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ARTICLE IN PRESS

Water Research 38 (2004) 2918–2926

Behavior of pharmaceuticals, cosmetics and hormones in a


sewage treatment plant
Marta Carballaa, Francisco Omila,*, Juan M. Lemaa, Mar!ıa Llompartb,
Carmen Garc!ıa-Jaresb, Isaac Rodr!ıguezb, Mariano Gómezc, Thomas Ternesd
a
Department of Chemical Engineering, School of Engineering, University of Santiago de Compostela,
E-15782 Santiago de Compostela, Spain
b
Department of Analytical Chemistry, Institute of Food Science, University of Santiago de Compostela,
E-15706 Santiago de Compostela, Spain
c
Central Laboratory, Aquagest Galicia, Isidro Parga Pondal, 9, E-15702 Santiago de Compostela, Spain
d
Bundesanstalt für Gewässerkunde, Am Mainzer Tor 1, D-56068 Koblenz, Germany
Received 31 July 2003; received in revised form 22 January 2004; accepted 10 March 2004

Abstract

Two cosmetic ingredients (galaxolide, tonalide), eight pharmaceuticals (carbamazepine, diazepam, diclofenac,
ibuprofen, naproxen, roxithromycin, sulfamethoxazole and iopromide) and three hormones (estrone, 17b-estradiol and
17a-ethinylestradiol) have been surveyed along the different units of a municipal Sewage Treatment Plant (STP) in
Galicia, NW Spain. Among all the substances considered, significant concentrations in the influent were only found for
the two musks (galaxolide and tonalide), two anti-inflammatories (ibuprofen and naproxen), two natural estrogens
(estrone, 17b-estradiol), one antibiotic (sulfamethoxazole) and the X-ray contrast medium (iopromide), where the other
compounds studied were below the limit of quantification. In the primary treatment, only the fragrances (30–50%) and
17b-estradiol (20%) were partially removed. On the other hand, the aerobic treatment (activated sludges) caused an
important reduction in all compounds detected, between 35% and 75%, with the exception of iopromide, which
remained in the aqueous phase. The overall removal efficiencies within the STP ranged between 70–90% for the
fragrances, 40–65% for the anti-inflammatories, around 65% for 17b-estradiol and 60% for sulfamethoxazole.
However, the concentration of estrone increased along the treatment due to the partial oxidation of 17b-estradiol in the
aeration tank.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Pharmaceuticals; Cosmetics; Hormones; PPCP; Wastewaters; Sewage treatment plant; Adsorption; Elimination;
Antibiotics; Estrogens; Anti-inflammatories

1. Introduction chemicals will be collectively referred to as ‘‘Pharma-


ceutical & Personal Care Products’’ (PPCPs).
Municipal wastewaters contain many organic com- Generally, drugs are absorbed by the organism after
pounds, among them, active ingredients of pharmaceu- intake and are subject to metabolic reactions. However,
ticals and personal care products, which are used in a significant fraction of the original substances leave
large quantities throughout the world. Both groups of human or animal organisms unmetabolized via urine or
feces being therefore emitted into raw sewage, sewage
*Corresponding author. Tel.: +34-981-56-31-00x16778; fax: sludge or manure. For example, Høverstad et al. [1]
+34-981-54-71-68. determined several antibiotics in human feces during 6
E-mail address: eqomil@usc.es (F. Omil). days of regular application. Furthermore, some of the

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.03.029
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M. Carballa et al. / Water Research 38 (2004) 2918–2926 2919

