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Water Research 39 (2005) 4790–4796
www.elsevier.com/locate/watres
Removal of cosmetic ingredients and pharmaceuticals insewage primary treatment
Marta Carballa, Francisco Omil�, Juan M. Lema
School of Engineering, Department of Chemical Engineering, University of Santiago de Compostela,
E-15782 Santiago de Compostela, Spain
Received 5 November 2004; received in revised form 12 September 2005; accepted 12 September 2005
Available online 24 October 2005
Abstract
Two physico-chemical processes, coagulation–flocculation and flotation, have been assessed for enhancing the
removal of some selected pharmaceutical and personal care products (PPCPs) present in sewage. Eight compounds,
representative of three main groups of PPCPs according to their physico-chemical properties, have been selected:
lipophilic compounds (the synthetic musks Galaxolide and Tonalide), neutral compounds (the tranquillizer Diazepam
and the antiepileptic Carbamazepine) and acidic compounds (the anti-inflammatories Ibuprofen, Naproxen and
Diclofenac). During the coagulation–flocculation assays, the main parameters considered were the selection of the
additives, their doses and the temperature of operation (12 or 25 1C). Musks—which are highly lipophilic and
Diclofenac—with significant sorption affinity—were removed around 50–70% at both temperatures independently of
the dose and type of coagulant used. However, the rest of the compounds, which are more hydrophilic, were affected to
a lesser degree (with maximum reductions below 25%). The exceptions to this behavior were Carbamazepine and
Ibuprofen, which were not removed under any condition tested. During the flotation assays, the parameters studied
were the initial content of fat in wastewaters and temperature. Again, musks were removed to a greater degree
(35–60%), followed by Diazepam (40–50%) and Diclofenac (20–45%) and, to a lesser extent, Carbamazepine
(20–35%), Ibuprofen (10–25%) and Naproxen (10–30%). The best results were always obtained at 25 1C, although in
some cases the operation at 12 1C gave similar results. The removal of musks and neutral compounds was higher in
wastewaters with a high fat content (around 150mg l�1).
r 2005 Elsevier Ltd. All rights reserved.
Keywords: Pharmaceuticals; Musks; Sewage; Coagulation–flocculation; Flotation; Adsorption; Fat; Temperature
1. Introduction
Pharmaceuticals and personal care products (PPCPs)
constitute a diverse group of chemicals that have
recently been recognized as particular contaminants of
the aquatic environment, especially in urbanized areas
e front matter r 2005 Elsevier Ltd. All rights reserve
atres.2005.09.018
ing author. Tel.: +34 981 59 44 88x16778;
80 50.
ess: eqomil@usc.es (F. Omil).
(Daughton and Ternes, 1999). PPCPs comprise all
prescription and over-the-counter drugs, diagnostic
agents, and other consumer chemicals, such as poly-
cyclic musk compounds frequently used as fragrances in
perfumes and other household products.
Due to the large amount of PPCPs consumed in
developed societies, significant concentrations of these
compounds can be found in wastewaters (Ternes, 1998;
Kanda et al., 2003; Kolpin et al., 2004; Cargouet et al.,
2004). However, conventional sewage treatment plants
d.
ARTICLE IN PRESSM. Carballa et al. / Water Research 39 (2005) 4790–4796 4791
(STPs) have been reported not to be an effective barrier
to these substances because of their low concentrations
and specific metabolic properties (Paxeus, 2004). There-
fore, those compounds which resist the treatment
processes commonly used in STPs or other transforma-
tions which can naturally occur in the environment, can
end up in surface and groundwaters, as well as in
sediments and soils.
Different mechanisms, such as sorption, biodegrada-
tion, volatilization and fotooxidation, can be considered
for PPCPs removal in STPs. Although in many cases,
the differences between them cannot be easily distin-
guished, recent works (POSEIDON Project (EVK1-CT-
2000-00047), 2005) have concluded that only two of
them, microbial degradation and sorption to suspended
solids, are really relevant. The effectiveness of these
removal mechanisms greatly depends on the physico-
chemical properties and the chemical structure of each
substance.
