w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

Available at www.sciencedirect.com

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

Comprehensive assessment of the design configuration of

constructed wetlands for the removal of pharmaceuticals
and personal care products from urban wastewaters
Mara Hijosa-Valsero a,*, Vctor Matamoros c, Ricardo Sidrach-Cardona d,
Javier Martn-Villacorta a, Eloy Becares e, Josep M. Bayona b
a

Facultad de Ciencias Biologicas y Ambientales, Departamento de Qumica y Fsica Aplicadas, Universidad de Leon,
Campus de Vegazana s/n, 24071 Leon, Spain
b
IDAEA-CSIC, C/Jordi Girona 18-26, 08034, Barcelona, Spain
c
Facultat de Cie`ncies, Departamento de Qumica, Universitat de Girona, Campus Montilivi s/n, 17071 Girona, Spain
d
Instituto de Medio Ambiente, Universidad de Leon, C/La Serna 58, 24007 Leon, Spain
e
Facultad de Ciencias Biologicas y Ambientales, Departamento de Biodiversidad y Gestion Ambiental, Universidad de Leon, Campus de
Vegazana s/n, 24071 Leon, Spain

article info

abstract

Article history:

Seven mesocosm-scale constructed wetlands (CWs) of different configurations were

Received 12 February 2010

operated outdoors for nine months to assess their ability to remove pharmaceuticals and

Received in revised form

personal care products (PPCPs) from urban wastewaters. CWs differed in some design

10 April 2010

parameters, namely the presence of plants, the species chosen (i.e., Typha angustifolia vs

Accepted 22 April 2010

Phragmites australis), flow configuration (i.e., surface flow vs subsurface flow) and the

Available online 29 April 2010

presence of a gravel bed. A nearby conventional activated-sludge wastewater treatment

plant (WWTP) fed with the same sewage was simultaneously monitored for comparison.

Keywords:

The PPCPs ketoprofen, naproxen, ibuprofen, diclofenac, salicylic acid, carbamazepine,

PPCPs

caffeine, galaxolide, tonalide and methyl dihydrojasmonate were monitored. The presence

Constructed wetlands

of plants favoured the removal of some PPCPs. The performance of the mesocosm studied

Urban wastewater

was compound-dependant, soilless CWs showing the highest removal efficiency for

WWTP

ketoprofen, ibuprofen and carbamazepine, while free-water CWs with effluent leaving

Wetland configuration

through the bottom of the tank performed well for the degradation of ketoprofen, salicylic

Removal efficiency

acid, galaxolide and tonalide. Finally, subsurface horizontal flow CWs were efficient for the
removal of caffeine. Significant linear correlations were observed between the removal of
some PPCPs and temperature or redox potential. Hence, microbiological pathways appear
to be the most probable degradation route for PPCPs in the CWs studied.
2010 Elsevier Ltd. All rights reserved.

1.

Introduction

Urban wastewaters contain a large variety of pharmaceuticals

and personal care products (PPCPs) and their metabolites,

originating from direct human intake and other personal care

use (Stumpf et al., 1999; Kim et al., 2007) before disposal in the
sewerage system. However, since wastewater treatment
plants (WWTPs) are not designed for removing PPCPs, many of

* Corresponding author. Facultad de Ciencias Biologicas y Ambientales, Departamento de Qumica y Fsica Aplicadas, Universidad de
Leon, Campus de Vegazana s/n, 24071 Leon, Spain. Tel.: 34 987291000x5158; fax: 34 987291945.
E-mail addresses: mhijv@unileon.es (M. Hijosa-Valsero), victor.matamoros@udg.edu (V. Matamoros), rsidm@unileon.es (R. SidrachCardona), jmarv@unileon.es (E. Martn-Villacorta), ebecm@unileon.es (E. Becares), jbtqam@cid.csic.es (J.M. Bayona).
0043-1354/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2010.04.022

3670

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

them are released into surface waters (Joss et al., 2006), where,
despite their low concentrations, their ecotoxicological effects
are unpredictable because of the large number of compounds
possibly present and their design as biologically active molecules (Daughton and Ternes, 1999).
Constructed wetlands (CWs) possess the ability to remove
some PPCPs (Conkle et al., 2008; Park et al., 2009) but the
mechanisms involved are largely unknown. The coexistence
of several micro-environments in CWs allows for a variety of
microbiological communities, which might be able to offer
different metabolic pathways leading to PPCP degradation.
This coexistence is related to the variation of physico-chemical parameters on different gradients inside CWs (Imfeld
et al., 2009). Some of these variations may be generated by
the organisms inhabiting the CW (Stottmeister et al., 2003).
Although CWs have been observed to be able to remove PPCPs
to some extent, the most efficient configuration for their
removal is still unknown.
Up to now, due to the high surface/equivalent-inhabitant
ratio required to achieve wastewater quality parameters, CWs
are only feasible in small urban communities (European
Commission, 2001) or as tertiary treatments dealing with
a small, diverted fraction of conventional WWTP effluents
(Matamoros et al., 2008a). However, both alternatives are
attractive because CWs show a high capacity to remove organic
micropollutants, particularly PPCPs, consuming little energy
and with relatively low maintenance costs.
Our aim was to compare the efficiency of several mesocosmscale CWs in removing PPCPs from urban wastewater. These
CWs differed in some design parameters, namely, the presence
or absence of plants, their species (Typha angustifolia or Phragmites australis), the flow configuration (i.e., free-water surface
flow e FW-SF, free-water flow with effluent leaving through the
bottom of the tank e FW-bottom e or conventional horizontal
subsurface flow e SSF) and the presence or absence of soil
matrix. To the best of our knowledge, this is the first time that
such a variety of mesocosm has been screened to assess the best
design characteristics of CWs for PPCP removal. The efficiency
comparison of the different systems was carried out by analysing mass removal. The PPCPs studied comprised a variety of
analgesic/anti-inflammatory drugs (ketoprofen, naproxen,
ibuprofen, diclofenac and salicylic acid), an anti-epileptic drug
(carbamazepine), lipid regulators (clofibric acid), a diuretic drug
(furosemide), a stimulant (caffeine) and fragrances (ambretolide, celestolide, cashmeran, galaxolide, tonalide and methyl
dihydrojasmonate). Table S1 (see Supplementary Data section)
includes chemical information about all the studied PPCPs.
Physico-chemical parameters (i.e., temperature, pH, dissolved
oxygen and redox potential) were concurrently measured in all
CWs to study their relationship with PPCP removal efficiency.
The influence of seasonal variability on the operational results
was also studied over a nine-month period.

