Anda di halaman 1dari 7

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

Contents lists available at ScienceDirect

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 and/or water reclamation facilities (WRFs) (Tran et al., 2014a, 2018).
PPCPs have been detected in waste and reclaimed waters at ng/L to
Approximately 12,000 pharmaceuticals and personal care products μg/L levels (Pedrouzo et al., 2007; Tran and Gin, 2017; Yang et al., 2011).
(PPCPs) have been distributed for human use worldwide. PPCPs include The presence of PPCPs in reclaimed water has received great atten-
a variety of chemical substances, including human and veterinary drugs, tion owing to their potentially adverse influences on human health
disinfectants or fragrances in personal care products such as lotions, lip- and ecosystems (Tran et al., 2014a; Tran and Gin, 2017; Yang et al.,
sticks, hair sprays/dyes, body cleaning products, and sun-screens 2011). PPCPs are potentially hazardous to the aquatic ecosystem, and
(Balmer et al., 2005; Gago-Ferrero et al., 2011), and household can cause endocrine disruption and other severe side effects resulting
chemicals (Boxall et al., 2012; Bu et al., 2013; Lin et al., 2016). After from the specific biological effects they were developed to induce
their use in hospitals, households, and industries, residual PPCPs can (Clara et al., 2005; Nakada et al., 2007; Tran and Gin, 2017; Tran et al.,
enter the aquatic environment via wastewater treatment systems 2014b; Vulliet et al., 2011). Wastewater can be reclaimed and reused
through various engineering techniques and natural or passive treat-
⁎ Corresponding author. ment processes. Most WRFs employ multiple barrier approaches, in-
E-mail address: wtlee@kumoh.ac.kr (W. Lee). 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 2.3. Target PPCPs
PPCPs by WRFs is reportedly inefficient (Nakada et al., 2006; Santos et
al., 2007; Tran et al., 2018) and depends on compound-specific proper- Among the diverse array of PPCPs, we selected 22 compounds that
ties as well as factors related to WRFs, such as the types of treatment are common in aquatic systems, and the physical and chemical proper-
processes or age of sludge (Tran et al., 2013, 2018). ties of these target compounds are presented in the supplementary ma-
Water reuse can be facilitated by purposefully recharging reclaimed terial (Table A.1). The compounds were selected to represent different
water into aquifers for natural treatment prior to recovery and reuse. antibiotics, such as chlortetracycline, lincomycin, oxytetracycline,
This artificial recharge is called “managed aquifer recharge (MAR)”, sulfachloropyridazine, sulfamethazine, sulfamethoxazole, sulfathiazole,
and is a natural water treatment process that induces the flow of tetracycline, and trimethoprim; antiepileptics, such as carbamazepine
water the soil. MAR provides a natural buffer, provides a residence and primidone; antihypertensive drugs, such as atenolol, metoprolol,
time that can facilitate the removal of biodegradable organic matters and propranolol; anti-inflammatory drugs, such as acetaminophen,
and pathogens, improves the quality of the treated wastewater, includ- diclofenac, ibuprofen, and naproxen; antilipidemics, such as gemfibro-
ing PPCPs, and reduces the cost of seasonal peak demands (Dillon et al., zil; contrast media, such as iopromide; herbicides, such as atrazine;
2008; Levantesi et al., 2010; Page et al., 2010a, 2010b). and stimulants, such as caffeine. These compounds were listed among
MAR has not yet been applied for water reuse in Korea, although the 30 most frequently detected organic wastewater contaminants re-
this technology has been studied and applied in other countries, such ported by the United States Geological Survey (Kolpin et al., 2002).
as the United States and Australia. PPCPs are an ideal group of com- Atenolol, carbamazepine, gemfibrozil, ibuprofen, and sulfamethoxazole
pounds for assessing the removal mechanisms of emerging contami- were among the top ten high-priority pharmaceuticals identified in a
nants by MAR owing to their varied chemical properties. The European PPCP assessment (Global Water Research Coalition, 2008).