1.1. Physical properties of PPCPs
The sorption of micropollutants onto solids and,
accordingly, their behavior during the physico-chemical
treatment, depends basically on their physico-chemical
properties, such as lipophilicity or acidity. Two types of
coefficients have been mostly used to determine the
sorption effectiveness and the affinity of a given
substance to organic matter: the octanol-water partition
coefficient (Kow) and the organic carbon partition
coefficient (Koc). Kow is defined as the ratio between
the equilibrium concentrations of a certain compound in
octanol and water at a specific temperature and Koc
relates the concentrations sorbed to organic carbon and
Table 1
Physico-chemical properties of the PPCPs considered in this work (w
Galaxolide Tonalide Diclofenac Diazep
Structure
Solubility 1.8� 10�3a 1.2� 10�3a 2.4� 10�3a,b 5.0� 1
pKa — — 4.0–4.2a,b 3.3–3.4
logKow 5.9–6.3a 4.6–6.4a 4.5–4.8a,b 2.5–3.0
logKdc: 3.3–3.7 3.4–3.7 1.2–2.7 1.3–1.6
aLiebig (2004).bSyracuse Research Corporation (2004).cTernes et al. (2004).dKummerer (2000).eJones et al. (2002).fThe Kd value for Naproxen has been assumed based on its similar p
sludge (data not shown).
dissolved in water. However, some limitations have been
found in literature (Holbrook et al., 2004; Lai et al.,
2000) for the applicability of these coefficients to explain
the sorption behavior of some PPCPs. Therefore, the
solid–water distribution coefficient (Kd), defined as the
ratio between the concentrations of a substance in the
solid and in the aqueous phase at equilibrium conditions
(Eq. (1)), has been proposed as the most suitable
parameter (Schwarzenbach et al., 2003; Ternes et al.,
2004):
Kd ¼X
S(1)
where Kd is the solid–water distribution coefficient
(l kg�1); X the concentration in the solid phase
(mgPPCPkg solid�1); and S the concentration in the
aqueous phase (mg PPCP l�1).
This coefficient takes into account the two main
sorption mechanisms: absorption (hydrophobic interac-
tions characterized by the Kow value) and adsorption
(electrostatic interactions related to the substance
tendency to be ionized or dissociated in aqueous phase,
which is characterized by the dissociation constant,
pKa).
According to their physico-chemical properties,
PPCPs can be divided into three main groups: lipophilic
(with high Kow values), neutral (non-ionic) and acidic
(hydrophilic and ionic) compounds. Substances from
different therapeutical classes and representative of each
group have been considered in this work (Table 1): two
fragrances (Galaxolide and Tonalide), one tranquillizer
(Diazepam), one antiepileptic (Carbamazepine) and
three anti-inflammatories (Ibuprofen, Naproxen and
Diclofenac).
ater solubility in g l�1; Kd in l kg�1)
am Ibuprofen Naproxen Carbamazepine
0�2a,b 2.1� 10�2a,b 1.6� 10�2b 1.8� 10�2a,b
a,b,d 4.9–5.7a,b,d,e 4.2b,e 13.9e
a,b,d 3.5–4.5a,b,d,e 3.2b,e 2.3–2.5a,b,d,e
0.9 0.9f 0.1
roperties with Ibuprofen and other Kd measurements in digested
ARTICLE IN PRESS
Table 2
Measured concentrations of PPCPs in the spiked samples of
urban wastewater used in the coagulation–flocculation and
flotation assays (mg l�1)
Name Coagulation–
flocculation
Flotation
LF HF
Galaxolide 2–4 3–4 1–2
Tonalide 1–3 2–3 1–2
Diazepam 10–13 10–16 7–12
Carbamazepine 10–12 11–13 8–11
Ibuprofen 13–15 10–13 12–13
Naproxen 16–18 9–13 10–18
Diclofenac 14–18 10–18 12–23
M. Carballa et al. / Water Research 39 (2005) 4790–47964792
Galaxolide and Tonalide are very lipophilic com-
pounds with logKow values around 5.5–6.0. However,
while Carbamazepine and Diazepam are neutral sub-
stances, as derived from their chemical structure, the
anti-inflammatories are very acidic compounds (low pKa
values).
