Journal of Environmental Management 117 (2013) 96e102

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Journal of Environmental Management

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

Evaluation of a coagulation/flocculation-lamellar clarifier and

filtration-UV-chlorination reactor for removing emerging
contaminants at full-scale wastewater treatment plants in Spain
Víctor Matamoros*, Victòria Salvadó
Department of Chemistry, University of Girona, Campus Montilivi, E-17071 Girona, Spain

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

Article history: The presence and elimination of 25 emerging contaminants in two full-scale Spanish wastewater
Received 9 April 2012 treatment plants was studied. The tertiary treatment systems consisted of coagulation, flocculation
Received in revised form lamellar settlement and filtration (pulsed-bed sand filters) units, and disinfection was carried out by
8 October 2012
medium pressure UV light lamps and chlorination. Diclofenac and carbamazepine were found to be the
Accepted 24 December 2012
emerging contaminants with the highest concentrations in secondary effluents. Photodegradable
Available online 24 January 2013
emerging contaminants (e.g. ketoprofen, triclosan and diclofenac) were removed by filtration-UV light
radiationechlorination whereas most hydrophobic compounds (e.g. galaxolide and tonalide) were
Keywords:
Emerging contaminants
eliminated by coagulationeflocculation followed by lamellar clarification, a unit in which a seasonal
Wastewater reclamation trend was observed. Overall mass removal efficiency was about 60%. 1-(8-Chlorocarbazolyl) acetic acid,
Clarification an intermediate product of the photodegradation of diclofenac, was detected after filtration-UV-
Filtration chlorination, but not after coagulationeflocculation and lamellar clarification. This study demonstrated
UV-Cl2 desinfection potential for general applicability of two established tertiary treatment systems to eliminate emerging
contaminants.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction contaminants meet little resistance there and so are found in

Reclaimed water has become an increasingly important supply
source in areas such as the Mediterranean where freshwater re-
sources are scarce (Levine and Asano, 2004; Oki and Kanae, 2006).
Emerging contaminants are a large, relatively new group of un-
regulated compounds such as pharmaceuticals, personal care
products, plasticizers, surfactants and herbicides about which there
is relatively little toxicological information (Murray et al., 2010).
The presence of these new contaminants in both fresh and
reclaimed waters is a major problem with largely unknown con-
sequences (Daughton, 2005; Kümmerer, 2009). Of the better
studied cases, triclosan has been found to be toxic for algal growth
and to create bacterial resistance (Orvos et al., 2002) whereas drug
mixtures containing carbamazepine, ibuprofen, and clofibric acid
have also been found to be toxic for algae (Cleuvers, 2003).
As conventional wastewater treatment plants (WWTPs) are
only designed for the elimination of organic matter, emerging
* Corresponding author.
E-mail addresses: victor.matamoros@udg.edu, vmmqam@gmail.com
(V. Matamoros).
treated wastewater (Ternes et al., 2004). Advanced water reclama-
tion treatments can improve their removal (Deng, 2009; Gogate
and Pandit, 2004) by the oxidation of recalcitrant, toxic and non-
biodegradable compounds to give various by-products. Diclofenac,
for example, produces more than eighteen compounds (Coelho
et al., 2009) and, in some cases, inert end products (Klavarioti
et al., 2009). The toxicity of the treated effluent has varied consid-
erably between studies and has at times been found to be greater
than in untreated effluent (Coelho et al., 2009; Dantas et al., 2008). A
further drawback is the lack of data regarding the long-term expo-
sure of non-target organisms and, particularly, how continuous
exposure to the treated effluent over several generations of the or-
ganisms may affect the population as a whole (Santos et al., 2010).
In the present study we evaluate ultraviolet (UV) light radiation
and chlorination, two established oxidation methods for waste-
water disinfection (Montemayor et al., 2008; Oh et al., 2007) as well
as a coagulationeflocculation and lamellar clarifier, a conventional
tertiary treatment technology that effectively removes suspended
solids and attached microorganisms (Adin and Asano, 1998).
Although there have been many laboratory scale studies eval-
uating UV light and chlorination for the removal of emerging
contaminants (Kim and Tanaka, 2009; Kim et al., 2009b; Quintana