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
2.4. Determination of water quality parameters and target PPCPs
observed in other countries. Though previous studies have elucidated
the removal characteristics of several PPCPs in MAR, few have system-
All samples were filtered through membrane filters (0.4 μm,
atically evaluated the relationship between the removals of PPCPs and
Whatman, USA) to remove any particulate materials, and stored at 4 °C
operational conditions with respect to the PPCPs' properties. This
in the dark. All water samples were extracted within one week for fur-
study addresses these questions by monitoring the removals of 22
ther analysis if necessary. DOC was measured by a TOC analyzer (TOC-
PPCPs in a full-scale water reclamation facility in Korea and a labora-
VCPH, Shimadzu, Japan) using the non-purgeable organic carbon
tory-scale MAR.
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
2. Materials and methods
(ThermoFisher, USA).
A highly sensitive analytical method was developed and validated
2.1. Laboratory-scale soil column set-up and operation
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-
MAR was simulated using a laboratory-scale soil column set-up,
tion of a sample into the chromatograph (Tran et al., 2016; Tran and Gin,
which consisted of four 1000-mm acrylic glass columns in series with
2017; Vymazal et al., 2017). A 1290 High-Performance Liquid Chro-
an inner diameter of 150 mm. The columns were filled with native allu-
matograph tandem with a 6490 Triple Quad Mass Spectrophotometer
vial material (diameter b 2 mm). The porosity was 0.4, and the perme-
(LC/MS-MS) (Agilent 1200 series rapid-resolution liquid chromato-
ability coefficient was 0.013 cm/s. The system was positioned in a
graph (Waldbronn, Germany), triple quadrupole 6490 Mass) was used
temperature-controlled room at 20 °C, and feed water was injected
in the electrospray ionization (ESI; positive/negative) mode. ESI separa-
into the soil column system by a peristaltic pump at 0.5 m/day (volu-
tion was conducted on an Eclipse C18 analytical column (100 × 2.1 mm,
metric flow rate of 6.13 mL/min) upward flow, considering the typical
3.5 μm particle size, Agilent). The mobile phase for material separation
residence time of water in MAR systems (Racz et al., 2012). To eliminate
contained de-ionized water (solvent a) and acetonitrile/methanol
the effect of varying hydraulic recharge conditions, the experiment ran
(4:1, V/V) (solvent b). Both solvents A and B were added with 0.1%
at a fixed flow rate over the whole experimental period (from Septem-
formic acid, and the fractions of solvents A and B were changed over
ber 2016 through August 2017). The columns were initially saturated
time to efficiently separate the target material. Analytical conditions
with ambient groundwater and subsequently rinsed with the final efflu-
for the LC/MS-MS are summarized in the supplementary material
ent. The initial increase in electrical conductivity was used as a tracer for
(Table A.2). Limit of quantification (LOQ) for PPCPs was 1 ng/L, except
determining the hydromechanical properties of the columns. The soil
naproxen (20 ng/L). All standards were of high purity grade (N99%)
columns were kept saturated at all times.
and purchased from Sigma-Aldrich (USA).

2.2. WRF and feed water to MAR 3. Results and discussion

The simulated MAR system was fed with the final effluent of a WRF 3.1. Removal of target PPCPs by the WRF
in an industrial complex in Gumi, Korea, which had a capacity of
50,000 m3/d and received wastewater from the surrounding industrial The target compounds were selected to represent different PPCPs,
complex. The WRF consisted of primary treatment followed by a biolog- such as antihypertensive drugs (such as atenolol), stimulants (such as
ical process, coagulation/filtration, and UV disinfection. Prior to MAR caffeine), antilipidemics (such as gemfibrozil), antibiotics (such as sulfa-
test, concentrations of target PPCPs in the influent, biological process, methoxazole), and antiepileptics (such as carbamazepine and
coagulation/filtration process, and effluent were monitored for the 12- primidone). Seven of the twenty-two target compounds were detected
month period (sampled every other month) from January to December at every sampling campaign of the WRF for the 12-month period from
2015. The final effluent of the facility was collected and used as the feed January to December 2015, and they were listed in Table 1. Table 1 sum-
water for the laboratory-scale MAR from September 2016 through Au- marizes the average, minimum, and maximum concentrations of the
gust 2017. The feed water was filtered through glass fiber filters with target PPCPs in the influent and biological process, coagulation/filtra-
a pore size of 0.7 μm after collection. 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 sludge process through biodegradation. The presence of electron donat-
(Table 1). These compounds are steroid and analgesic, and they are ing groups (\\CH3) in caffeine molecules tends to increase the electron
among the most widely used PPCPs in Korea. The caffeine concentra- density in the regions where these groups are attached. This causes caf-
tions of the influents varied from approximately 873 to 2104 ng/L, feine to experience a large imbalance in its electrostatic distribution.