1.2. Physico-chemical processes
Coagulation–flocculation processes enhance the re-
moval of suspended solids and colloids, because the
addition of metal salts or organic compounds causes the
agglomeration of these particles, thus allowing their
elimination by decantation or filtration (Li and Gregory,
1991).
Lipophilic trace pollutants in water and wastewater
treatment systems are likely to be found associated with
colloids because in natural systems most colloids have
an organic coating (Stumm and Morgan, 1996). In
addition, positive charged molecules can be associated
to these colloids by means of low strength Van der
Waals bonds.
Literature information about the removal of PPCPs
by coagulation–flocculation processes is scarce. When
some data is available, it is related to either a post-
treatment (Romero et al., 2003) or drinking water
treatment, and normally they are combined with other
technologies, such as activated carbon or filtration
(Ternes et al., 2002; Boyd et al., 2003; Stackelberg
et al., 2004).
Flotation techniques, in which finely suspended parti-
cles are separated by adhering to the surface of rising
bubbles, have proved to be efficient, practical and
reliable methods for the removal of fat, as well as other
contaminants, such as oils, biomolecules or suspended
solids from water (Zouboulis and Avranas, 2000).
Besides, micropollutants like lipophilic PPCPs can be
removed from the wastewaters by flotation due to their
solubilization in the lipid fractions or sorption onto
small aggregates. For instance, Paxeus (2004) associated
the removal of Carbamazepine in a STP with the
presence of an unusual high content of silicone oil in the
wastewaters.
1.3. Objectives
The aim of this work is to improve the removal
efficiencies of three groups of PPCPs (musks, neutral
and acidic pharmaceuticals), which have different
sorption properties, during sewage primary treatment
by coagulation–flocculation and flotation processes.
This objective is based on the hypothesis that the
distribution of PPCPs between the solids and the
aqueous phase can be modified by the addition of some
chemicals (coagulants, flocculants, tensoactives, etc.).
The influence of the main operational parameters, such
as the type and dose of coagulant, the fat content of the
wastewaters and the temperature has been studied.
2. Material and methods
2.1. Wastewaters
The wastewaters used in this work were collected from
an urban STP located in Santiago de Compostela (NW
of Spain). The STP, which was surveyed in a previous
work (Carballa et al., 2004), corresponds to 100,000
inhabitants approximately and comprises three main
sections: pre-treatment (coarse/fine screening and grit/fat
removal), primary treatment (sedimentation) and biolo-
gical treatment (conventional activated sludge). The inlet
flow to the primary clarifier was used for coagulation–
flocculation experiments, whereas the inlet to the fat
separator was used for flotation assays. The main
characteristics of the wastewater are: total solids (TS),
500–900mg l�1; volatile solids (VS), 200–500mg l�1; total
suspended solids (TSS), 100–400mg l�1; volatile sus-
pended solids (VSS); 100–300mg l�1; total chemical
oxygen demand (CODt), 200–800mg l�1; soluble chemi-
cal oxygen demand (CODs), 100–500mg l�1; and fat
content, 60–70mg l�1.
2.2. PPCPs
The PPCPs used in this work were Galaxolide,
Tonalide, Carbamazepine, Diazepam, Ibuprofen, Na-
proxen and Diclofenac. Two solutions, one containing
musks plus the neutral pharmaceuticals and the other
one with the acidic substances, were spiked to 10L of
urban wastewater in order to attain higher levels than
those found in raw wastewaters (Carballa et al., 2004).
Once prepared, the resulting PPCPs concentrations were
measured (Table 2). These values include both the
background content (already present in sewage) and the
spike.