0301-4797/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvman.2012.12.021
 V. Matamoros, V. Salvadó / Journal of Environmental Management 117 (2013) 96e102 97

et al., 2010), little attention has been paid to the capacity of full-
scale coagulation/flocculation-lamellar clarifiers and UV light
radiationechlorination reactors for this purpose.
Our aim in this study was to evaluate the seasonal capacity of
two full-scale WWTPs with tertiary treatment systems consisting
of coagulation/flocculation-lamellar clarifier and filtration-UV-
chlorination to remove emerging contaminants by sorption or
oxidation processes respectively. The emerging contaminants
included in this survey were selected on the basis of their con-
centration and high frequency of detection in river waters
and WWTP effluents (Calderón-Preciado et al., 2011). Table 1
supplementary material (SM) shows the physicochemical prop-
erties of studied contaminants. Furthermore, intermediate degra-
dation products were assessed after the treatment by coagulation/
flocculation-lamellar clarifier and UV light radiationechlorination.
lamps, maximum dosage of 48 mJ cm2, Berson Inline 400 Special
10 kW), and chlorination (3 mg L1). Both tertiary treatments
operate on demand. Reclaimed water is used for non-potable urban
applications (Tossa de Mar WWTP) and for aquifer recharge of the
River Tordera (Blanes WWTP). The hydraulic retention time (HRT) in
both tertiary treatments ranges between 60 and 120 min, making it
possible to calculate the removal efficiencies in each treatment unit.
In both cases, water is discharged through an underwater pipeline
when production exceeds demand. Table 1 shows the conventional
water quality parameters of the WWTPs. BOD in raw wastewater
was around 300 mg L1 in both WWTPs with a final tertiary effluent
between 4 and 12 mg L1. Reclaimed water complied with the
Spanish regulations for water reuse (R.D. 1620/2007).
2.3. Sampling strategy