with an average concentration of 1336 ng/L. Caffeine is a stimulant Therefore, it is assumed that the biodegradation of caffeine tends to be
that is also commonly used in beverages and foods. Similar levels of initiated at the electron donating groups (\\CH3). Previous studies
these compounds have been observed in the raw wastewater of other demonstrated that N-demethylation is one of the main pathways for
municipal wastewater treatment plants in other countries (Benotti the biodegradation of caffeine (Summers et al., 2015; Yu et al., 2015).
and Brownawell, 2007; Tran et al., 2018; Vieno et al., 2005). For exam- Additionally, caffeine is readily biodegradable (Okuda et al., 2008;
ple, caffeine in abundant in the influents of WRFs in other countries, at Thomas and Foster, 2005; Valsero et al., 2016).
concentrations ranging from below the method quantification limit to The removal rate of ibuprofen (analgesic drug) was also high (~80%)
120,000 ng/L (Tran et al., 2018). Yang et al. (2011) reported caffeine in previous studies (Ferrari et al., 2003; Nakada et al., 2007; Yu et al.,
concentrations ranging from 54,000–120,000 ng/L in the USA; Behera 2006). The excellent elimination rates of ibuprofen by biological waste-
and Kim (2011) reported caffeine concentrations ranging from 1608 water treatment processes could also be caused by the higher strength
to 3217 ng/L in wastewater in Korea; Tran et al. (2014b) reported con- of electron donation groups, such as alkyl groups (\\CH2\\CH[CH3]2),
centrations ranging from below the detection limit to 16,249 ng/L in an than the electron withdrawing groups (\\CH[CH3]\\COOH) in these
urban catchment area in Singapore; and Li et al. (2013) measured caf- molecules. Similar to caffeine, the biotransformation of ibuprofen
feine concentrations of 51,300–57,700 ng/L in a wastewater treatment often takes place at the electron donating group (\\CH2\\CH[CH3]2)
plant in Illinois, USA. on the aromatic ring via the hydroxylation or demethylation pathways
In this study, the ibuprofen concentrations of the influents varied (Tran and Gin, 2017).