2.

Material and methods

2.1.

Description of the mesocosms-scale CWs

The experiment lasted from January to September 2008.

Seven mesocosm-scale CWs were set up in the open air

within the grounds of the Leon WWTP, in northwest Spain.

All CWs consisted of a fibreglass container (80 cm
wide  130 cm long  50 cm high) with a surface area of 1 m2,
but had certain design differences, which are summarised in
Fig. 1. Systems CW1 and CW5 had no gravel bed, since they
were designed as soilless systems with floating macrophytes
and a surface flow (FM-SF). Systems CW2, CW3 and CW4 had
a 25-cm layer of free-water over a 25-cm layer of siliceous
gravel (d10 4 mm). Systems CW6 and CW7 had a 45-cm layer
of siliceous gravel (d10 4 mm). System CW2 had a conventional free-water surface flow (FW-SF), CW3 and CW4 had
a free-water flow but with the effluent leaving through the
bottom of the tank (FW-bottom), whereas CW6 and CW7 had
a conventional horizontal subsurface flow (SSF). The effluent
pipe was located at the bottom of the tank for FW-bottom and
SSF systems (CW3, CW4, CW6 and CW7) and at the top for
FM-SF and FW-SF systems (CW1, CW2 and CW5). In May 2007
seedlings were collected in nearby wet areas and planted in
wetlands CW1, CW2, CW3, CW5 and CW6 with a density of
50 plants m2. Wetlands CW1, CW2 and CW3 were planted
with T. angustifolia. Wetlands CW5 and CW6 were planted
with P. australis. Vegetation coverage was nearly 100% in all
cases. Wetlands CW4 and CW7 were left unplanted to act as
controls. Immediately after the planting, the seven systems
began to operate. Plants were not harvested during the
experimental period. The theoretical hydraulic retention
time (tHRT) values of tanks CW1, CW2, CW3, CW4, CW5, CW6
and CW7 were, respectively, 2.1, 3.3, 5.1, 6.1, 2.9, 2.5 and 2.6
days.
Leon WWTP is a conventional plant described in the
Supplementary Data (SD) section. Urban wastewater from the
primary clarifier of Leon WWTP was conducted to a homogenisation tank of 1 m3. All the CWs were fed with this homogenised wastewater at a continuous flow rate of 50 l day1
(input load 50 mm day1). CWs received a higher pollutant
concentration during cold months (the organic input mass
load was approximately 3 g m2 day1 BOD5 in summer and
10 g m2 day1 BOD5 in winter). This was inevitable, as our
influent wastewater came directly from the primary clarifier
and the season-variability of its pollutant load was related to
the operational regime of the WWTP.

2.2.

Sampling procedure

The systems started up in May 2007. After a stabilization

period, two sampling campaigns were carried out, one in
winter 2008 (JanuaryeMarch 2008) and the other in summer
(JulyeSeptember 2008). Influent and effluent grab samples
were collected once a week (n 8 in winter and n 7 in
summer) at the seven CWs and Leon WWTP. Wastewater
samples were always collected on the same day and at the
same time. Influent and effluent samples were collected in
one-litre amber glass bottles, which were transported refrigerated (4  C) to the laboratory, where they were analysed
within 24 h. In addition, physico-chemical parameters
(temperature, pH, dissolved oxygen and redox potential) were
measured in situ at two different depths (5 cm below water
surface and 5 cm above the bottom of the tank) in each CW
and the homogenisation tank. Conventional wastewater

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

3671

Fig. 1 e Schematic design characteristics of the CWs.

quality parameters (COD, BOD5, TSS, NH

4 and orthophosphate) were controlled weekly to characterise the wastewater.
Average temperatures during the sampling period were
7.0  C in winter (with values ranging between 2.6 and 18.2  C)
and 19.9  C in summer (with recorded values from 4.0 to
31.8  C). Accumulated rainfall was 29.72 mm in the winter
campaign and 4.82 mm in the summer campaign. These data
were obtained from the nearest weather station (La Virgen del
Camino, Leon, Spain).