excreted metabolites can even be transformed back to the receiving environment [13]. In this way, many PPCPs
the original active drug [2]. remain in the aqueous phase, such as the anti-
inflammatories and the antibiotics, whereas some of
1.1. Sewage treatment plants them are adsorbed to the sludges, such as the musks and
the estrogens [14].
Some of the most representative PPCPs found in The overall removal rates published in literature vary
Sewage Treatment Plants (STP) are antibiotics, lipid strongly. In Germany, reported efficiencies range from
regulators, anti-inflammatories, antiepileptics, tranquil- 10% to 90% depending on the nature of the compound
lizers, contrast media and contraceptives with very [5]. In Brazil, removal efficiencies for pharmaceutical
different chemical structures. Because of them, a polar compounds vary from 12% to 90%, where the
considerable effort is being made in order to develop efficiencies obtained in activated sludge processes were
the analytical techniques needed to quantify their higher than in biofilters [15]. Another study, carried out
occurrence in effluents, but also to assess their chemical in the USA concluded that many PPCPs (around 80%)
properties, their biodegradability potential, etc. were removed [30]. In all these cases, removal includes
Recent works have reported the presence of a large both degradation and adsorption and the difference
variety of PPCPs in STP effluents and surface between both mechanisms has not been assessed yet. In
waters, with concentrations up to several mg l 1 [23]. In the case of polar compounds, such as carboxylic acids,
fact, more than 50 PPCPs have been detected during for which the adsorption effects are expected to be very
the last years in different environmental samples, due low, the main mechanism of elimination is attributed to
to the continuous improvement of the analytical biodegradation. However, the studies carried out by
techniques. Many of these samples have been taken Schäfer and Waite [16] indicate that less than 10% are
from wastewater [3–5], but also from surface or effectively biodegraded.
groundwaters [6,7]. Significant differences in the concentrations found can
Most of these compounds come either from domestic be observed between different geographical areas as
sewage or from hospital or industrial discharges and mentioned by Heberer [17] for fragrances and their
enter municipal STPs. Modern STPs can effectively occurrence in the environment. So far, most of the
accomplish carbon and nitrogen removal, as well as studies focused on PPCPs have been carried out in the
microbial pollution control. However, urban STPs USA and central and northern countries of the EU, both
normally receive streams that contain a lot of different areas with moderate climates. On the other hand, data
trace polluting compounds (synthetic and natural), for from treatment plants located in Southern Europe are
which conventional treatment technologies have not scarce, a lack of information that should be dealt with to
been specifically designed. Their removal efficiencies are have a complete picture of the occurrence and fate of
influenced, apart by the chemical properties of specific these compounds in the whole EU, as well as to compare
compounds, by microbial activity and environmental the situation in areas with moderate and hot climates.
conditions [8–10]. The aim of this study was therefore to investigate the
Recent studies have clearly shown that the elimina- behavior of 13 cosmetic and pharmaceutical compounds
tion of PPCPs in municipal STPs is often incomplete [5], belonging to different groups (musks, anti-inflamma-
with efficiencies ranging between 60% and 90% for a tories, antiepileptics, tranquillizers, antibiotics, natural
variety of polar compounds. Their removal can be and synthetic estrogens and contrast media) along the
attributed not only to biodegradation, but also to different units of a municipal STP located in Galicia
adsorption onto solid surfaces [11,12]. As a conse- (NW Spain). The removal efficiency from the water
quence, significant fractions of PPCPs are discharged phase of each substance in each particular unit has been
with the final effluent of the STP into the aquatic determined.
environment. Besides, these substances can also imply
an important pollution source for the soil if primary and
secondary sludges (to which they are adsorbed) are 2. Materials and methods
spread on land.
A major factor influencing the efficiency of pollutants 2.1. Sewage treatment plant
removal from water is their ability to interact with solid
particles, both natural (clay, sediments, microorgan- The sewage treatment plant studied in this work
isms) or added to the medium (active carbon, coagu- corresponds to a population of approximately 100,000
lants), because this facilitates their removal by physical– inhabitants located in Galicia (NW Spain). The plant
chemical (settling, flotation) or biological processes includes three main sections: pre-treatment, primary
(biodegradation). However, compounds with low ad- treatment and secondary treatment (Fig. 1). After the
sorption coefficients tend to remain in the aqueous reception and pumping of the inlet wastewaters, the pre-
phase, which favors their mobility through the STP and treatment section comprises units for coarse screening
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2920 M. Carballa et al. / Water Research 38 (2004) 2918–2926

SO SPS SB SSS SF

Pretreatment Primary Biological Secondary


Sedimentation reactor Sedimentation

Air Effluent

Air

Influent
Reception
of waste
Solid waste sludges

Treatment
of sludges

Recirculation of liquid supernatant Solid waste

Fig. 1. Diagram of the municipal sewage treatment plant and location of the sampling points.