from approximately 641 to 1768 ng/L, with an average concentration The carbamazepine and primidone removal levels achieved by the
of 1077 ng/L. This pharmaceutical is widely used to relieve pain or sup- WRF were below 20% in average. Several PPCPs with low removal effi-
press inflammation, and often detected in the influents of WRFs at con- ciencies, such as carbamazepine and primidone, are hardly biodegraded
centrations reaching several hundreds of micrograms per liter (Miége et or removed by treatment processes, regardless of the type of system
al., 2009). Similarly, the concentrations of ibuprofen in the influents of used (Behera and Kim, 2011; Clara et al., 2004; Joss et al., 2005; Miao
WRFs in previous studies varied from below the method quantification et al., 2005; Wang et al., 2014). The ineffective removal of PPCPs creates
limit to a few micrograms per liter (Kasprzyk-Hordern et al., 2009; by-products or metabolites and the causes the target PPCPs to conjugate
Kosma et al., 2010, 2014; Miége et al., 2009; Papageorgiou et al., 2016; (Miao et al., 2005). The absence of electron donating group in carbamaz-
Tran et al., 2018). Ferrari et al. (2003) reported an ibuprofen concentra- epine could be the reason resulting in poor removal in biological waste-
tion range of 3900–15,000 ng/L in the USA; Santos et al. (2007) reported water treatment processes (Tran and Gin, 2017). Also, the results for
an average concentration of 93,925 ng/L in Seville, Spain; and Carballa et primidone indicate that it is resistant to activated sludge, coagulation,
al. (2004, 2008) reported an ibuprofen concentration range of 3697–
19,000 ng/L in Galicia, Spain. 100
PPCP removal by WRFs is a complicated process and depends on the January
chemical and biological properties of the pollutants, such as their hydro- March
philicity, solubility (Evgenidou et al., 2015), volatility, and biodegrad- 80
May
July
ability (Jones et al., 2005), and the adsorption capability of the 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,
40
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
20
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
0
MAR system. PPCP levels of the samples varied over the duration of 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
the experiment. However, no statistical trends was observed between 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
PPCP levels and the four seasons. Overall, caffeine was found at the Ac l Ca Su
Su
highest level of 328 ng/L in average, followed by iopromide (76 ng/L)
and carbamazepine (74 ng/L). General water quality parameters such Fig. 2. Removal efficiencies of PPCPs by the simulated MAR (n = 37; box plot: average; ⌶:
as DOC, UVA254, EC, and pH were also monitored and no substantial dif- standard deviation).
ference was observed between water quality levels and any of the four
seasons. from column #1 (travel time 2 days), column #2 (travel time 4 days),
Removal efficiencies of PPCPs by the simulated MAR was assessed by column #3 (travel time 6 days), and column #4 (travel time 8 days)
measuring concentrations of PPCPs in outflows from columns #1 (travel were 24.5%, 29.8%, 35.1%, and 42.6%, respectively, during the steady pro-
time of 2 days), #2 (travel time of 4 days), #3 (travel time of 6 days), cess period, excluding those during day 1 to day 30.
and #4 (travel time of 8 days). The results of PPCP removals from the Based upon the simulated MAR test results over one year, the re-
soil column experiments in travel time 2 and 8 days were presented moval efficiencies of atenolol, propranolol, and trimethoprim were
in Fig. 2. Overall, removal rates of most compounds were higher after higher (N80%) than other PPCPs (Fig. 2). Propranolol has a high bioaccu-
8 days of traveling in the soil columns than 2 days of traveling. Both bio- mulation potential as indicated by its high lipophilicity (log Kow =
degradation and sorption could be major removal mechanisms for the 3.48), and the removal rate of propranolol (average 88% removal) in
compounds, but we could not differentiate each mechanism in this this study is a good agreement with this. Both the chemical structures
study because we did not inject biocide to the system. DOC and its hy- and physicochemical properties of PPCPs significantly influence the de-
drophobic portions, represented by UVA254, were removed during the gree of biodegradation (Maeng et al., 2010). Trimethoprim has an affin-
soil column experiment, indicating both biodegradation and sorption ity for sorption to the sediment, and our result (89% removal) is in
occurred. As the travel time increased in the MAR system, both DOC agreement with previous study (WateReuse Foundation, 2007). The re-
and UVA254 decreased (Table 3). Removal of UVA254 was higher than movals of propranolol and trimethoprim fluctuated very little between
that of DOC, which resulted in lowering specific ultraviolet absorbance sampling dates from beginning to day ~150, suggesting that the biodeg-
(SUVA) values. SUVA is a calculated parameter by dividing a sample's radation and adsorption reached a pseudo-steady state (Fig. 4). During
UVA254 by the DOC concentration, and then multiplying by 100. SUVA this period, atenolol, propranolol, and trimethoprim were suitably
values indicate the degree of hydrophobicity or aromaticity of dissolved removed by passage through the soil columns. The analysis of later
organics (Chin et al., 1994). The removal of UVA254 by biodegradation 210-day period from days 151 to 360 demonstrated that propranolol
and adsorption occurred throughout the column experiments as pre- and trimethoprim removal fluctuated slightly between sampling
sented in Fig. 3. The average UVA254 removal efficiencies of outflows 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- 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.