2. Materials and methods
2.1. Chemicals and reagents
Gas chromatography (GC) grade (Suprasolv) hexane, methanol,
and ethyl acetate were supplied by Merck (Darmstadt, Germany).
Analytical-grade hydrogen chloride was obtained from Panreac
(Barcelona, Spain). Salicylic acid, benzothiazole, hydrocinnamic
acid, dimethyl phthalate, cashmeran, ibuprofen, p-tert-Octylphe-
nol, 2-(methylthio)-benzothiazole, tributyl phosphate, methyl
dihydrojasmonate, celestolide, tris(2-chloroethyl)phosphate, dia-
zinone, caffeine, galaxolide, tonalide, terbutryn, carbamazepine,
naproxen, oxybenzone, bisphenol A, triclosan, ketoprofen, diclofe-
nac, furosemide, clofibric acid, dicamba, 2,20 -dinitrophenyl, and
dihydrocarbamazepine were supplied by SigmaeAldrich (Stein-
heim, Germany). 2,4,5-trichlorophenoxypropionic acid (2,4,5-TPA)
was from Reidel-de-Haen (Seelze, Germany). Trimethylsulfonium
hydroxide (TMSH) was purchased from Fluka (Buchs, Switzerland).
Strata-X polymeric SPE cartridges (200 mg) were obtained from
Phenomenex (Torrance, CA, USA), and the 0.7 mm glass fibre filters
of B ¼ 47 mm were obtained from Whatman (Maidstone, UK).
2.2. Description of the water reclamation plants
The two water reclamation plants studied, Blanes WWTP
(109,000 population equivalent) and the Tossa de Mar WWTP
(43,100 population equivalent), are located in the north-east of
Spain (Fig. 1, Supplementary Data). The tertiary treatment at Blanes
(800 m3 h1) consisted of coagulation and flocculation followed by
lamellar settlement and filtration (pulsed-bed sand filters); dis-
infection with UV light (four banks of eight lamps, maximum dosage
of 189 mJ cm2) and chlorination (3 mg L1). The tertiary treatment
in Tossa de Mar (35 m3 h1) consisted of coagulation and floccu-
lation followed by lamellar settlement and filtration (Dynasand
continuous-flow filter), disinfection with UV light (two banks of two
Sampling was performed daily for five days from Monday to
Friday in July 2009 (summer season) and five days in March 2010
(winter season). At Blanes WWTP, samples were taken after sec-
ondary treatment, after passing through the lamellar clarifier as
well as after the filtration-UV-chlorination units in order to eval-
uate the individual capacity of the two tertiary treatment reactors.
At Tossa de Mar WWTP, samples were taken after secondary
treatment and at the end of the tertiary treatment. Downstream
samples from the river and stream next to the WWTPs were also
collected (Fig. 1, Supplementary Data). It should be noted that no
rainfall events were recorded during the whole of the sampling
period. A total of 55 grab water samples were taken. The removal
was determined using Eq. (1).
n  
1X Ca  Ci
Removal efficiency ¼ (1)
n i¼1 Ca
where Ca is the concentration of a selected compound at the
influent of each treatment technology in each individual sampling
day, Ci is the concentration at the effluent of the technology in each
individual sampling day and n is the number of samples collected
by sampling campaign (n ¼ 5).
All samples were collected in 1000 mL clean amber glass bottles,
which were transported under refrigeration to our laboratory
where they were stored at 4  C until analysis. The sample holding
time was less than 24 h.
2.4. Analytical methodology
Emerging contaminants and their intermediate degradation
products were determined as follows. Water samples were filtered
and processed as previously reported (Matamoros and Bayona,
2006). Briefly, a sample volume of 500 mL was spiked with 1 mg
of a surrogate standard (2,20 -dinitrophenyl, dihydrocarbamazepine

Table 1
General quality parameters from the different sampling points.

Sampling site Temperature ( C) Conductivity (mS cm2) TSS (mg L1)a E. coli (CFU 100 mL1)a

July 2009 March 2010 July 2009 March 2010 July 2009 March 2010 July 2009 March 2010
Blanes 1 26 1 18  1 951  47 1115  47 7.4 7.7 1.5  10þ5 3.2  10þ3
Blanes 2 26 1 17  1 957  46 1116  60 e e e e
Blanes 3 26 1 18  1 963  50 1125  60 2.8 3.3 2 2
River Tordera e 12  1 e 491  23 e e e e
TM 1 26 1 15  1 1033  19 981  58 11.8 8.4 3  10þ5 1.1  10þ4
TM 2 27 1 15  1 1090  29 1002  15 3.5 1.3 <1 <1
Tossa de Mar stream 21 1 12  1 714 2 315  8 e e e e
a
Consorci de la Costa Barva (www.ccbgi.org). Blanes 1: after secondary treatment, Blanes 2: after passing through the lamellar clarifier and Blanes 3: at the outlet of the
Blanes water reclamation plant. TM 1: after secondary treatment, TM 2: at the outlet of the Tossa de Mar water reclamation plant. CFU, colony-forming units.
98 V. Matamoros, V. Salvadó / Journal of Environmental Management 117 (2013) 96e102