(bar racks), fine screening and aerated chambers for grit 2.2. Analytical methods
and fat removal. The primary treatment is carried out in
circular sedimentation tanks. Finally, the secondary Total solids (TS), volatile solids (VS), total suspended
treatment is carried out in biological reactors using the solids (TSS), volatile suspended solids (VSS), pH and
conventional activated sludge process (mixed reactors total and soluble chemical oxygen demand (CODt and
followed by a sedimentation tank). The supernatant of CODs, respectively) were determined by Standard
the secondary sedimentation unit constitutes the final Methods [18]. Total organic carbon (TOC) was mea-
effluent of the plant. sured with a Shimazdu model TOC-5000 total organic
The excess of secondary sludges, together with the carbon analyzer, TOC concentrations were calculated by
solids obtained from the primary sedimentation, are the difference between total carbon (TC) and inorganic
treated in a specific unit from which a solid waste and a carbon (IC).
liquid stream, recycled to the inlet of the plant, are NO2 , NO3 , Cl , PO34 and SO24 were analyzed by
obtained (Fig. 1). capillary electrophoresis (Waters Capilary Ion Analyzer,
The sampling points for analysis are the following CIA model). Sodium chromate was used as electrolyte
(Fig. 1): (i) inlet to the grit removal unit (So); (ii) inlet to (0.005 mol l 1) as well as an electro-osmotic modifier
the primary sedimentation tank (Sps); (iii) inlet to the CIA-Pakt OFM Anion BT (Waters) 0.46 mM [19].
biological reactor (Sb); (iv) inlet to the secondary The soluble content of the fragrances, anti-inflamma-
sedimentation tank (Sss) and; (v) outlet of the secondary tories, carbamazepine and diazepam was determined
sedimentation tank (Sf). after solid-phase extraction (SPE) of 500 ml samples
Three analytical campaigns, during 1 year, were using 60 mg OASIS HLB cartridges (Waters, Milford,
carried out. Taking into account that the operating MA, USA). Meclofenamic acid and dihydrocarbamaze-
hydraulic retention time (HRT) in the STP is 24 h, the pine were added to the samples as surrogate standards.
integrated samples were obtained by mixing the 24 All compounds were quantitatively eluted from the
liquid samples collected every hour by an automatic cartridge using 3 ml of ethyl acetate. This extract was
device at each sample point. All compounds were then divided into two fractions: one of them was used
measured during the three integrated campaigns, with for the direct determination of the soluble content of
the exception of estrogens, antibiotics and contrast carbamazepine, diazepam and fragrances; the second
media, which were only analyzed for the samples one was employed for the determination of the anti-
obtained in the last campaign (April 2002). In order to inflammatory species. In the latter case compounds were
avoid estrogens degradation during the samples trans- silylated previously to their gas chromatographic
portation to Germany, the pH was adjusted to 2 after separation according to a previously published method
collecting the samples. [20]. In both cases, GC/MS was used to determine the
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M. Carballa et al. / Water Research 38 (2004) 2918–2926 2921