cesses, which were followed by biological processes. Ferrari, B., Paxeus, N., Giudice, R.L., Pollio, A., Garric, J., 2003. Ecotoxicological impact of
This reclaimed water passed through a laboratory-scale soil column pharmaceuticals found in treated wastewaters: study of carbamazepine, clofibric
set-up at 0.5 m/d over one year, simulating MAR system. Overall, re- 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
moval rates of most compounds increased as traveling time in the soil treated sewage sludge from wastewater treatment plants. Chemistry 84 (8),
columns increased. Both biodegradation and sorption could be major 1158–1165.
removal mechanisms for the compounds, considering removals of Global Water Research Coalition, 2008. Development of an International Priority List of
Pharmaceuticals Relevant for the Water Cycle.
both DOC and UVA254. The removal rates of atenolol, propranolol, and Huntcha, S., Rodriguez Velosa, D.M., Schroth, M.H., Hollender, J., 2013. Degradation of
trimethoprim by the simulated MAR were high (N80%), and that of polar organic micropolluants during riverbank filtration: complementary results
atenolol exhibited was particularly high (N99%). However, atrazine, car- from spatiotemporal sampling and push-pull tests. Environ. Sci. Technol. 47 (20),
11512–11521.
bamazepine, lincomycin, primidone, and sulfamethazine were not read-
Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2005. Human pharmaceuticals in wastewater
ily removed by the soil column (removal rates below 20%). Therefore, it treatment processes. Crit. Rev. Environ. Sci. Technol. 35 (4), 401–427.
may be more efficient to monitor and manage these persistent com- Joss, A., Keller, E., Alder, A.C., Gobel, A., McArdell, C.S., Ternes, T., Siegrist, H., 2005. Removal
pounds at the WRF, rather than establishing effluent limits for all of pharmaceuticals and fragrances in biological wastewater treatment. Water Res. 39,
3139–3152.
PPCPs. Also, these persistent compounds can be anthropogenic markers Kasprzyk-Hordern, B., Dinsdale, R.M., Guwy, A.J., 2009. The removal of pharmaceuticals,
and can be used to determine dilution of recharge water (reclaimed personal care products, endocrine disruptors and illicit drugs during wastewater
water) with native groundwater in MAR systems. 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
Acknowledgements
U.S. streams, 1999–2000: a national reconnaissance. Environ. Sci. Technol. 36,
1201–1211.
This research was supported by the Korea Ministry of Environment Kosma, C.I., Lambropoulou, D.A., Albanis, T.A., 2010. Occurrence of iodinated X-ray con-
(MOE) as “Geo-Advanced Innovative Action” Program (Project No. trast media and their biotransformation products in the urban water cycle. Environ.
Sci. Technol. 45 (20), 8723–8732.
2015000560002) and by the National Research Foundation of Korea Kosma, C.I., Lambropoulou, D.A., Albanis, T.A., 2014. Investigation of PPCPs in wastewater
(NRF) grant funded by the Korea government (No. NRF- treatment plants in Greece: occurrence, removal and environmental risk assessment.
2017R1A2B4009908). 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
Appendix A. Supplementary data pathogenic microorganisms and microbial indicators in three wastewater reclama-
tion and managed aquifer recharge facilities in Europe. Sci. Total Environ. 408 (21),
4923–4930.
Supplementary data to this article can be found online at https://doi. Li, X., Zheng, W., Kelly, W.R., 2013. Occurrence and removal of pharmaceutical and hor-
org/10.1016/j.scitotenv.2018.05.221. 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
References wastewater treatment processes in Taiwan. J. Hazard. Mater. 167 (1–3),
1163–1169.
