and illicit drugs in wastewater: a review. Sci. Total
Environ. 505, 905–926.
Federle, T.W., Kaiser, S.K., Nuck, B.A., 2002. Fate and effects of triclosan in activated sludge.
Environ. Toxicol. Chem. 21 (7), 1330–1337.
Ferrari, B., Paxeus, N., Giudice, R.L., Pollio, A., Garric, J., 2003. Ecotoxicological impact of
pharmaceuticals found in treated wastewaters: study of carbamazepine, clofibric
acid, and diclofenac. Ecotoxicol. Environ. Saf. 55 (3), 359–370.
Gago-Ferrero, P., Diaz-Curz, M.S., Barcelo, D., 2011. Occurrence of multiclass UV filters in
treated sewage sludge from wastewater treatment plants. Chemistry 84 (8),
1158–1165.
Global Water Research Coalition, 2008. Development of an International Priority List of
Pharmaceuticals Relevant for the Water Cycle.
Huntcha, S., Rodriguez Velosa, D.M., Schroth, M.H., Hollender, J., 2013. Degradation of
polar organic micropolluants during riverbank filtration: complementary results
from spatiotemporal sampling and push-pull tests. Environ. Sci. Technol. 47 (20),
11512–11521.
Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2005. Human pharmaceuticals in wastewater
treatment processes. Crit. Rev. Environ. Sci. Technol. 35 (4), 401–427.
Joss, A., Keller, E., Alder, A.C., Gobel, A., McArdell, C.S., Ternes, T., Siegrist, H., 2005. Removal
of pharmaceuticals and fragrances in biological wastewater treatment. Water Res. 39,
3139–3152.
Kasprzyk-Hordern, B., Dinsdale, R.M., Guwy, A.J., 2009. The removal of pharmaceuticals,
personal care products, endocrine disruptors and illicit drugs during wastewater
treatment and its impact on the quality of receiving waters. Water Res. 43 (2),
363–380.
Kolpin, D.W., Furlong, E.T., Meyer, M.T., Thurman, E.M., Zaugg, S.D., Barber, L.B., Buxton, H.
T., 2002. Pharmaceuticals, hormones, and other organic wastewater contaminants in
U.S. streams, 1999–2000: a national reconnaissance. Environ. Sci. Technol. 36,
1201–1211.
Kosma, C.I., Lambropoulou, D.A., Albanis, T.A., 2010. Occurrence of iodinated X-ray con-
trast media and their biotransformation products in the urban water cycle. Environ.
Sci. Technol. 45 (20), 8723–8732.
Kosma, C.I., Lambropoulou, D.A., Albanis, T.A., 2014. Investigation of PPCPs in wastewater
treatment plants in Greece: occurrence, removal and environmental risk assessment.
Sci. Total Environ. 466-467, 421–438.
Levantesi, C., La-Mantia, R., Masciopinto, C., Böckelmann, U., Ayuso-Gabella, M.N., Salgot,
M., Tandoi, V., Van-Houtte, E., Wintgens, T., Grohmann, E., 2010. Quantification of
pathogenic microorganisms and microbial indicators in three wastewater reclama-
tion and managed aquifer recharge facilities in Europe. Sci. Total Environ. 408 (21),
4923–4930.
Li, X., Zheng, W., Kelly, W.R., 2013. Occurrence and removal of pharmaceutical and hor-
mone contaminants in rural wastewater treatment lagoons. Sci. Total Environ. 445–
446, 21–28.
Lin, A.Y.C., Yu, T.H., Lateef, S.K., 2009. Removal of pharmaceuticals in secondary
wastewater treatment processes in Taiwan. J. Hazard. Mater. 167 (1–3),
1163–1169.
Lin, T., Yu, S., Chen, W., 2016. Occurrence, removal and risk assessment of pharmaceuti-
cals and personal care products (PPCPs) in an advanced drinking water treatment
plant (ADWTP) around Taihu Lake in China. Chemistry 152, 1–9.
Liu, J.L., Wong, M.H., 2013. Pharmaceuticals and personal care products (PPCPs): a review
on environmental contamination in China. Environ. Int. 59, 208–224.