concentration of the investigated compounds in the SPE chemical structures of the selected compounds are
extract. shown in Fig. 2.
In the cases of galaxolide and tonalide, complemen-
tary methodology was used to determine the overall 2.3. Calculations
amount present in samples containing solids: the total
load. A previously developed method [21,22], based on a Removal efficiencies from the aqueous phase for all
solid phase micro-extraction (SPME) technique using PPCPs were calculated taking into account the measured
PDMS/DVB fiber was used for this purpose. The whole concentration at the inlet of the plant (So), inlet of the
sample, including the soluble fraction and the solid biological reactor (Sb) and the final effluent (Sf). The
particles, was thermostatized and magnetically stirred percentage related to the primary treatment was then
during the extraction process. The SPME fiber was calculated as (So Sb)/So  100, the percentage related
exposed to the headspace over the sample. After the to the biological reactor was obtained using (Sf Sb)/So
sampling time (30 min), the fiber was desorbed into the and the overall efficiency using (So Sf)/So. In all cases,
GC injector and GC-MS analysis was performed. So was used as the reference in order to be able to
Due to their occurrence as ingredients in all kinds of compare and to add the partial percentages and obtain
cleansing products and cosmetics, the risk of sample the overall one.
contamination with musks during analyses is significant,
so it is advisable to take extreme precautions to avoid
sources of interference in the laboratory environment. 3. Results and discussion
To prevent sample contamination, appropriate steps
should be taken. Blank samples of the whole process Table 2 shows the values obtained in the different
have been analyzed every set of samples to discard integrated campaigns for the main characteristics of the
potential contamination. In addition, spiked water wastewaters, such as solids content (total and sus-
samples have been analyzed periodically to evaluate pended), chemical oxygen demand, total organic carbon,
the performance of the method. nitrogen, chloride, sulfate and phosphate are shown.
Antibiotics, X-ray contrast media and estrogens were The overall efficiencies achieved for COD and TSS
analyzed by the group of Dr. Ternes in Germany. along the entire STP were 80–94% and 92–94%,
Antibiotics and X-ray contrast media were analyzed by respectively.
LC electrospray tandem MS after an enrichment step
using an SPE method and elution with methanol [23]. 3.1. Occurrence of drugs in wastewaters
Estrogens were analyzed by GC (ion trap) MS/MS after
an enrichment step using an SPE method, elution with Among all PPCPs considered in this work, the
acetone and derivatization with MSTFA/DTE/TMSI following have been detected in the wastewaters
for 1 h at 60 C [24]. investigated: galaxolide and tonalide (fragrances), ibu-
Quantification limits and recoveries are given in profen and naproxen (anti-inflammatories), sulfa-
Table 1. Values given for the different samples of the methoxazole (antibiotic), estrone and 17b-estradiol
STP considered in this work correspond to the mean (natural estrogens) and iopromide (contrast medium).
value of two aliquots of each composite sample. The However, diazepam, carbamazepine, diclofenac, roxi-

Table 1
Selected PPCPs, limits of detection (LOD) and quantification (LOQ) in ng l 1, and recovery rates (%) of the analytical methods

Name Application CAS Formula LOD LOQ Recovery (%)

Galaxolide Fragrance 1222-05-5 C18H26O 1.2 4 88


Tonalide Fragrance 1506-02-1 C18H26O 1.8 6 90
Diazepam Tranquillizer 439-14-5 C16H13ClN2O 18.9 63 99
Carbamazepine Antiepileptic 298-46-4 C15H12N2O 22.2 74 67
Diclofenac Anti-inflammatory 15307-86-5 C14H11Cl2NO2 16.7 50 105
Ibuprofen Anti-inflammatory 15687-27-1 C13H18O2 6.7 20 90
Naproxen Anti-inflammatory 22204-53-1 C14H14O3 6.7 20 88
Roxithromycin Antibiotic 80214-83-1 C41H76N2O15 6.7 20 75
Sulfamethoxazole Antibiotic 723-46-6 C10H11N3O3S 6.7 20 75
Iopromide Contrast medium 73334-07-3 C18H24I3N3O8 6.7 20 75
Estrone Natural estrogen 53-16-7 C18H22O2 0.5 1 84
17b-estradiol Natural estrogen 50-28-2 C18H24O2 0.5 1 80
17a-ethinylestradiol Synthetic estrogen 57-63-6 C20H24O2 0.5 1 82
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Musks Pharmaceuticals
O
N
O
N
H3C
O N
C NH 2