Balmer, M.E., Buser, H.-R., Müller, M.D., Poiger, T., 2005. Occurrence of some organic UV Lin, T., Yu, S., Chen, W., 2016. Occurrence, removal and risk assessment of pharmaceuti-
filters in wastewater, in surface waters, and in fish from Swiss Lakes. Environ. Sci. cals and personal care products (PPCPs) in an advanced drinking water treatment
Technol. 39 (4), 953–962. plant (ADWTP) around Taihu Lake in China. Chemistry 152, 1–9.
Behera, S.K., Kim, H.W., Oh, J.E., Park, H.S., 2011. Occurrence and removal of antibiotics, Liu, J.L., Wong, M.H., 2013. Pharmaceuticals and personal care products (PPCPs): a review
hormones and several other pharmaceuticals in wastewater treatment plants of the on environmental contamination in China. Environ. Int. 59, 208–224.
largest industrial city of Korea. Sci. Total Environ. 409, 4351–4360. McClellan, K., Halden, R.U., 2010. Pharmaceuticals and personal care products in archived
Benotti, M.J., Brownawell, B.H., 2007. Distributions of Pharmaceuticals in an Urban Estu- U.S. biosolids from the 2001 EPA national sewage sludge survey. Water Res. 44 (2),
ary During Both Dry- and Wet-weather Conditions. pp. 5795–5802. 658–668.
Boxall, A.B.A., Rudd, M.A., Brooks, B.W., Caldwell, D.J., 2012. Pharmaceuticals and personal Maeng, S.K., Ameda, E., Sharma, S.K., Grützmacher, G., Amy, G., 2010. Organic
care products in the environment: what are the big questions? Environ. Health micropollutant removal from wastewater effluent-impacted drinking water sources
Perspect. 120, 1221–1229. during bank filtration and artificial recharge. Water Res. 44 (14), 4003–4014.
Bu, Q., Wang, B., Huang, J., Deng, S., Yu, G., 2013. Pharmaceuticals and personal care prod- Miao, X.S., Yang, J.J., Metcalfe, C.D., 2005. Carbamazepine and its metabolites in wastewa-
ucts in the aquatic environment in China: a review. J. Hazard. Mater. 262, 189–211. ter and in biosolids in a municipal wastewater treatment plant. Environ. Sci. Technol.
Bulloch, D.N., Nelson, E.D., Carr, S.A., Wissman, C.R., Armstrong, J.L., Schlenk, D., Larive, C. 39, 7469–7475.
K., 2015. Occurrence of halogenated transformation products of selected pharmaceu- Miége, C., Choubert, J.M., Ribeiro, L., Eusébe, M., Coquery, M., 2009. Fate of pharmaceuti-
ticals and personal care products in secondary and tertiary treated wastewaters from cals and personal care products in wastewater treatment plants conception of a data-
Southern California. Environ. Sci. Technol. 49 (4), 2044–2051. base and first results. Environ. Pollut. 157 (5), 1721–1726.
Carballa, M., Omil, F., Lema, J.M., Llompart, M., Jares, C.G., Rodriguez, I., Gomez, M., Ternes, Nakada, N., Tanishima, T., Shinohara, H., Kiri, K., Takada, H., 2006. Pharmaceutical
T., 2004. Behavior of pharmaceuticals cosmetics and hormones in a sewage treatment chemicals and endocrine disrupters in municipal wastewater in Tokyo and their re-
plant. Water Res. 38, 2918–2926. moval during activated sludge treatment. Water Res. 41 (19), 3297–3303.
Carballa, M., Omil, F., Lema, J.M., 2008. Comparison of predicted and measured concentra- Nakada, N., Shinohara, H., Murata, A., Kiri, K., Managaki, S., Sato, N., Takada, H., 2007. Re-
tions of selected pharmaceuticals, fragrances and hormones in Spanish sewage. moval of selected pharmaceuticals and personal care products (PPCPs) and endo-
Chemistry 72, 1118–1123. crine-disrupting chemicals (EDCs) during sand filtration and ozonation at a
Chin, Y.P., Aiken, G., O'Loughlin, E., 1994. Molecular weight, polydispersity, and spectro- municipal sewage treatment plant. Water Res. 41 (19), 4373–4382.