2.3.

Analytical procedure

PPCPs in wastewater samples were analysed following

a previously described GCeMS methodology (Matamoros
et al., 2005). Chromatographic conditions, data processing
and validation of the methodology were described elsewhere
(Matamoros and Bayona, 2006). Detailed information about
reagents, materials, instrumentation and analytical methods
for the determination of physico-chemical parameters,
conventional wastewater quality parameters and PPCPs is
given as SD.

2.4.

Statistics

Experimental results were statistically evaluated using the

SPSS 16 package (Chicago, IL). Data normality and homoscedasticity were checked with a ShapiroeWilk W test and
a Levene test respectively. Comparisons of CW efficiencies
were performed with non-parametric ManneWhitney U tests.

The existence of linear correlations between variables was

analysed by using the Spearman coefficient (non-parametric
statistics). Differences were considered significant when
p < 0.05.

3.

Results and discussion

3.1.

Influent wastewater characteristics

Physico-chemical parameters of influent wastewater

(temperature, pH, dissolved oxygen and redox potential) are
shown in Table S2. Seasonal influent concentrations of COD,
BOD5, TSS and nutrients are shown in Table S3.

3.2.

PPCP occurrence in raw wastewater

Table 1 shows PPCP mean concentrations and standard

deviations in the raw wastewater. Five (ambretolide, celestolide, cashmeran, furosemide and clofibric acid) out of
fifteen PPCPs were below the detection limit in all samples.
Ketoprofen was only detected above quantitation limits in
winter (ketoprofen LOQ 0.89 mg l1). Mean PPCP influent
concentrations ranged between 0.37 mg l1 for diclofenac in
summer, and 67.34 mg l1 for caffeine in winter. Some
substances showed clearly higher influent concentrations in
winter, like caffeine, naproxen, methyl dihydrojasmonate,
ketoprofen and ibuprofen. Caffeine, salicylic acid, ibuprofen
and methyl dihydrojasmonate exhibited the highest

3672

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

Table 1 e Mean values and standard deviations of PPCP

concentrations (mg lL1) in the influent water.
Winter

Summer

Analgesic antiinflammatory drugs

Ketoprofen
Naproxen
Ibuprofen
Diclofenac
Salicylic acid

1.79  0.39
3.53  0.91
24.19  8.45
0.83  0.20
9.93  7.72

<0.89
1.35  0.28
8.38  1.87
0.37  0.10
10.29  4.92

Anti-epileptic drugs
Carbamazepine

1.36  0.70

1.52  1.99

Stimulant drugs
Caffeine

67.34  25.31

22.59  5.21

Fragrances
Methyl dihydrojasmonate
Galaxolide
Tonalide

11.55  4.72
0.94  0.26
0.39  0.15

3.95  0.89
1.22  0.80
0.37  0.25

Removal efficiencies

Since influent contaminant concentrations varied throughout

the experimental period (Table 1), the removal efficiency of
CWs cannot be determined just from effluent concentrations,
as these depend on influent concentrations and follow a first
order removal kinetics (Matamoros and Bayona, 2006).
Therefore, to make more reliable removal efficiency comparisons between CWs, the mass removal efficiency (MRE) was
calculated as follows:
MRE%

Mr
Ci Qi  Ce Qe
 100
 100
Mi
Ci Qi

(1)

where Mr (mg day1) is the removed mass of a pollutant in the

wetland, Mi (mg day1) is the mass of a pollutant which enters
the wetland, Ci (mg l1) is the influent concentration of
a pollutant, Qi (l day1) is the influent flow rate, Ce (mg l1) is
the effluent concentration of a pollutant and Qe (l day1) is the
effluent flow. MRE (expressed as a percentage) includes both
influent and effluent flows and thus takes evapotranspiration
into account. Evapotranspiration water loss is an important
factor in the operation of CWs. Table 2 shows a summary of
evapotranspiration data in the CWs studied. In addition, MRE
allows for the comparison of winter and summer samples
because it is a normalized value calculated by dividing the
removed mass (Mr) by the influent mass (Mi CiQi), which
eliminates the problem of different influent concentrations.
WWTP removal efficiencies were calculated in a slightly
different way and assuming that no evapotranspiration took
place. This simplification is quite acceptable, since losses by
evaporation in a WWTP are considered negligible compared
with the great volumes of water treated. Leon WWTP removal
efficiencies were calculated using the following equation
WWTP removal efficiencies %

Ci  Ce
 100
Ci

CW1
CW2
CW3
CW4
CW5
CW6
CW7

Winter

Summer

16.52
14.63
19.45
9.30
13.43
11.57
3.41

29.58
25.33
25.09
6.21
27.66
32.90
5.94

Fig. 2 shows MREs for the seven CWs and the WWTP in winter
and summer. Higher percentages indicate higher removal efficiencies. In our study, winter efficiencies were generally lower
than summer ones (Fig. 2).

concentrations throughout the experimental period. These

results are in agreement with other studies dealing with the
behaviour of PPCPs in WWTPs (Buser et al., 1999; Carballa
et al., 2004; Bendz et al., 2005).

3.3.