and 2,4,5-TPA). Spiked samples were percolated through a previ-
ously activated polymeric solid-phase extraction cartridge (200 mg
Strata X). Elution was performed with 10 mL of hexane/ethyl ace-
tate (1:1). The eluted extract was evaporated until ca. 100 mL under
a gentle nitrogen stream and 186 ng of triphenylamine was added
as an internal standard. Finally, the vial was reconstituted to 300 mL
with ethyl acetate.
Methylation of the acidic carboxyl group was performed in a hot
GC injector (270  C) by adding 10 mL of TMSH solution
(0.25 mol L1in methanol) to a 50 mL sample before injection.
Derivatized samples were injected into a DSQ GCeMS (Thermo-
Finnigan, Dietrich, Germany) in the electron impact mode (70 eV
ionization energy). The chromatographic column was a TRB5-MS
(30 m  0.25 mm i.d., 0.25 mm film thickness) coated with 5%
diphenyl 95% dimethylpolysiloxane from Teknokroma (Sant Cugat
del Vallès, Spain). A volume of 2 mL of sample was injected in the
splitless mode. Chromatographic conditions, data processing and
validation of the methodology have been described elsewhere
(Matamoros and Bayona, 2006; Matamoros et al., 2010). The limit of
detection (LOD) and limit of quantification (LOQ) of the analytical
methodology were determined (using Milli-Q water) from the
mean of the background noise plus 3 or 10 times the standard
deviation of the background noise, respectively. LOD and LOQ
ranged from 1 to 40 ng L1 and from 3 to 80 ng L1, respectively.
Recoveries and repeatability were always higher than 90% and
lower than 20%, respectively.
2.5. Statistical analysis
Experimental results were statistically evaluated using the SPSS
v.15 package (Chicago, IL, US). Adjustment of data sets to a normal
distribution was always verified to ensure that parametric statistics
were applicable. Normal distributions were obtained by the
KolmogoroveSmirnov test. The correlation coefficient between the
concentration removal of the selected emerging contaminants and
their log Kow was calculated using parametric statistics (Pearson
coefficient).
3. Results and discussion
3.1. Emerging contaminants in WWTP effluents
The concentration of emerging contaminants in secondary-
treated wastewater effluents from Blanes and Tossa de Mar
WWTPs ranged from 6 ng L1 to 2061 ng L1 (Fig. 1). Diclofenac,
galaxolide and carbamazepine were the most abundant
(>1000 ng L1 on average), partially agreeing with earlier reports
that found diclofenac and carbamazepine to be the most recalci-
trant contaminants in conventional activated sludge WWTPs
(Heberer, 2002; Miège et al., 2009). Since it has been reported that
over 70% of galaxolide is eliminated in conventional WWTPs, the
abundance of this compound must be explained by its presence in
the raw wastewater (Carballa et al., 2005). In contrast, compounds

3000
Summer season
2500
Concentration (ng L-1)

2000

1500

1000

500

3000
Winter season
2500
Concentration (ng L-1)

2000

1500

1000

500

0
th ja lth l
hy p ide

se te
O To ide

lic nzo e

is th le, -O hm rin
N ca e

ic ne
zi n
e

nz sp te

ro ph pro e
ba a en

hl ih m ph n

nn sp n
Bi mic ate
C hen id
lo st A
ric ide

ba
im K lax ac

Be pho ona -

ic id
H but Ib iaz e
oe ro hy no
Fu hth en

)
Sa be lid

az in
yl n

ia a
hi p- C Ter on

-c l d -( yl ra
ap ci

yd yl u ol
h t

c i o fe
yl) sm io

D Ac
c
ro ala

ot ha

C ele ol
a n

Tr Me zo rt as but

am
Tr epi
D los
a r C rox

sp a
m
et eto ol

f i b ol
m ffe

or yd et e
f

a h
(2 y 2 c t e
xy na
G ofe

l p ro

n
i
l
ic
D

e
C

i
Tr
D

a
ot
nz
Be

Fig. 1. Seasonal occurrence of emerging contaminants in the secondary effluents from Blanes and Tossa de Mar WWTPs (n ¼ 20).
 V. Matamoros, V. Salvadó / Journal of Environmental Management 117 (2013) 96e102 99