scopic properties of aquatic humic substances. Environ. Sci. Technol. 28, 1853–1858. Okuda, T., Kobayashi, Y., Nagao, R., Yamashita, N., Tanaka, H., Tanaka, S., Fujii, S., Konishi,
Clara, M., Strenn, B., Kreuzinger, N., 2004. Carbamazepine as a possible anthropogenic C., Houwa, I., 2008. Removal efficiency of 66 pharmaceuticals during wastewater
marker in the aquatic environment: investigations on the behavior of carbamazepine treatment process in Japan. Water Sci. Technol. 57, 65–71.
in wastewater treatment and during groundwater infiltration. Water Res. 38 (4), Page, D., Dillon, P., Toze, S., Bixio, D., Genthe, B., Cisneros, B.E.J., Wintgens, T., 2010a. Val-
947–954. uing the subsurface pathogen treatment barrier in water recycling via aquifers for
Clara, M., Strenn, B., Gans, O., Martinez, E., Kreuzinger, N., Kroiss, H., 2005. Removal of se- drinking supplies. Water Res. 44 (6), 1841–1852.
lected pharmaceuticals, fragrances and endocrine disrupting compounds in a mem- Page, D., Dillon, P., Toze, S., Sidhu, J.P.S., 2010b. Characterising aquifer treatment for path-
brane bioreactor and conventional wastewater treatment plants. Water Res. 39 ogens in managed aquifer recharge. Water Sci. Technol. 62 (9), 2009–2015.
(19), 4797–4807. Papageorgiou, M., Kosma, C., Lambropoulou, D., 2016. Seasonal occurrence, removal, mass
Dillon, P., Page, D., Vanderzalm, J., Pavelic, P., Toze, S., Bekele, E., Sidhu, J., Prommer, H., loading and environmental risk assessment of 55 pharmaceuticals and personal care
Higginson, S., Regel, R., Rinck-Pfeiffer, S., Purdie, M., Wintgens, T., 2008. A critical eval- products in a municipal wastewater treatment plant in Central Greece. Sci. Total En-
uation of combined engineered and aquifer treatment systems in water recycling. viron. 543 (Pt A), 547–569.
Water Sci. Technol. 57 (5), 753–762. Pedrouzo, M., Reverté, S., Borrull, F., Pocurull, E., Marcé, R.M., 2007. Pharmaceutical deter-
Drewes, J.E., Heberer, T., Rauch, T., Reddersen, K., 2003. Fate of pharmaceuticals during mination in surface and wastewaters using high-performance liquid chromatogra-
ground water recharge. Groundw. Monit. Remediat. 23 (3), 64–72. phy-(electrospray)-mass spectrometry. J. Sep. Sci. 30 (3), 297–303.
Evgenidou, E.N., Konstantinou, I.K., Lambropoulou, D.A., 2015. Occurrence and removal of Racz, A.J., Fisher, A.T., Schmidt, C.M., Lockwood, B.S., Huertos, M.L., 2012. Spatial and tem-
transformation products of PPCPs and illicit drugs in wastewater: a review. Sci. Total poral infiltration dynamics during managed aquifer recharge. Groundwater. 50 (4),
Environ. 505, 905–926. 562–570.
S. Park, W. Lee / Science of the Total Environment 640–641 (2018) 671–677 677

Santos, J.L., Aparicio, I., Alonso, E., 2007. Occurrence and risk assessment of pharmaceuti- Vieno, N.M., Tuhkanen, T., Kronberg, L., 2005. Seasonal variation in the occurrence of
cally active compounds in wastewater treatment plants. A case study: Seville city pharmaceuticals in effluents from a sewage treatment plant and in the recipient
(Spain). Environ. Int. 33 (4), 596–601. water. Environ. Sci. Technol. 39, 8220–8226.