McClellan, K., Halden, R.U., 2010. Pharmaceuticals and personal care products in archived
U.S. biosolids from the 2001 EPA national sewage sludge survey. Water Res. 44 (2),
658–668.
Maeng, S.K., Ameda, E., Sharma, S.K., Grützmacher, G., Amy, G., 2010. Organic
micropollutant removal from wastewater effluent-impacted drinking water sources
during bank filtration and artificial recharge. Water Res. 44 (14), 4003–4014.
Miao, X.S., Yang, J.J., Metcalfe, C.D., 2005. Carbamazepine and its metabolites in wastewa-
ter and in biosolids in a municipal wastewater treatment plant. Environ. Sci. Technol.
39, 7469–7475.
Miége, C., Choubert, J.M., Ribeiro, L., Eusébe, M., Coquery, M., 2009. Fate of pharmaceuti-
cals and personal care products in wastewater treatment plants conception of a data-
base and first results. Environ. Pollut. 157 (5), 1721–1726.
Nakada, N., Tanishima, T., Shinohara, H., Kiri, K., Takada, H., 2006. Pharmaceutical
chemicals and endocrine disrupters in municipal wastewater in Tokyo and their re-
moval during activated sludge treatment. Water Res. 41 (19), 3297–3303.
Nakada, N., Shinohara, H., Murata, A., Kiri, K., Managaki, S., Sato, N., Takada, H., 2007. Re-
moval of selected pharmaceuticals and personal care products (PPCPs) and endo-
crine-disrupting chemicals (EDCs) during sand filtration and ozonation at a
municipal sewage treatment plant. Water Res. 41 (19), 4373–4382.
Okuda, T., Kobayashi, Y., Nagao, R., Yamashita, N., Tanaka, H., Tanaka, S., Fujii, S., Konishi,
C., Houwa, I., 2008. Removal efficiency of 66 pharmaceuticals during wastewater
treatment process in Japan. Water Sci. Technol. 57, 65–71.
Page, D., Dillon, P., Toze, S., Bixio, D., Genthe, B., Cisneros, B.E.J., Wintgens, T., 2010a. Val-
uing the subsurface pathogen treatment barrier in water recycling via aquifers for
drinking supplies. Water Res. 44 (6), 1841–1852.
Page, D., Dillon, P., Toze, S., Sidhu, J.P.S., 2010b. Characterising aquifer treatment for path-
ogens in managed aquifer recharge. Water Sci. Technol. 62 (9), 2009–2015.
Papageorgiou, M., Kosma, C., Lambropoulou, D., 2016. Seasonal occurrence, removal, mass
loading and environmental risk assessment of 55 pharmaceuticals and personal care
products in a municipal wastewater treatment plant in Central Greece. Sci. Total En-
viron. 543 (Pt A), 547–569.
Pedrouzo, M., Reverté, S., Borrull, F., Pocurull, E., Marcé, R.M., 2007. Pharmaceutical deter-
mination in surface and wastewaters using high-performance liquid chromatogra-
phy-(electrospray)-mass spectrometry. J. Sep. Sci. 30 (3), 297–303.
Racz, A.J., Fisher, A.T., Schmidt, C.M., Lockwood, B.S., Huertos, M.L., 2012. Spatial and tem-
poral infiltration dynamics during managed aquifer recharge. Groundwater. 50 (4),
562–570.
 S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677
Santos, J.L., Aparicio, I., Alonso, E., 2007. Occurrence and risk assessment of pharmaceuti-
cally active compounds in wastewater treatment plants. A case study: Seville city
(Spain). Environ. Int. 33 (4), 596–601.
Summers, R.M., Mohanty, S.K., Gopishetty, S., Subramanian, M., 2015. Genetic characteri-
zation of caffeine degradation by bacteria and its potential applications. Microb.
Biotechnol. 8, 369–378.
Thomas, P.M., Foster, G.D., 2005. Tracking acidic pharmaceuticals, caffeine, and triclosan
through the wastewater treatment process. Environ. Toxicol. Chem. 24, 25–30.
Tran, N.H., Gin, K.Y.H., 2017. Occurrence and removal of pharmaceuticals, hormones, per-
sonal care products, and endocrine disrupters in a full-scale water reclamation plant.