Cl O
Galaxolide Tonalide
Diazepam Carbamazepine

HOOC H
Cl
COOH N

COOH
O
Cl
Ibuprofen Naproxen Diclofenac

R1
CH3 OH
O N
O HO OR 2
H OH N OH
H 2N S N HO I I
O O O H
O O
N O O N
O O O CH 3
H3C N
I O
H
OH
O OH
OH

sulfamethoxazole Roxithromycin Iopromide

Hormones
O OH HO

HO HO HO

Estrone 17β-estradiol 17α-ethinylestradiol

Fig. 2. Chemical structures of the PPCPs selected.

thromycin and 17a-ethinylestradiol were below the had high percentages of treated sewage (maximum
quantification limits (Table 1). concentrations of 10 mg l 1).
Table 3 shows the concentrations of the PPCPs The acidic compounds, ibuprofen and naproxen, were
detected during the three sampling campaigns at the detected in the ranges 2.6–5.7 and 1.8–4.6 mg l 1,
different sampling points. significantly higher than the ones previously reported
by Stumpf et al. [26] in a Brazilian STP influent, with
3.2. Concentration in raw wastewaters concentrations around 0.3 and 0.6 mg l 1, respectively.
In the cases of selected antibiotics, sulfamethoxazole
Apart from the usual variation between samples at the was quantified with concentrations of around 0.6 mg l 1
inlet of the STP (point So), it can be seen that all these whereas roxithromycin was below the LOQ. According
compounds are present in the range of 0.6–6.6 mg l 1. to the results reported by Hirsch et al. [23] these values
The two polycyclic musks, galaxolide and tonalide, are in the same range as those reported for German
were detected in the ranges 2.1–3.4 and 0.9–1.7 mg l 1, wastewaters. Iopromide was found in the range of
respectively. These values are lower than those reported 6–7 mg l 1, quite a high value comparing it with other
by Heberer et al. [25] in surface waters in Berlin, which studies [27]. Finally, the natural estrogens detected in
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Table 2
Characterization of the wastewaters along the different units of the STP (in mg l 1)

Month Sample TS VS TSS VSS CODt CODs TC TOC TN Cl SO24 HPO24

October 2001 So 581 330 258 191 331 137 51.2 22.6 16.5 42.6 — —
Sps 553 308 223 175 299 134 70.2 34.3 21.7 56.3 42.4 4.0
Sb 368 195 65 55 107 99 52.6 20.5 19.5 54.5 32.5 —
Sss 2573 1843 2234 1787 1432 436 79.2 55.6 9.1 59.0 43.6 12.6
Sf 323 105 20 18 49 40 28.1 13.0 11.3 51.6 40.8 —

January 2002 So 863 500 298 235 503 149 81.1 40.8 12.7 51.3 — —
Sps 835 418 268 220 497 136 72.6 36.2 26.0 85.6 92.7 1.9
Sb 500 240 85 78 242 84 66.8 37.4 21.2 53.0 59.8 4.0
Sss 2510 1878 2123 1718 3196 259 103.0 74.3 19.7 57.0 63.9 24.1
Sf 335 118 23 18 30 14 41.2 17.2 13.9 50.3 44.9 —

April 2002 So 530 305 258 207 — 265 53.8 23.0 18.1 45.1 — —
Sps 515 295 243 197 275 172 45.5 17.5 15.9 41.9 48.2 3.9
Sb 500 195 170 88 272 145 61.3 30.0 15.6 51.1 76.0 1.7
Sss 1110 695 860 697 2017 811 234.7 218.0 6.2 50.5 76.2 5.9
Sf 345 110 15 15 56 52 28.5 11.8 9.8 48.4 73.3 1.1

Table 3
Profiles of galaxolide (GLX), tonalide (TON), ibuprofen (IBU), naproxen (NPX), sulfamethoxazole (SFMT), estrone (E1), estradiol
(E2) and iopromide (IOP) along the different units of the selected municipal STP

Month Sample GLX TON IBU NPX SFMT IOP E1 E2


(mg l 1) (mg l 1) (mg l 1) (mg l 1) (mg l 1) (mg l 1) (ng l 1) (ng l 1)