Table 2 e Mean percentages (%) of water losses by

evapotranspiration in the CWs. Data for winter (n [ 17)
and summer (n [ 22). These values were calculated from
influent and effluent weekly flow data.

(2)

3.3.1.

WWTP performance

The WWTP had good removal efficiencies (around 80%) for

salicylic acid in both winter and summer (Fig. 2). Ternes et al.
(2004) also reported good results (99%) for the removal of this
compound in a conventional activated-sludge WWTP. Nevertheless, our WWTP showed a season dependence for the
degradation of several substances like naproxen (62% in
winter; 89% in summer), ibuprofen (41% in winter; 90% in
summer), caffeine (29% in winter; 86% in summer) and methyl
dihydrojasmonate (38% in winter; 86% in summer) (Fig. 2).
Other authors have observed that the degradation efficiencies
of these PPCPs in WWTPs were 78e93% for naproxen (Stumpf
et al., 1999; Bendz et al., 2005), 96e99% for ibuprofen (Bendz
et al., 2005; Clara et al., 2005; Ternes et al., 2007), 94e99% for
caffeine (Bendz et al., 2005; Ternes et al., 2007) and 82% for
methyl dihydrojasmonate (Simonich et al., 2002). PPCPs not
degraded or only slightly degraded by our WWTP, include
galaxolide, tonalide, carbamazepine and diclofenac. These
results are in agreement with other studies, which observed
removal efficiencies of 22e33% for diclofenac (Bendz et al.,
2005; Ternes et al., 2007) and 0e14% for carbamazepine
(Clara et al., 2005), but differ from others reporting removal
efficiencies of 44e63% for galaxolide and 63e70% for tonalide
(Bester, 2004; Ternes et al., 2007). Unfortunately, in our study,
ketoprofen removal efficiency could only be measured in
winter (33%) because of its low concentration in summer.
Other authors have found variable results (51e99%) for the
removal of this substance in WWTPs (Lindqvist et al., 2005).

3.3.2.

General PPCP removal efficiencies in the CWs

The degradation behaviour of the different groups of PPCPs

(Fig. 2) is described below.

3.3.2.1. Analgesic antiinflammatory drugs. Ketoprofen removal

efficiencies in CWs ranged from 11 to 50% in winter and the best
performances were observed in the FW-bottom-CWs (CW3,
CW4), the FW-SF-CW (CW2) and in the FM-SF-CWs (CW1, CW5).
Despite weak winter insolation, this would seem reasonable, for
ketoprofen degradation is believed to be related to photodegradation processes (Lin and Reinhard, 2005; Pereira et al.,
2007) and treatment systems of these kinds would let in more

Ketoprofen

Naproxen
120
Winter

100
80
60
40
20

Mass removal efficiency (%)

Winter
Summer

100
80
60
40
20

Mass removal efficiency (%)

80
60
40
20

Winter
Summer

100
80
60
40
20

C
W
5

C
W
6
C
W
7
W
W
TP

C
W
1

C
W
6
C
W
7
W
W
TP

C
W
5

C
W
4

C
W
2
C
W
3

C
W
1

Salicylic acid

C
W
4

C
W
2
C
W
3

Carbamazepine

100
80
60
40
20

Mass removal efficiency (%)

120
Winter
Summer

80
60
40
20

C
W
6
C
W
7
W
W
TP

C
W
4

C
W
5

C
W
2
C
W
3

C
W
1

C
W
5

C
W
6
C
W
7
W
W
TP

C
W
2
C
W
3

C
W
4

C
W
1

100

Winter
Summer

Methyl dihydrojasmonate

Caffeine
120

120
100

Mass removal efficiency (%)

Winter
Summer

80
60
40
20

Winter
Summer

100
80
60
40
20

C
W
5

C
W
6
C
W
7
W
W
TP

C
W
4

C
W
1

C
W
5

C
W
6
C
W
7
W
W
TP

C
W
4

C
W
2
C
W
3

C
W
1

C
W
2
C
W
3

Tonalide

Galaxolide
120
Winter
Summer

100
80
60
40
20

Mass removal efficiency (%)

120

Winter
Summer

100
80
60
40
20

C
W
5

C
W
6
C
W
7
W
W
TP

C
W
2
C
W
3

C
W
6
C
W
7
W
W
TP

C
W
4

C
W
5

C
W
2
C
W
3

C
W
1

C
W
1

C
W
4

Mass removal efficiency (%)

Winter
Summer

100

120

Mass removal efficiency (%)

C
W
5

120

Mass removal efficiency (%)

C
W
6
C
W
7
W
W
TP

Diclofenac

Ibuprofen
120

Mass removal efficiency (%)

C
W
4

C
W
1

C
W
5

C
W
6
C
W
7
W
W
TP

C
W
4

C
W
2
C
W
3

C
W
1

C
W
2
C
W
3

Mass removal efficiency (%)

120

Fig. 2 e Mean CW mass removal efficiency (MRE) in winter and summer. Mean WWTP removal efficiency in winter and
summer. Error bars represent standard deviation.