such as ibuprofen, caffeine and methyl dihydrojamonate which are
often found at high concentrations in raw wastewaters, were
detected at low concentrations in the secondary effluents, probably
due to their high biodegradation rates (over 90%) in conventional
activated sludge WWTPs (Carballa et al., 2004; Kagle et al., 2009;
Ternes et al., 2004). The concentration of carbamazepine was
higher in winter than in summer as has been found in other studies
(Daneshvar et al., 2010; Palmer et al., 2008).
3.2. The effect of coagulation/flocculation-lamellar clarifier
Fig. 2 shows the removal efficiency of emerging contaminants
during coagulationeflocculation followed by lamellar clarifier at
Blanes WWTP. The elimination of emerging contaminants ranged
from no detectable removal to 50%. Although compounds sorbed to
the particulate matter were not determined in this study, due in
part to the low TSS concentrations (Table 1), we observed that
compounds with a log Kow >4 at pH ¼ 7e8 (galaxolide, tonalide,
celestolide, cashmeran, and octylphenol, see Table 1-SM) were
eliminated more efficiently from the aqueous phase. These com-
pounds are mainly adsorbed in the organic matter, which in turn
are eliminated by the lamellar clarifiers.
Some laboratory scale studies have found coagulatione
flocculation not to be suitable processes for the removal of cer-
tain antibiotics and other polar compounds such as naproxen and
ibuprofen (Adams et al., 2002). Nevertheless, Carballa et al. (2005)
observed that during coagulationeflocculation, lipophilic com-
pounds such as musks were adsorbed in the lipidic fractions of
the sludge, while acidic compounds such as diclofenac were
also adsorbed due to electrostatic interaction. Compounds
with lower Kd values, such as carbamazepine, ibuprofen and nap-
roxen, were reduced to a lesser extent (Carballa et al., 2005).
Gasperi et al. (2010) observed that in lamellar clarifiers used as
primary treatments at full-scale WWTPs, priority organic con-
taminants with a strong hydrophobic character (log Kow >4.5)
were removed to a significant extent (approx. 85%), while hydro-
philic compounds (log Kow <3.5) were poorly removed (<20%). In
our study, although the organic matter present was lower (TSS
value in Table 1), a statistical significant correlation between log
Kow at pH ¼ 8 and removal efficiency of emerging contaminants
was observed (p < 0.05, Pearson correlation coefficient ¼ 0.469),
indicating the high suitability of hydrophobicity for assessing
contaminant removal in the coagulation/flocculation-lammellar
clarifier reactor.

100
Coagulation-flocculation-lamellar Clarifier

80
(a) Bed filter-UV reactor-Chlorination
Removal efficiency (%)

60

40

20

*
0

100

Coagulation-flocculation-lamellar Clarifier
80 (b) Bed filter-UV reactor-Chlorination
Removal efficiency (%)