Summers, R.M., Mohanty, S.K., Gopishetty, S., Subramanian, M., 2015. Genetic characteri- Vulliet, E., Cren-Olive, C., Grenier-Loustalot, M.F., 2011. Occurrence of pharmaceuticals
zation of caffeine degradation by bacteria and its potential applications. Microb. and hormones in drinking water treated from surface waters. Environ. Chem. Lett.
Biotechnol. 8, 369–378. 9 (1), 103–114.
Thomas, P.M., Foster, G.D., 2005. Tracking acidic pharmaceuticals, caffeine, and triclosan Vymazal, J., Bˇrezinová, T.D., Koˇzeluh, M., Kule, L., 2017. Occurrence and removal of phar-
through the wastewater treatment process. Environ. Toxicol. Chem. 24, 25–30. maceuticals in four full-scale constructed wetlands in the Czech Republic – the first
Tran, N.H., Gin, K.Y.H., 2017. Occurrence and removal of pharmaceuticals, hormones, per- year of monitoring. Ecol. Eng. 98, 354–364.
sonal care products, and endocrine disrupters in a full-scale water reclamation plant. Wang, D., Sui, Q., Lu, S.G., Zhao, W.T., Qiu, Z.F., Miao, Z.W., Yu, G., 2014. Occurrence and
Sci. Total Environ. 599–600, 1503–1516. removal of six pharmaceuticals and personal care products in a wastewater treat-
Tran, N.H., Urase, T., Ngo, H.H., Hu, J., Ong, S.L., 2013. Insight into metabolic and ment plant employing anaerobic/anoxic/aerobic and UV processes in Shanghai,
cometabolic activities of autotrophic and heterotrophic microorganisms in the bio- China. Environ. Sci. Pollut. Res. 21 (6), 4276–7285.
degradation of emerging trace organic contaminants. Bioresour. Technol. 146, WateReuse Foundation, 2007. Reclaimed Water Aquifer Storage and Recovery Potential
721–731. Changes in Water Quality. Water Reuse Foundation.
Tran, N.H., Urase, T., Ta, T.T., 2014a. A preliminary study on the occurrence of pharmaceu- Wilde, M.L., Mahmoud, W.M.M., Kümmerer, K., Martins, A.F., 2013. Oxidation–coagula-
tically active compounds in hospital wastewater and surface water in Hanoi, tion of β-blockers by K2FeVIO4 in hospital wastewater: assessment of degradation
Vietman. Clean: Soil, Air, Water 42 (3), 267–275. products and biodegradability. Sci. Total Environ. 452–453, 137–147.
Tran, N.H., Li, J., Hu, J., Ong, S.L., 2014b. Occurrence and suitability of pharmaceuticals and Yang, X., Flowers, R.C., Weinberg, H.S., Singer, P.C., 2011. Occurrence and removal of phar-
personal care products as molecular markers for raw wastewater contamination in maceuticals and personal care products (PPCPs) in an advanced wastewater reclama-
surface water and groundwater. Environ. Sci. Pollut. Res. 21, 4727–4740. tion plant. Water Res. 45, 5218–5228.
Tran, N.H., Chen, H., Do, T.V., Reinhard, M., Ngo, H.H., He, Y., Gin, K.Y.H., 2016. Simulta- Yu, J.T., Bouwer, E.J., Coelhan, M., 2006. Occurrence and biodegradability studies of se-
neous analysis of multiple classes of antimicrobials in environmental water samples lected pharmaceuticals and personal care products in sewage effluent. Agric. Water
using SPE coupled with UHPLC-ESI-MS/MS and isotope dilution. Talanta 163–173. Manag. 86, 72–80.
Tran, N.H., Reinhard, M., Gin, K.Y.H., 2018. Occurrence and fate of emerging contaminants Yu, C.L., Summers, R.M., Li, Y., Mohanty, S.K., Subramanian, M., Pope, R.M., 2015. Rapid
in municipal wastewater plants from different geographical regions-a review. Water identification and quantitative validation of a caffeine-degrading pathway in
Res. 133, 182–207. Pseudo-monas sp. J. Proteome Res. 14, 95–146.
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.