3674

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

sunlight (especially CW4) than the SSF-CWs (CW6, CW7). Naproxen removal efficiencies varied somewhat among CWs, with
values of 27e66% in winter and 27e83% in summer. The FWbottom-CWs (CW3, CW4) offered the best year-round removal
efficiencies, although CW5 and CW6 gave better results in
summer. Ibuprofen, with removal efficiencies of 27e74% in
winter and 6e96% in summer, was more easily degraded by
FM-SF-CWs (CW1, CW5), followed by FW systems (CW2, CW3,
CW4). The least efficient systems were the SSF-CWs (CW6,
CW7). Naproxen and ibuprofen removal efficiencies in other
CWs have also been found to be variable and dependent on
system configuration parameters, like the depth of the gravel
matrix (Matamoros et al., 2005; Matamoros and Bayona, 2006)
and flow type (Matamoros et al., 2009). Diclofenac only showed
continuous removal efficiencies in CW4, CW5 and CW6 (which
are very different from each other). Their efficiency ranged from
17 to 26% in winter and 36 to 52% in summer. The other CWs
showed lower values, especially during summer. Other authors
have also found low efficiency values (<45%) for diclofenac
removal in horizontal SSF-CWs (Matamoros and Bayona, 2006;
Matamoros et al., 2009). However higher efficiencies (65e96%)
have been reported in hybrid systems including different kinds
of wetlands connected in series (Hijosa-Valsero et al., 2010), in
pond systems (Hijosa-Valsero et al., 2010) and in SF-CWs
working as tertiary treatments (Matamoros et al., 2008a). Salicylic acid was an easily degradable substance in all CWs, with
removal efficiencies from 35 to 85% in winter and from 84 to 89%
in summer. FW-bottom-CWs (CW3, CW4) were best at removing
salicylic acid. Several other studies report high removal efficiencies for salicylic acid (77e98%) in different types of CWs
(Matamoros and Bayona, 2006; Hijosa-Valsero et al., 2010;
Matamoros et al., 2009).

lipophilic fragrances (Table S1), tend to adsorb to suspended

solids and other surfaces. Their removal efficiencies ranged
between 0 and 65% in winter and 30e80% in summer. The
FW-bottom-CWs (CW3, CW4) and the Typha-FM-SF-CW (CW1)
gave the best results for their removal. These relatively low
values are common in the literature. For example, Matamoros
and Bayona (2006) measured removal values of 31e61% for
galaxolide and 32e65% for tonalide in horizontal SSF-CWs.
However, higher values (85e90%) were reported for both
substances in a SF-CW working as a tertiary treatment
(Matamoros et al., 2008a) and Hijosa-Valsero and co-workers
(unpublished data) observed removals of 68e86% for galaxolide and 51e80% for tonalide during summer 2008 in hybrid
systems combining different CW-configurations, in NW-Spain
(systems described in Hijosa-Valsero et al., 2010).
In short, some CWs offered at least as good efficiencies as the
WWTP for the removal of most PPCPs: ketoprofen, ibuprofen,
diclofenac, carbamazepine, caffeine, methyl dihydrojasmonate,
galaxolide or tonalide. Certain CW-designs seemed more efficient for the degradation of some PPCP classes. For instance,
FM-SF-CWs (CW1, CW5), performed well in the removal of
ketoprofen, ibuprofen and carbamazepine; FW-bottom-CWs
(CW3, CW4) were efficient for the degradation of ketoprofen,
salicylic acid, galaxolide and tonalide; and conventional horizontal SSF-CWs (CW6, CW7) were efficient for the removal of
caffeine.

3.4.
Efficiency comparisons between CWs. The effect of
design parameters on PPCP removal
Pairs of CWs differing in only one design parameter were
compared. These pairs were divided into groups and are listed
below:

3.3.2.2. Anti-epileptic drug. Carbamazepine removal was low

in the CWs. During the experimental period, FM-SF-CWs
(CW1, CW5) showed relatively constant values (24e36% in
winter; 48% in summer). The planted SSF-CW (CW6) performed similarly. Our poor results agree with other authors
(Conkle et al., 2008; Matamoros et al., 2008a,b, 2009). The
removal of this substance in CWs has rarely surpassed 60%
(Park et al., 2009), and it is has been suggested that this drug is
retained or adsorbed inside CWs (Matamoros et al., 2005,
2008a,b; Park et al., 2009).

a. Vegetal species. T. angustifolia vs P. australis: CW1 vs CW5

b. Planted vs unplanted CWs
b.1. FW-bottom-CWs: CW3 vs CW4
b.2. Conventional horizontal SSF-CWs: CW6 vs CW7
c. Absence of soil matrix vs presence of soil matrix
c.1. SF-CWs: CW1 vs CW2
c.2. SF vs SSF: CW5 vs CW6
d. Relative height of the effluent pipe: CW2 vs CW3
e. FW-bottom-CW vs SSF-CW: CW4 vs CW7

3.3.2.3. Stimulant drug. Caffeine removal efficiencies were

high in all the CWs studied (23e58% in winter and 82e99% in
summer), especially in conventional SSF-CWs (CW6, CW7).
Such high summer efficiencies have been reported by other
authors in various CW-configurations (Matamoros and
Bayona, 2006; Conkle et al., 2008; Hijosa-Valsero et al., 2010;
Matamoros et al., 2009).