ARTICLE IN PRESSM. Carballa et al. / Water Research 39 (2005) 4790–4796 4793
2.3. Coagulation–flocculation assays
Coagulation–flocculation assays were carried out in a
Jar-Test device, in vessels of 1 l of liquid volume. The
influence of three additives was studied: ferric chloride
(FeCl3, 50 g l�1), aluminum sulfate (Al2(SO4)3, 50 g l
�1)
and aluminum polychloride (PAX, 17.5% w/w). The
assays were conducted at two temperatures, 12 and
25 1C, simulating winter and summer conditions, respec-
tively. The test included an initial 3min period of rapid
stirring (150 rpm), after the addition of the coagulant
and lime for neutralization, followed by 5min of slow
mixing (50 rpm) for emulsion breaking and floc forma-
tion, and finally 1 h period without mixing, for floc
separation. The influence of the type and dose of
coagulant and the temperature was studied. Since the
objective of the work was to enhance PPCPs removal
during sewage primary treatment, all the experiments
were carried out at the neutral pH necessary for the
further biological treatment.
2.4. Flotation assays
Flotation assays were carried out in a unit consisting
of a pressurized vessel of 2 l (where air was dissolved into
the wastewater) and a flotation cell of 1 l (Metcalf and
Eddy, 1991). The pressurized cell has two inlets (for air
and water), and one outlet for the pressurized liquid.
Also, a manometer was set up in the air line to check the
pressure. The dissolved air was then introduced into the
flotation cell where the fine air bubbles produced by
depressurization helped flocs flotation. The influence of
the content of fat in wastewaters and the temperature
was studied. The assays were carried out in duplicate.
Two types of wastewater with different concentrations
of fat were used: a low fat (LF) and high fat (HF)
wastewater, with approximately 60 and 150mg l�1,
respectively. While the LF wastewater was directly
taken from the STP considered, the HF wastewater
was synthetically prepared by adding fat (as liquid
butter) to the LF wastewater, in order to evaluate
exclusively the influence of the wastewater fat content.
2.5. Analytical techniques
TS, VS, TSS, VSS, COD and fat were analyzed
according to Standard Methods (APHA, 1999). pH was
determined using a selective electrode and temperature
with a digital thermometer. The soluble content of the
fragrances, anti-inflammatories, Carbamazepine and
Diazepam was determined after a solid-phase extraction
(SPE) of 500ml samples using 60mg OASIS HLB
cartridges (Waters, Milford, MA, USA). Meclofenamic
acid and dihydrocarbamazepine were added to the
samples as surrogate standards. All compounds were
quantitatively eluted from the cartridge using 3ml of
ethyl acetate. This extract was then divided into two
fractions: one of them being used for the direct
determination of the soluble content of Carbamazepine,
Diazepam and fragrances; the other for the determina-
tion of the soluble content of the anti-inflammatories. In
the latter case, compounds were silylated previously to
their gas chromatographic separation (Rodriguez et al.,
2003). In both cases, GC/MS was used to determine the
concentration of the investigated compounds in the
SPE extract. Values given for the different samples
correspond to the average value of two aliquots of
each sample.
3. Results and discussion
3.1. Coagulation–flocculation assays
Preliminary assays with FeCl3, Al2(SO4)3 and PAX
were performed at 12 and 25 1C without PPCPs addition
in order to adjust the dose range for each coagulant.
Several concentrations of FeCl3, (100–500mg l�1),
Al2(SO4)3 (100–500mg l�1) and PAX (250–1250mg l�1)
were tested and the parameters monitored were the TSS
and CODt concentrations in the supernatant. Although
the differences were not significant in the range
considered, it was observed (data not shown) that the
higher removal efficiencies for TSS and CODt were
achieved in the following dose range: 200–300mg l�1
(FeCl3), 250–350mg l�1 Al2(SO4)3 and 700–950mg l�1
(PAX).