October 2001 So 2.10 0.90 2.75 3.45 nm nm nm nm


Sps 4.40 1.50 2.83 3.75 nm nm nm nm
Sb 1.40 0.60 2.84 3.48 nm nm nm nm
Sss 45.40 3.25 0.20 1.40 nm nm nm nm
Sf 0.60 0.20 0.91 1.85 nm nm nm nm

January 2002 So 3.40 1.69 5.70 4.60 nm nm nm nm


Sps 3.10 1.63 5.80 4.10 nm nm nm nm
Sb 1.60 0.97 5.80 4.80 nm nm nm nm
Sss 28.70 14.78 0.60 2.10 nm nm nm nm
Sf 0.50 0.15 2.10 2.60 nm nm nm nm

April 2002 So 3.18 1.53 2.64 1.79 0.58 6.60 2.40 nm


Sps 2.30 1.14 2.81 1.78 0.47 7.50 2.40 3.00
Sb 1.82 0.94 2.95 1.59 0.64 7.20 3.40 2.40
Sss 17.72 7.82 0.52 0.65 0.25 8.80 nm oLOQ
Sf 0.49 0.16 0.97 0.80 0.25 9.30 4.40 oLOQ

nm: not measured.

these wastewaters were in the range of 2–3 ng l 1 3.3. Behavior of PPCPs along the STP
whereas 17a-ethinylestradiol was below the LOQ. These
values are low, even in the case of natural estrogens, Fig. 3 shows the removal efficiencies calculated during
since previous works have given 15 and 27 ng l 1 for both the primary and the secondary treatments.
17b-estradiol and estrone, respectively, in municipal It can be seen (Fig. 3a) that fragrances are well
German STPs; or 21 and 40 ng l 1, respectively, in removed during the primary treatment, with values of
Brazilian STPs [24]. around 40% in most cases, as well as 17b-estradiol
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100 100
80
80
60
40 60
Removal (%)

Removal (%)
20
0 40
-20
20
-40
-60 0
-80
-100 -20
(A) GLX TON E1 E2 (B) IBU NPX SFMT

Fig. 3. Removal efficiencies (%) obtained for the PPCPs detected in the STP during primary, biological and overall treatment.