60

40

20

*
0 *
af e
ax e

ba rb e
az rin
O r e
na e

Ke iclo A

se ac
hm te
ol rt-O up an

et ri m ph n

ih l p lth l

oe C mo te
yl) les te
os ide

zi e
hy ic le

C tha id

ro sp )-

he ne

p n
l d ty thy no

Bi en n

Fu clof n

e
C on
al in

ar Te lid

ap in
M T 2-( tyl ofe

ia t

To lid

to sa
yd ho io
h c
et am zo

D pha

e
as la

s a
th e na

b e

id
Tr nol

ro en
m ut

sp zo
az e Ib er
lp a

G fe
ph tol

N ep
hy bu e e

D rof
xy ox
ja h

m
n
im n ia

c r
D cin th
ro zo

i
yd en
B

C
e,
hi p-t

or
H

hl
-c
ot

i(2
nz

Tr
Be

Fig. 2. Removal efficiency of emerging contaminants after coagulation/flocculation-lamellar clarifier and UV-chlorination reactor units in summer (a) and winter (b) seasons at
Blanes WWTP (n ¼ 10). * <LOQ.
100 V. Matamoros, V. Salvadó / Journal of Environmental Management 117 (2013) 96e102
A greater, presumably temperature-related, seasonality was
found in the elimination of hydrophobic compounds in the lamellar
clarifier. It has been established that the higher the temperature,
the faster the reaction, and the more effective the coagulation
(Bratby, 2006).
3.3. The effect of filtration-UV-chlorination
The effect of UV light radiation was evaluated after the effluent
passed through the bed filter-UV reactor-chlorination unit at Blanes
WWTP. Fig. 2 shows that the removal efficiency of the emerging
contaminants studied during this step was compound dependent.
In general, bed filter-UV light radiationechlorination was found to
be more efficient than coagulation/flocculation-lamellar clarifier.
As the most efficiently removed compounds were those that have
previously been identified as highly photodegradable in water
with UV treatment (i.e. diclofenac, ketoprofen and triclosan) (Kim
and Tanaka, 2009), the effect of UV light radiation seems to be
more significant in the elimination of emerging contaminants than
bed filtration and chlorination. Diclofenac and ketoprofen were
particularly abundant in the secondary effluents as biodegradation
or the sorption processes involved in the activated sludge WWTP
have little capacity to eliminate these compounds. Nonetheless, it
is important to take into consideration the possible effect of
chlorination as recent laboratory scale studies have observed
a moderate capacity of chlorine to oxidize certain pharmaceuticals
such as amoxicillin, salicylic acid, naproxen, diclofenac and indo-
methacine (Acero et al., 2010; Quintana et al., 2010).
Gagnon et al. (2008) found that UV radiation at 25 mJ cm2 was
only able to eliminate between 25% and 40% of diclofenac, naproxen
and triclosan, whereas Kim et al. (2009a) found that UV radiation at
923 mJ cm2 removed more than 90% of diclofenac and ketoprofen.
The power of the UV light radiation used in Blanes and Tossa de Mar
WWTPs (48e189 mJ cm2) was much higher than that reported by
Gagnon et al., but lower than that reported by Kim et al. Laboratory
studies with higher UV light radiation intensities or greater radia-
tion time exposure found that the elimination of these compounds
was over 90% (Kim and Tanaka, 2009; Kim et al., 2009b). The results
show almost no seasonality in the removal of emerging contami-
nants during filtration-UV-chlorination, which is consistent with
the little variation in the degree of physicochemical wastewater
treatment processes.
3.4. Identification of intermediate degradation products
It is difficult to identify intermediate degradation products
in full-scale water reclamation plants due to the low concentra-
tions of the target products in comparison with the matrix com-
ponents. Comparison of GCeMS chromatograms of the water
samples collected before and after lamellar clarifier and filtration-
UV-chlorination units at Blanes water reclamation plant allow