Afterwards, the influence of coagulant dose (in those
ranges) and temperature on PPCPs removal was
analyzed. From the results obtained (data not shown),
it can be concluded that there is no significant influence
(less than 5%) either of the coagulant dose or of the
temperature (12 or 25 1C) on PPCPs removal in the
considered range. Because of that, the following assays
were carried out at 25 1C with the following coagulant
concentration: 250mg FeCl3 l�1, 300mg Al2(SO4)3 l
�1
and 850mg PAX l�1. Besides, a blank assay (an
experiment without any additive) was carried out to
monitor the removal of these compounds merely
associated with the sedimentation of solids in the
beakers. The results obtained are summarized in Fig. 1.
Except for Carbamazepine and Ibuprofen, which were
not affected by the addition of any coagulant, Fig. 1
shows that the use of an additive increased the removal
efficiencies of all PPCPs tested. In the case of musks,
while ferric chloride and aluminum sulfate lead to
similar eliminations of both substances (around 50%),
the use of aluminum polychloride improved the removal
efficiencies of each: 63% for Galaxolide and 71% for
Tonalide. Conversely, the elimination of Diclofenac was
higher with ferric chloride and aluminum sulfate
(around 70%), although PAX also gave a significant
ARTICLE IN PRESS
Galaxolide
Tonalide
Diclofenac
Diazepam
Naproxen
2010 40 50 60 70 80 90 1000 30
2010 40 50 60 70 80 90 1000 30
Removal (%)
BlankFeCl3Al2(SO4)3PAX
BlankFeCl3Al2(SO4)3PAX
BlankFeCl3Al2(SO4)3PAX
BlankFeCl3Al2(SO4)3PAXBlankFeCl3Al2(SO4)3PAX
Fig. 1. Removal efficiencies from the aqueous phase obtained
during the coagulation–flocculation assays.
20100 30 40 100
Galaxolide
Tonalide
Diazepam
Carbamazepine
Diclofenac
Naproxen
Ibuprofen
12°C25°C
12°C25°C
12°C25°C
12°C25°C
50 60
12°C25°C
12°C25°C
12°C25°C
70 80 90
Removal (%)20100 30 40 10050 60 70 80 90
Fig. 2. Removal efficiencies from the aqueous phase obtained
during the flotation assays with low fat (60mg l�1) wastewaters.
M. Carballa et al. / Water Research 39 (2005) 4790–47964794
reduction (around 50%). The concentrations of Diaze-
pam and Naproxen were reduced by 20–25%. While for
Diazepam there were no significant differences between
ferric chloride and aluminum sulfate, Naproxen was
only removed with ferric chloride. In both cases, PAX
was the less effective additive (below 5%).
The different behavior obtained in coagulation–floc-
culation assays for each compound can be explained by
their different physico-chemical properties. In this way,
the good removal of musks is concordant with their high
ability to attach to solid particles (logKd values between
3.3 and 3.7), mainly due to hydrophobic interactions
with the lipid fractions of the sludge cells membrane
(absorption).
The maximum removal efficiency expected for a given
compound can be estimated from its distribution
between the solid (Eq. (2)) and the aqueous (Eq. (3))
phases, using the Kd value and the PPCP concentration
in the aqueous (S) and solid (X) phase. For musks, these
maximum values ranged from 60% to 85%, very close
to those obtained in these experiments (50–70%):
% solid phase ¼Kd SS
1þ Kd SS� 100, (2)
% liquid phase ¼1
1þ Kd SS� 100. (3)
When applying the same methodology for calculating
the elimination of Diclofenac, which could be obtained
after a coagulation–flocculation treatment, just con-
sidering its Kd value (logKd ranged from 1.2 to 2.7), the
foreseen figures (15–40%) appear to be quite lower that
those obtained in the experiments (50–70%). This can be
due to the acidic nature of this compound (pKa�4),
which in aqueous phase remains partially ionized. The
coagulant enhances the binding of Diclofenac to the
suspended solids throughout the trivalent cations, thus
allowing a further removal from the water phase.