(20%). These efficiencies calculated for both types of clear indication of the important adsorption of these
PPCPs are closely related to those obtained for neutral compounds to solids, especially on the sludges
suspended solids which indicates that adsorption onto from the biological reactor. The overall removal
solid particles is the key mechanism involved. In fact, efficiencies from the water phase along the plant were
among all the substances studied in this work, these 70–85% for galaxolide and 75–90% for tonalide.
compounds are more likely to have a high partition In the cases of the anti-inflammatories detected, signi-
coefficient between the solid and liquid phase. ficant overall removal efficiencies were also achieved
However, no significant reduction was observed in the (60–70% for ibuprofen, 40–55% for naproxen),
pre-treatment and sedimentation steps for ibuprofen and although the elimination only took place during the
naproxen (Fig. 3b). This is concordant with their acidic biological treatment.
structures, with very low solid–liquid partition coeffi- Sulfamethoxazole was quantified in these waste-
cients, which results in their presence mainly in the waters, which is removed, around 67%, during the
aqueous phase. Previous works carried out in a Brazilian biological step. Similar average concentrations of this
STP report removal efficiencies of around 75% and 78% substance (below 1.0 mg l 1) were reported in the effluent
for both compounds, respectively [26]. The same of other STP [23].
behavior was observed for sulfamethoxazol, iopromide Concerning the hormones, 17b-estradiol was removed
and estrone. Furthermore, their concentration is higher during the biological treatment (47%), resulting in
after their passage through the primary sedimentation concentrations below the LOQ in both the effluent of
tank. These results are likely to be due to the analytical this unit and of the overall plant. On the contrary,
deviation caused by the different characteristics of the estrone concentrations increased over the course of
waters. However, in the particular case of the estrone, a treatment, illustrating the fact that under oxidizing
higher concentration is always detected at the end of this conditions, 17b-estradiol is quickly converted into
step very likely due to the oxidation of the 17b-estradiol estrone, which is much more slowly degraded [15].
present, which explains the high negative removal Taking into account the initial concentration of the 17b-
efficiencies obtained for the estrone and the positive estradiol (3 ng l 1) and the limit of quantification (LOQ)
reduction of 17b-estradiol. Furthermore, during the first of 1 ng l 1, it can be assumed that at least 2 ng l 1 were
steps of the treatment, the concentrations of both removed, which agrees with the concentration detected
natural estrogens increase, which can be explained by for the estrone. As mentioned before for the primary
the cleavage of the glucuronides (Fig. 3a). treatment, this hypothesis would explain the negative
All the PPCPs detected, except iopromide, are removal efficiencies obtained for the estrone (Fig. 3a).
removed during biological treatment with efficiencies The results obtained for the investigated contrast
between 30% and 75%. The elimination of musks in this medium, iopromide, indicate that there is no significant
case (30–40% for galaxolide, 45–50% for tonalide) once removal of this compound throughout the plant. In fact,
again comprises adsorption and biodegradation. It is these compounds are designed to be highly stable so they
important to mention the high concentration peaks for are not readily biodegradable [27], although some batch
galaxolide and tonalide in the samples containing solids experiments carried out with activated sludges yielded
(total load), especially in the outlet of the biological biotransformation into two metabolites but no miner-
reactor (point Sss, Table 3). When these samples were alization [28].
filtered (to obtain the soluble load), the concentra- With the exception of the fragrances, all the other
tions in the liquid were extremely low (around 2 and compounds analyzed in this work have been measured
0.5 mg l 1 for galaxolide and tonalide, respectively), a in filtered samples only. However, as it is evidenced in
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M. Carballa et al. / Water Research 38 (2004) 2918–2926 2925

this work for tonalide and galaxolide, previous studies consideration the treatment of the excess of sludges,
have already shown that unfiltered samples can give a topic which requires a further study.
more complete information about the real presence of
these substances in the environment [14,29]. It is
important to take into account that even the PPCPs According to the conclusions stated before, some
with medium or low partition coefficients could be modifications or improvements can be implemented in
present mainly in the solid phase in streams containing a existing STPs. In the primary treatment (coagulation–
high suspended solids concentration, such as those flocculation and flotation units) the use of some
obtained from purges or recycling sludges from biolo- additives as well as the proper adjustment of the
gical reactors. operating conditions could be a tool to remove PPCPs
from the water phase prior to the biological treatment.
During biological treatment, the variation of opera-
tional parameters, such as solids retention time (SRT),
4. Conclusions or the combination of anoxic/aerobic steps could
improve the efficiency. Finally, the concentrations of
A group of 13 PPCPs corresponding to different kinds some PPCPs in sludges are expected to be quite high,
of substances (musks, pharmaceuticals and hormones) and therefore an effort should be made to quantify this
has been used as an indicator of the presence of this type load, either by developing analytical techniques to
of pollution in the municipal wastewaters generated by a measure PPCPs concentrations in sludge samples or by
city of around 100,000 inhabitants in Galicia (NW the determination of adsorption coefficients (Kd) to
Spain). Most of the few works found in literature on this calculate indirectly those concentrations.
issue study the overall removal of PPCPs along STPs
(difference between the influent and effluent loads),
being the main goal of this work, the assessment of their
Acknowledgements
fate along the different units in order to evaluate the
possible improvements for enhancing the removal
This work was supported by the EU Project Poseidon
efficiency.
(EVK1-CT-2000-00047).
The eight compounds which were detected in raw
wastewaters (galaxolide, tonalide, ibuprofen, naproxen,
sulfamethoxazole, estrone, 17b-estradiol and iopromide)
had a different behavior along the units of STP: References

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adsorption onto solid surfaces allows an important enterol 1986;21:997–1003.
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vated sludges) all compounds detected have been Lebensmittelhygiene 1986;37(4):99–102 (in German).
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