us to identify intermediate degradation products. Only 1-(8-
Chlorocarbazolyl)acetic acid (Fig. 2, supplementary data), a photo-
degradation intermediate product of diclofenac, was identified at
the three different sampling sites (Fig. 3). The compound was
identified by comparison with published mass spectra. The mass-
to-charge ratios (m/z) of the methyl ester derivative of the photo-
degradation intermediate are 213/241/273 (Poiger et al., 2001). 1-
(8-Chlorocarbazolyl)acetic acid was only observed after UV light
radiation treatment, in agreement with laboratory studies of the
effects of this treatment (Musa and Eriksson, 2009; Poiger et al.,
2001). Although it is also important to note that this compound
exhibits clear photohemolytic activity while diclofenac is practi-
cally inactive in the same conditions (Encinas et al., 1998), no in-
formation is available regarding its ecotoxicological effects.
0.4
1-(8-Chlorocarbazolyl)acetic acid
0.3
Relative area (A/A’)
(n=5)
Cl O
0.2 H
N
OH
0.1
0.0
BLANES 1 BLANES 2 BLANES 3
Fig. 3. Relative area abundance of diclofenac photodegradation intermediate prod-
uct (1-(8-Chlorocarbazolyl)acetic acid) at the Blanes water reclamation plant.
A ¼ abundance of the analyte; A0 abundance of the internal standard. Blanes 1: after
secondary treatment, Blanes 2: after passing through the coagulation/flocculation-
lamellar clarifier and Blanes 3: after passing through the filtration-UV-chlorination
reactor.
In summary, our results found that the content of emerging
contaminants is lower in the final reclaimed water than in the
secondary effluent, but also that reclaimed water contains degra-
dation by-products that may cause adverse effects on biota.
3.5. Overall removal efficiency
Table 2 shows the removal efficiencies of the 26 compounds
studied at the Blanes and Tossa de Mar water reclamation plants.
These compounds can be classified in three groups in accordance
with their removal efficiency: high removal (>70%, diclofenac and
ketoprofen), moderate removal (from 40% to 70%, triclosan and
naproxen) and poor or no removal (<30%, the remaining emerging
contaminants investigated). Although most compounds have been
classified as not being removed or having been removed only
poorly, the overall mass removal, calculated through the concen-
tration and removal of each individual compound, was around 60%.
This is explained by the high capacity of lamellar clarifier and UV
light radiation units to adsorb and photodegrade the most abun-
dant compounds (i.e. diclofenac, ketoprofen and galaxolide).
Whereas water reclamation technologies using ultrafiltration pro-
cesses achieve elimination efficiencies of around 80% and other
advanced processes, such as ozone and photo-Fenton reactions and
reverse osmosis, can give even better results (Klamerth et al., 2010;
Klavarioti et al., 2009; Teijon et al., 2010), the system described here
has the major advantage of being significantly more economic. The
total costs of UV irradiation are together with chlorine the lowest
(0.03e0.10 V m3) in comparison with the other disinfection
methods, roughly about 2e3 time lower than ozonation and 5e15
times lower than membrane filtration (Fuhrmann and Rudolph,
2009).
3.6. Occurrence of emerging contaminants in final receiving waters
Table 2 shows the concentration of emerging contaminants in
the final receiving waters, the River Tordera and the stream at Tossa
de Mar. The concentrations in the River Tordera were higher than
those found in the stream at Tossa de Mar, presumably as in the
case of Tossa de Mar some of the emerging contaminants were
eliminated by infiltration of the reclaimed water in the local lagoon
 V. Matamoros, V. Salvadó / Journal of Environmental Management 117 (2013) 96e102 101