Diazepam and Naproxen removal is also improved by
the action of coagulants (20–25%), although in a lower
extent than Diclofenac, which can be explained by their
lower Kd values.
Finally, Carbamazepine and Ibuprofen were not
eliminated at any tested conditions, which is in
accordance with their very low Kd values.
3.2. Flotation assays
Preliminary assays were carried out to determine the
pressurized liquid flow necessary to produce fat separa-
tion in the flotation cell. This value was adjusted to
200ml operating inside the pressurized cell at 6.4 atm.
These conditions implied the following air–solid ratios
(A/S): 0.07 (12 1C) and 0.01 (25 1C).
The effect of the initial content of fat in wastewaters
and temperature (12 and 25 1C) was studied. Two types
of wastewaters with different concentrations of fat were
used: a LF and HF wastewater, with approximately 60
and 150mg l�1. The assays were carried out in duplicate.
Fig. 2 shows the results obtained for the different
PPCPs considered when LF wastewaters were used. A
similar behavior between both musks can be observed:
their concentrations in the aqueous phase were
substantially reduced at both temperatures (35–45%),
with the highest removal by efficiencies being obtained
at 25 1C. The elimination of Diazepam was similar to
that obtained for musks (40–45%), although no
significant difference was observed between both tem-
peratures. However, according to its lower lipophilicity
(logKow around 2.4), Carbamazepine was removed
to a lesser extent (around 20%) independently of the
ARTICLE IN PRESSM. Carballa et al. / Water Research 39 (2005) 4790–4796 4795
temperature. The anti-inflammatories were also affected
by flotation, the highest removals being those obtained
for Diclofenac (20–40%). For these three compounds,
temperature influenced removal significantly and, as for
musks, the highest values were obtained at 25 1C.
Fig. 3 shows the results obtained for the different
PPCPs studied when HF wastewaters were used. It can
be observed that the elimination of musks is higher
(around 60%) under these conditions and that tempera-
ture did not significantly influence removal. This
behavior was also observed for Carbamazepine and
Diazepam, with removals increasing to 35% and 50%,
respectively. Once again, these rates were uninfluenced
by temperature. Since the soluble content of the anti-
inflammatories was independent on the fat content in
the wastewaters, their removal patterns were similar to
those observed in the assays with LF wastewaters:
20–45% for Diclofenac, 10–30% for Naproxen and
10–20% for Ibuprofen. Temperature clearly influence
removal efficiencies, since the best results were obtained
once again at 25 1C.
The different affinities of PPCPs for organics can be
clearly seen when HF wastewaters were used. While the
removal of lipophilic substances, such as musks, is
enhanced, the elimination of more polar compounds
remains at the same level. Furthermore, there are no
significant differences in the removal of these substances
when LF or HF wastewaters are used. This shows that
not only the physico-chemical properties of the PPCPs
has to be considered, but also the presence of the other
substances in the medium, such as the fat globules, the
colloidal matter or the flocs formed during coagula-
tion–flocculation assays.
The influence of temperature in the various flotation
assays depends on the type of PPCP. For Carbamaze-
20100 30 40 100
Galaxolide
Tonalide
Diazepam
Carbamazepine
Diclofenac
Naproxen
Ibuprofen
12°C25°C
12°C25°C
12°C25°C
12°C25°C
50 60
12°C25°C
12°C25°C
12°C25°C
70 80 90
Removal (%)20100 30 40 10050 60 70 80 90
Fig. 3. Removal efficiencies from the aqueous phase obtained
during the flotation assays with high fat (150mg l�1) waste-
waters.
pine and Diazepam, and regardless of the initial fat
content, no effect was observed. However, for anti-
inflammatories, the best results were obtained at 25 1C
with both LF and HF wastewaters. In the case of musks,
while higher removal efficiencies were attained at 25 1C
when LF wastewaters were used, no significant
differences between both temperatures were observed
with HF wastewaters.