Sci. Total Environ. 599–600, 1503–1516.
Tran, N.H., Urase, T., Ngo, H.H., Hu, J., Ong, S.L., 2013. Insight into metabolic and
cometabolic activities of autotrophic and heterotrophic microorganisms in the bio-
degradation of emerging trace organic contaminants. Bioresour. Technol. 146,
721–731.
Tran, N.H., Urase, T., Ta, T.T., 2014a. A preliminary study on the occurrence of pharmaceu-
tically active compounds in hospital wastewater and surface water in Hanoi,
Vietman. Clean: Soil, Air, Water 42 (3), 267–275.
Tran, N.H., Li, J., Hu, J., Ong, S.L., 2014b. Occurrence and suitability of pharmaceuticals and
personal care products as molecular markers for raw wastewater contamination in
surface water and groundwater. Environ. Sci. Pollut. Res. 21, 4727–4740.
Tran, N.H., Chen, H., Do, T.V., Reinhard, M., Ngo, H.H., He, Y., Gin, K.Y.H., 2016. Simulta-
neous analysis of multiple classes of antimicrobials in environmental water samples
using SPE coupled with UHPLC-ESI-MS/MS and isotope dilution. Talanta 163–173.
Tran, N.H., Reinhard, M., Gin, K.Y.H., 2018. Occurrence and fate of emerging contaminants
in municipal wastewater plants from different geographical regions-a review. Water
Res. 133, 182–207.
Valsero, M.H., Contreras, C.R., Dominguez, G., Becares, E., Bayona, J.M., 2016. Behavior of
pharmaceuticals and personal care products in constructed wetland compartment:
influent, effluent, pore water, substrate and plant root. Chemistry 145, 508–517.
677
Vieno, N.M., Tuhkanen, T., Kronberg, L., 2005. Seasonal variation in the occurrence of
pharmaceuticals in effluents from a sewage treatment plant and in the recipient
water. Environ. Sci. Technol. 39, 8220–8226.
Vulliet, E., Cren-Olive, C., Grenier-Loustalot, M.F., 2011. Occurrence of pharmaceuticals
and hormones in drinking water treated from surface waters. Environ. Chem. Lett.
9 (1), 103–114.
Vymazal, J., Bˇrezinová, T.D., Koˇzeluh, M., Kule, L., 2017. Occurrence and removal of phar-
maceuticals in four full-scale constructed wetlands in the Czech Republic – the first
year of monitoring. Ecol. Eng. 98, 354–364.
Wang, D., Sui, Q., Lu, S.G., Zhao, W.T., Qiu, Z.F., Miao, Z.W., Yu, G., 2014. Occurrence and
removal of six pharmaceuticals and personal care products in a wastewater treat-
ment plant employing anaerobic/anoxic/aerobic and UV processes in Shanghai,
China. Environ. Sci. Pollut. Res. 21 (6), 4276–7285.
WateReuse Foundation, 2007. Reclaimed Water Aquifer Storage and Recovery Potential
Changes in Water Quality. Water Reuse Foundation.
Wilde, M.L., Mahmoud, W.M.M., Kümmerer, K., Martins, A.F., 2013. Oxidation–coagula-
tion of β-blockers by K2FeVIO4 in hospital wastewater: assessment of degradation
products and biodegradability. Sci. Total Environ. 452–453, 137–147.
Yang, X., Flowers, R.C., Weinberg, H.S., Singer, P.C., 2011. Occurrence and removal of phar-
maceuticals and personal care products (PPCPs) in an advanced wastewater reclama-
tion plant. Water Res. 45, 5218–5228.
Yu, J.T., Bouwer, E.J., Coelhan, M., 2006. Occurrence and biodegradability studies of se-
lected pharmaceuticals and personal care products in sewage effluent. Agric. Water
Manag. 86, 72–80.
Yu, C.L., Summers, R.M., Li, Y., Mohanty, S.K., Subramanian, M., Pope, R.M., 2015. Rapid
identification and quantitative validation of a caffeine-degrading pathway in
Pseudo-monas sp. J. Proteome Res. 14, 95–146.