Table 2
Overall removal efficiency and concentration of emerging contaminants in the final effluents of the two tertiary treatments systems and their receiving waters.

Name Blanes WWTP effluent (n ¼ 10) River Tordera Tossa de Mar WWTP effluent Tossa de Mar stream
(n ¼ 2) (ng L1) (n ¼ 10) (n ¼ 3) (ng L1)

Removal (%) Concentration Removal (%) Concentration

(ng L1) (ng L1)
Very efficiently removed (>70%)
Diclofenac 78  16 406  247 74  30 78  26 223  226 41
Ketoprofen 90  2 53  37 13  2 63  32 271  211 <4

Moderately removed (40e70%)

Triclosan 54  12 93  13 36  20 73  4 41  4 71
Naproxen 41  17 116  85 42  2 62  29 73  66 <2

Poorly or not removed (<40%)

Salicylic acid n.r. 342  92 122  36 n.r. 478  255 259  39
Benzothiazole 46 40  1 <39 9  13 59  3 <39
Hydrocinnamic acid n.r. 909  1221 <10 n.r. 199  134 198  43
Dimethyl phthalate 20  28 329  209 <50 69 199  147 111  12
Cashmeran 16  4 110  23 106  47 17  3 92  113 <5
Ibuprofen 46 23  1 40  10 n.r. 63  154 88  20
p-tert-Octylphenol 49  29 39  9 <12 46 49  24 24  2
Benzothiazole, 2-(methylthio)- 14  10 46  20 <10 28  40 66  76 <10
Tributyl phosphate 31 47  31 <25 11  16 50  31 <25
Methyl dihydrojasmonate 12  17 283  349 288  32 20  28 227  147 <32
Celestolide 54  15 19  23 17  1 28  39 20  25 <5
Tris(2-chloroethyl) phosphate 24  18 128  60 31  2 21  29 183  37 71
Diazinone 28  14 46  6 14  2 55  48 41  16 <10
Caffeine 9  12 135  59 130  75 n.r. 410  168 40  13
Galaxolide 26  1 1308  125 100  5 31  6 700  17 <12
Tonalide 38  3 410  63 51  7 27  9 272  65 <6
Terbutryn 36  5 72  23 23  3 65  31 72  40 <11
Carbamazepine 95 1162  1236 205  52 26  1 456  767 27  4
Oxybenzone 47  18 34  48 28  2 22  20 236  225 34  2
Bisphenol A 51  15 71 14  3 14  9 83 146  107
Furosemide 38  27 29  2 <12 72  4 99  97 <12

n.r. no removal.

system. Concentrations in the River Tordera were similar to those
observed in other Mediterranean rivers affected by anthropogenic
activities (Ginebreda et al., 2010). Carbamazepine and methyl
dihydrojasmonate were the most abundant compounds in the
receiving waters followed by caffeine, galaxolide, celestolide and
salycilic acid. All other compounds were found at much lower
concentrations. The presence of carbamazepine could be accounted
for by the discharge from the Blanes WWTP, but the abundance of
other compounds such as caffeine cannot be explained by the in-
fluence of the Blanes WWTP as they are efficiently eliminated in
this type of plant. It would therefore seem clear that other waste-
water inputs into the river upstream of the Blanes WWTP may have
contributed to these results. When concentrations in the rivers
were compared with concentrations found in reclaimed waters, the
former were found to be lower, presumably as a result of dilution.
Studies in different Mediterranean rivers have found similar results
(Calderón-Preciado et al., 2011).
4. Conclusions
capacity of lamellar clarifier and UV light radiation units in elimi-
nating the most abundant compounds. There was a lesser presence
of selected emerging contaminants in receiving waters than in
reclaimed waters.
In summary, each treatment option has its own limitations and
benefits in removing trace levels of emerging contaminants.
However, in this particular case, coagulationeflocculation followed
by lamellar clarifiers and filtration-UV-chlorination were shown to
have potential as an efficient removal technologies. This technology
should particularly be considered in cases where the end use of the
recycled water is not human consumption.
Acknowledgments
This study has been financed by the Spanish Ministry of Science
and Innovation; project CTM2008-0647-C02-02/TECNO. Dr. VM
received a Juan de la Cierva contract from the Spanish Ministry of
Science and Innovation. We would like to thank Lluis Sala and the
plant operators from Blanes and Tossa de Mar WWTPs (Consorci de la
Costa Brava) for their collaboration during the sampling campaigns.

The concentrations of 25 emerging contaminants in two WWTP

secondary effluents ranged from 6 ng L1 to 2061 ng L1. Diclofe-
nac, carbamazepine and galaxolide were the most abundant. The
results showed that coagulationeflocculation followed by lamellar
clarification removed hydrophobic compounds (e.g. galaxolide and
tonalide) whereas filtration-UV-chlorination removed photo-
degradable emerging contaminants (e.g. ketoprofen, triclosan and
diclofenac). A photodegradation intermediate product from diclo-
fenac called 1-(8-Chlorocarbazolyl)acetic acid was only detected
after the filtration-UV-chlorination unit. Although the removal ef-
ficiency of individual emerging contaminants was in general lower
than 30%, overall mass removal efficiency was 60% due to the high
Appendix A. Supplementary material
Supplementary material related to this article can be found at
http://dx.doi.org/10.1016/j.jenvman.2012.12.021.
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