4. Conclusions
Compounds with high sorption properties (high
logKd values), such as musks (Galaxolide and Tonalide)
and Diclofenac, are significantly removed during coa-
gulation–flocculation with efficiencies of 70% in the
temperature range of 12–25 1C. Lipophilic compounds,
like musks, are mainly absorbed on the lipid fractions of
the sludge, while acidic compounds, like Diclofenac, are
mainly adsorbed due to electrostatic interactions.
Compounds with lower Kd values, such as Diazepam,
Carbamazepine, Ibuprofen and Naproxen, were reduced
to a lesser extent (Diazepam and Naproxen), up to 25%,
or not affected at any condition tested (Carbamazepine
and Ibuprofen). Although PAX gives the best results for
musks, the option of ferric chloride appears to be the
most suitable since the concentration of PAX required is
quite high.
All substances were removed during flotation assays
with higher efficiencies when HF wastewaters were used
(around 60% for musks, 35% for Carbamazepine, 50%
for Diazepam and 20–45% for the anti-inflammatories).
For musks, Carbamazepine and Diazepam, temperature
was not very important. However, in the case of
Diclofenac, Naproxen and Ibuprofen, the best results
were attained at 25 1C, independently of wastewater fat
content. Although the results obtained are quite
satisfactory for all PPCPs, it is possible that for some
of them removal could be improved by adding some
chemical which modifies surface properties.
Taking into account that some PPCPs, as well as
other micropollutants present in sewage, appear to be
not readily biodegradable, enhancing their removal in
the sewage primary treatment could be an interesting
strategy for minimizing costs in the biological and
tertiary treatment of STPs.
Acknowledgments
This work was supported by the EU (POSEIDON
project, EVK1-CT-2000-00047) and the Spanish Minis-
ter of Education and Science (FARMEDAR project,
CTM2004-04475).
ARTICLE IN PRESSM. Carballa et al. / Water Research 39 (2005) 4790–47964796
References
APHA–AWWA–WEF, 1999. In: Clesceri, L.S., Greenberg,
A.E., Eaton, A.D. (Eds.), Standard Methods for the
Examination of Water and Wastewater, 20th ed. American
Public Health Association, American Water Work Associa-
tion, Water Environment Federation, Washington, DC.
Boyd, G.R., Reemtsma, H., Grimm, D.A., Mitra, S., 2003.
Pharmaceuticals and personal care products (PPCPs) in
surface and treated waters of Louisiana, USA and Ontario,
Canada. Sci. Total Environ. 311, 135–149.
Carballa, M., Omil, F., Lema, J.M., Llompart, M., Garcıa-
Jares, C., Rodrıguez, I., Gomez, M., Ternes, T., 2004.
Behavior of pharmaceuticals, cosmetics and hormones in a
sewage treatment plant. Water Res. 38, 2918–2926.
Cargouet, M., Perdiz, D., Mouatassim-Souali, A., Tamisier-
Karolak, S., Levi, Y., 2004. Assessment of river contamina-
tion by estrogenic compounds in Paris area (France). Sci.
Total Environ. 324, 55–66.
Daughton, C.G., Ternes, T.A., 1999. Pharmaceuticals and
personal care products in the environment: agents of subtle
change? Environ. Health Persp. 107, 907–938.
Holbrook, R.D., Love, N.G., Novak, J.T., 2004. Sorption of
17b-estradiol and 17a-ethinylestradiol by colloidal organic
carbon derived from biological wastewater treatment
systems. Environ. Sci. Technol. 38 (12), 3322–3329.
Jones, O.A.H., Voulvoulis, N., Lester, J.N., 2002. Aquatic
environmental assessment of the top 25 English prescription
pharmaceuticals. Water Res. 36, 5013–5022.
Kanda, R., Griffin, P., James, H.A., Fothergill, J., 2003.
Pharmaceuticals and personal care products in sewage
treatment works. J. Environ. Monit. 5, 823–830.