The data chosen for this statistical analysis were the MRE
values. Table S4 summarises the statistical results of the
comparative removal efficiency of pairs of CWs. The significant differences within pairs of CWs yielded the following
information.
The presence of plants contributed to the removal of
naproxen, ibuprofen, diclofenac, carbamazepine, caffeine,
methyl dihydrojasmonate, galaxolide and tonalide (CW3 vs
CW4; CW6 vs CW7). Plants are generally considered beneficial
in a CW, as they can take up and assimilate nutrients, they act
as an anchoring surface for biofilm, they pump and release O2
to the bottom of the systems, they retain suspended particles
and they insulate against low temperatures (Tanner, 2001;
Kyambadde et al., 2004). Zhang et al. (2010a) demonstrated
that the diversity and community-level physiological profiles
of a microbial community in a full-scale vertical SSF-CW

3.3.2.4. Fragrances. Methyl dihydrojasmonate is an easily

degradable hydrophilic fragrance (Table S1). Its mass removal
efficiencies were relatively high in all the CWs, with values of
39e74% in winter and 79e96% in summer. Other studies point
out that different kinds of CWs are efficient for the removal of
this fragrance (61e99%), at least in summer (Matamoros and
Bayona, 2006; Hijosa-Valsero et al., 2010; Matamoros et al.,
2009). On the other hand, galaxolide and tonalide, as

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

strongly depended on the presence or absence of plants.

Similarly, the activities of many microbiological enzymes
depended on the presence or absence of plants in the
substrate of a full-scale CW (Zhang et al., 2010b). Plants have
proved positive for the removal of micropollutants other than
PPCPs (Ji et al., 2002; Mant et al., 2006; Braeckevelt et al., 2008;
Low et al., 2008; Ong et al., 2009; Rogers and Stringfellow,
2009). It cannot be discarded that plants actively participate
in PPCP removal via uptake; and, in that case, the compound
uptake rate would be associated with the evapotranspiration
rate. This was checked by evaluating possible linear correlations between evapotranspiration (Table 2) and MRE (Fig. 2) for
every pollutant. Only carbamazepine in winter (Spearman
coefficient 0.964) and methyl dihydrojasmonate in summer
(Spearman coefficient 0.893) showed significant ( p < 0.05)
positive correlations. Since different removal processes can
take place simultaneously in CWs, the absence of these
correlations does not imply the ruling out of plant uptake,
especially for those substances with log Kow values of 1e3.5
(Dietz and Schnoor, 2001). In our study, P. australis proved
more efficient than T. angustifolia in summer for the removal
of ibuprofen, diclofenac, caffeine and methyl dihydrojasmonate (CW1 vs CW5). In spite of the many plantcomparison studies carried out, there is no clear agreement on
which species is most efficient at removing organic matter
and nutrients from wastewater (Brisson and Chazarenc, 2009).
We believe that the ability of a plant to enhance pollutant
removal depends not only on the typical species characteristics, but also on many other factors like microbial communities related to them, wastewater nature and climate
conditions. In the present study, design parameters (gravel,
flow type) also influenced PPCP removal efficiency. For
instance, the unplanted FW-bottom-CW (CW4) was generally
more efficient at removing PPCPs (with the exception of
caffeine and methyl dihydrojasmonate) than the unplanted
conventional SSF-CW (CW7). It should be pointed out that the
tHRT in CW4 was clearly higher (see Section 2.1). If we also
consider that caffeine was better removed in a SSF-CW (CW6)
than in a FM-SF-CW (CW5), we could conclude that the best
system for removing caffeine from wastewater is a planted
conventional horizontal SSF-CW. When the planted FW
systems (CW2 and CW3) were compared, the one with the
effluent leaving through the bottom of the tank (CW3) was
more efficient to remove naproxen, ibuprofen, salicylic acid,
caffeine and the three fragrances. Once more, the best CW
(in this case, CW3) had a higher tHRT, although this fact
should not be considered as the only explanation. The presence of gravel (CW1 vs CW2; CW5 vs CW6) was not decisive for
the removal of PPCPs. To illustrate the importance of CWdesign, it can be added that the lowest ibuprofen removal
efficiencies in CWs have usually been found in horizontal SSFCWs (Matamoros et al., 2005, 2009) and the highest in vertical
SSF-CWs (Matamoros et al., 2009), hybrid systems combining
different kinds of CWs (Conkle et al., 2008; Hijosa-Valsero
et al., 2010) and SF-CWs (Matamoros et al., 2008a). Similarly,
diclofenac seems to be more easily removed by SF-CWs and
hybrid systems (Matamoros et al., 2008a; Hijosa-Valsero et al.,
2010) than by horizontal SSF-CWs (Matamoros and Bayona,
2006). Physico-chemical parameters (like redox potential and
insolation) in CWs are strongly influenced by the flow type.

3675

Some compounds are sensitive to photodegradation, like

ketoprofen (Lin and Reinhard, 2005; Pereira et al., 2007), naproxen (Valero and Carrillo, 2004; Pereira et al., 2007; MendezArriaga et al., 2008), diclofenac (Andreozzi et al., 2003;
Mendez-Arriaga et al., 2008) or even carbamazepine
(Doll and Frimmel, 2003) (but carbamazepine has very slow
kinetics). This would explain why the unplanted FW-bottomCW (CW4) gave better results for the removal of naproxen and
diclofenac than others (CW3 or CW7), although the higher
tHRT of CW4 could also be involved. Hijosa-Valsero et al.
(2010) reported a removal efficiency of 85% for naproxen and
65% for diclofenac in a pond system during summer (a season
with strong sunlight). An interesting fact observed in the
present study was the great importance of the design configuration for the removal of lipophilic fragrances (galaxolide
and tonalide). It is known that these musks are mainly
retained in CWs by adsorption processes (Matamoros and
Bayona, 2006; Matamoros et al., 2008a). It would seem logical
to think that conventional SSF-CWs (like CW6 and CW7),
owing to the greater presence of gravel and hence larger
adsorption surface, should be able to remove more musk
fragrances than other CWs (for instance, CW4). However, the
opposite was observed. As we have already said, SF-CWs and
hybrid systems remove galaxolide and tonalide more efficiently than horizontal SSF-CWs (Matamoros and Bayona,
2006; Matamoros et al., 2008a; Hijosa-Valsero et al., 2010).
This could be due to the presence of microscopic algae and
other suspended solids in the free-water layer of some kinds
of CWs e not forgetting macrophyte leaves, stems and roots e
which could act as important adsorption surfaces. Nevertheless, other explanations cannot be ruled out (i.e., photodegradation). A review carried out by Truu et al. (2009)
indicates that microbially mediated processes in CWs are
mainly dependent on hydraulic conditions, wastewater
properties, including substrate and nutrient quality and
availability, filter material or soil type, plants, and different
environmental factors.

3.5.
Correlation between contaminant removal and
physico-chemical parameters
The microbiological pathways and the physico-chemical
processes contributing to PPCP degradation in CWs have not
yet been thoroughly described, owing to their complexity
(Imfeld et al., 2009). Physico-chemical parameters (such as
temperature, insolation, pH or redox potential) influence
many abiotic processes. One example is the retention of some
organic compounds sorbed onto solid surfaces inside the CW,
a major process in the removal of lipophilic fragrances
(Matamoros and Bayona, 2006; Matamoros et al., 2008a).
Moreover, physico-chemical parameters (especially dissolved
oxygen and redox potential) determine the dominant microbiological populations present inside the CW and the metabolic pathways that PPCPs will take. In order to understand
some basic aspects of PPCP degradation in CWs and its
possible dependence on physico-chemical parameters,
statistical analyses (Spearman coefficient) were carried out to
check the existence of linear correlations in this regard. PPCP
degradation data were expressed as MRE (Fig. 2) and crossed

3676

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

with the values of physico-chemical parameters (Table S2).

Table S5 shows the results of this statistical analysis.

3.5.1.

Temperature effect

High temperatures had a significant positive effect on the

degradation of caffeine, naproxen, salicylic acid, methyl
dihydrojasmonate, galaxolide and tonalide. Microbial metabolism depends on temperature. Microorganisms living in CWs
usually reach their optimal activity at warm temperatures
(15e25  C), especially nitrifying and proteolytic bacteria (Truu
et al., 2009). On the other hand, abiotic processes like
adsorption are also temperature-dependent, since they are
exothermic processes, hence favoured by low temperatures.
Therefore, our observations indicate that microbiologically
mediated processes predominate over abiotic processes in the
degradation of these substances. The statistical analysis of
temperature data is strongly influenced by seasonality,
because higher temperatures were registered in summer. In
this regard, it may be more accurate to say that summer
conditions (e.g. warmth, plant activity and sunlight) enhance
the removal of the PPCPs mentioned, instead of just attributing this fact to temperature. Other studies dealing with PPCP
removal in CWs did not include winter data (Matamoros et al.,
2005, 2008b, 2009; Matamoros and Bayona, 2006; Conkle et al.,
2008; Hijosa-Valsero et al., 2010; Park et al., 2009) or included
very short winter sampling periods but in CWs used as tertiary
treatments (Matamoros et al., 2008a), so no comparison with
these previous studies is possible. However, Dordio et al.
(2010) did study winter and summer removal of ibuprofen,
carbamazepine and clofibric acid in planted microcosm CWs
and observed better efficiencies in summer (96% for
ibuprofen, 97% for carbamazepine and 75% for clofibric acid)
than in winter (82% for ibuprofen, 88% for carbamazepine and
48% for clofibric acid). More data exist for the degradation of
COD, BOD5 and nutrients: Akratos and Tsihrintzis (2007) found
positive linear correlations between temperature and the
removal of COD, BOD5, TKN, NeNH3, total phosphorous and
PePO3
4 in horizontal SSF-CWs fed with synthetic wastewater.
Conversely, in our study, a negative linear correlation
appeared between ketoprofen and diclofenac degradation and
temperature (for the latter, only in the bottom of the tank).
However, results for ketoprofen only include winter data
(because ketoprofen concentration was below the LOQ in
summer) and should be considered with caution.

3.5.2.

pH effect

The pH value did not seem very important in the removal of

PPCPs and no significant linear correlation was found
between pH and the MRE of any compound. Although the pH
of wastewater can be determinant for microbiologically
mediated processes, these results could be due to the narrow
range of pH-values recorded in our study (6.48e8.34,
Table S2). Optimal values for nitrification and heterotrophic
production in CWs are found at near-neutral pH values
(Truu et al., 2009).