Kolpin, D.W., Skopec, M., Meyer, M.T., Furlong, E.T., Zaugg,
S.D., 2004. Urban contribution of pharmaceuticals and
other organic wastewater contaminants to streams during
differing flow conditions. Sci. Tot. Environ. 328, 119–130.
Kummerer, K., 2000. Pharmaceuticals in the Environment:
Sources, Fate, Effects and Risks, second ed. Springer, Germany.
Lai, K.M., Johnson, K.L., Scrimshaw, M.D., Lester, J.N.,
2000. Binding of waterborne steroid estrogens to solid
phases in river and estuarine systems. Environ. Sci. Technol.
34 (18), 3980–3994.
Li, G., Gregory, J., 1991. Flocculation and sedimentation of
high turbidity waters. Water Res. 25, 1137–1143.
Liebig, M., 2004. Cooperation in POSEIDON project (EVK1-
CT-2000-00047). ECT Oekotoxikologie GmbH (personal
communication).
Metcalf Eddy, 1991. Wastewater Engineering: Treatment, Dis-
posal and Reuse, third ed. McGraw-Hill, New York, USA.
Paxeus, N., 2004. Removal of selected non-steroideal anti-
inflammatory drugs (NSAIDs), gemfibrozil, carbamazepine,
b-blockers, trimethoprim and triclosan in conventional
wastewater treatment plants in five EU countries and their
discharge to the aquatic environment. Water Sci. Technol.
50 (5), 253–260.
POSEIDON Project (EVK1-CT-2000-00047), 2005. Assessment
of technologies for the removal of pharmaceuticals and
personal care products in sewage and drinking water
facilities to improve the indirect potable water reuse. Final
Report, http://grdc.bafg.de/servlet/is/2888.
Rodriguez, I., Quintana, J.B., Carpinteiro, J., Carro, A.M.,
Lorenzo, R.A., Cela, R., 2003. Determination of acidic
drugs in sewage water by gas chromatography-mass
spectrometry as tert.-butyldimethylsilyl derivates. J. Chro-
matogr. A 985, 265–274.
Romero, J., Ventura, F., Folch, M., Salgot, M., Torrens, A.,
2003. Characterisation of volatile organic contaminants
after different pretreatment systems in reclaimed waste-
water. Water Sci. Technol. 3 (4), 139–143.
Schwarzenbach, R.P., Gschwend, P.M., Imboden, D.M., 2003.
Environmental Organic Chemistry. Wiley, New York,
Chichester, Brisbane, Toronto, Singapore.
Stackelberg, P.E., Furlong, E.T., Meyer, M.T., Zaugg, S.D.,
Henderson, A.K., Reissman, D.B., 2004. Persistence of
pharmaceutical compounds and other organic wastewater
contaminants in a conventional drinking water treatment
plant. Sci. Tot. Environ. 329, 99–113.
Stumm, W., Morgan, J.J., 1996. Aquatic Chemistry—Chemical
Equilibria and Rates in Natural Waters, third ed. Wiley-
Interscience, New York.
Syracuse Research Corporation, 2004. Physprop database.
http://www.syrres.com.
Ternes, T.A., 1998. Occurrence of drugs in German
sewage treatment plants and rivers. Water Res. 32 (11),
3245–3260.
Ternes, T.A., Meisenheimer, M., McDowell, D., Sacher, F.,
Brauch, H.J., Haiste-Gulde, B., Preuss, G., Wilme, U.,
Zulei-Seibert, N., 2002. Removal of pharmaceuticals during
drinking water treatment. Environ. Sci. Technol. 36,
3855–3863.
Ternes, T.A., Herrmann, N., Bonerz, M., Knacker, T., Siegrist,
H., Joss, A., 2004. A rapid method to measure the solid-
water distribution coefficient (Kd) for pharmaceuticals and
musk fragrances in sewage sludge. Water Res. 38 (19),
4075–4084.
Zouboulis, A.I., Avranas, A., 2000. Treatment of oil-in-water
emulsions by coagulation and dissolved-air flotation.
Colloids Surf. 172, 153–161.