3.5.3.

efficiencies. The presence of oxygen (O2) enhances microbial

processes depending on this electron acceptor, such as nitrification and aerobic respiration.

Oxygen effect

High oxygen concentrations significantly aided the degradation of diclofenac; whereas low ones favoured caffeine,
methyl dihydrojasmonate, galaxolide and tonalide removal

3.5.4.

Redox potential effect

A positive linear correlation appeared between redox potential

and ibuprofen, diclofenac, salicylic acid and carbamazepine
removal efficiencies. High redox potentials are related to
aerobic conditions and, therefore, aerobic metabolic pathways
are deduced for the degradation of these four PPCPs. In addition, ibuprofen, diclofenac and carbamazepine removal was
favoured by plant presence (see Section 3.4) and this fact could
be related to the modification of redox values near the roots
(usually creating aerobic environments). However, a negative
correlation was detected for caffeine, methyl dihydrojasmonate, galaxolide and tonalide removal but only for
tank-bottom redox values. Low redox potential values are
associated to less aerobic conditions. Zwiener and Frimmel
(2003) also reported that ibuprofen and diclofenac were more
easily degraded under oxic conditions in a biofilm reactor, and
Matamoros and Bayona (2006) compared two SSF-CWs with
different redox potential values, observing that the most
aerobic CW removed PPCPs most efficiently. Therefore, the
existence of positive or negative linear correlations between
redox conditions and the degradation of PPCPs indicates once
more that microbial metabolic pathways are involved in the
removal of many PPCPs. In any event, although we had related
the removal of ibuprofen, diclofenac, salicylic acid and carbamazepine to aerobic pathways, and that of caffeine, methyl
dihydrojasmonate, galaxolide and tonalide to anaerobic pathways, this does not mean that other microbiological pathways
or even abiotic processes cannot take place simultaneously.

4.

Conclusions

The simultaneous monitoring of seven different mesocosmsscale CWs fed with the same urban wastewater at the same
flow rate during a nine-month period allowed for the study of
the best design parameters for the removal of several PPCPs
(ketoprofen, naproxen, ibuprofen, diclofenac, salicylic acid,
carbamazepine, caffeine, galaxolide, tonalide and methyl
dihydrojasmonate).
 Whereas a WWTP dealing with the same wastewater was
not able to remove diclofenac, carbamazepine, galaxolide
and tonalide, the CWs removed all the substances to
a greater or lesser extent.
 FM-SF-CWs were efficient for the removal of ibuprofen
(51e54% in winter, 85e96% in summer) and carbamazepine
(24e36% in winter, 48% in summer). FW-bottom-CWs were
efficient for the removal of salicylic acid (76e85% in winter,
87e89% in summer), galaxolide (45e65% in winter, 75e76%
in summer) and tonalide (54e60% in winter, 71e77% in
summer). Conventional horizontal SSF-CWs were useful for
the removal of caffeine (58e65% in winter, 99% in summer).
Methyl dihydrojasmonate was in general easily removed in
all CWs (36e74% in winter, 79e96% in summer). Naproxen
removal efficiencies were lower and more variable (27e66%
in winter, 27e83% in summer). Ketoprofen could only be

w a t e r r e s e a r c h 4 4 ( 2 0 1 0 ) 3 6 6 9 e3 6 7 8

measured in winter and the best removal results were found

in FM-SF-CWs (33e38% in winter) and FW-bottom-CWs
(47e50% in winter).
 The presence of plants favoured the degradation of naproxen,
ibuprofen, diclofenac, caffeine, methyl dihydrojasmonate,
galaxolide and tonalide. Two plant species were compared
(T. angustifolia and P. australis). P. australis had a better
performance, at least during summer.
PPCP degradation was closely related to physico-chemical
parameters:
 High temperatures favoured the removal of naproxen, salicylic acid, caffeine, methyl dihydrojasmonate, galaxolide
and tonalide.
 High redox potentials (oxidant conditions) were beneficial
for the removal of ibuprofen, diclofenac, salicylic acid and
carbamazepine. The degradation of caffeine, methyl dihydrojasmonate, galaxolide and tonalide was related to more
anaerobic conditions.
 The PPCP removal dependence on high temperatures
(including the better summer results observed in general for
all the PPCPs) and on redox conditions indicates the existence of a biological process. Although other elimination
mechanisms can coexist, microbiological pathways are the
most probable degradation route for PPCPs inside CWs.

Acknowledgments
This study was funded by the Spanish Ministry of Science and
Innovation through projects CTM2008-06676-C05-04/TECNO
and CTM2005-06457-C05-03 and by the Castilla y Leon
Regional Government through the project LE009A07 and by
the Castilla y Leon Regional Government through projects
LE009A07 and LE037A10-2. One of us Ms. MH-V kindly
acknowledges a FPU fellowship from the Spanish Ministry of
Education; and Dr. VM acknowledges a Juan de la Cierva
contract. We thank Juan Carlos Sanchez Sanchez for the
maintenance of the systems. We thank Acciona Agua and
Mancomunidad de Saneamiento de Leon y su Alfoz for their technical support.

Appendix. Supplementary data

Supplementary data associated with article can be found in
online version at doi:10.1016/j.watres.2010.04.022.

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