Separation and Purification Technology 95 (2012) 89–96

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Separation and Purification Technology

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

Integration of nanofiltration, UV photolysis, and advanced oxidation processes

for the removal of hormones from surface water sources
Vanessa J. Pereira a,b, Joana Galinha a, Maria T. Barreto Crespo a,b, Cristina T. Matos c,⇑, João G. Crespo d
a
Instituto de Biologia Experimental e Tecnológica (IBET), Av. República, Qta. do Marquês (EAN), 2784-505 Oeiras, Portugal
b
Instituto de Tecnologia Química e Biológica (ITQB), Universidade Nova de Lisboa (UNL), Av. da República, Estação Agronómica Nacional, 2780-157 Oeiras, Portugal
c
Laboratório Nacional de Energia e Geologia, I.P., Unidade de Bioenergia, Estrada do Paço do Lumiar, 22, 1649-038 Lisboa, Portugal
d
REQUIMTE, Departamento de Química, Faculdade de Ciência e Tecnologia, Universidade Nova de Lisboa (UNL), 2829-516 Caparica, Portugal

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

Article history: This study evaluates the integration of nanofiltration with direct and indirect UV photolysis for drinking
Received 8 January 2012 water treatment in order to guarantee effective removal of different hormones with endocrine disruption
Received in revised form 16 March 2012 capabilities – mestranol, octylphenol, nonylphenol, progesterone, estrone, estriol, 17a-ethynylestradiol,
Accepted 16 April 2012
and b-estradiol – from real surface water matrices.
Available online 23 April 2012
The integration of nanofiltration previously to low pressure ultraviolet direct or indirect photolysis
reduces the level of turbidity as well as the micropollutant contamination levels in drinking water sup-
Keywords:
plies, due to rejection based on size exclusion and molecular interactions with the nanofiltration mem-
Hormones
Surface water
brane surface. The use of nanofiltration in the treatment of surface waters spiked with different
Nanofiltration hormones allowed their rejection at levels higher than 71% for all target hormones except estriol. Low
Low pressure direct photolysis pressure indirect photolysis with 100 mg/L of hydrogen peroxide was also efficient to degrade the
Advanced oxidation processes selected hormones with percent degradations higher than 74% achieved for all the hormones, except
nonylphenol (55%).
The integrated process (nanofiltration followed by direct photolysis or indirect photolysis) is extremely
efficient to remove all the target hormones from a real surface water matrix and guarantees the produc-
tion of water with extremely high chemical quality.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction Ultraviolet (UV) radiation is gaining importance in drinking

Water sources are potential carriers of contaminants to human
beings and may therefore constitute a direct threat to human
health. Therefore, the production and distribution of drinking
water with high chemical and microbiological quality is crucial
and has been object of growing interest by water providers and
researchers.
Hormones were reported to occur at low levels in the aquatic
environment (e.g. [1–6]). As an example, in surface water, hor-
mones such as estrone, b-estradiol, a-ethinylestradiol, progester-
one, octylphenol, nonylphenol, and estriol have been reported at
levels ranging from 0.2 to 110 ng/L [1,5,6]. Even though hormones
are currently not regulated, they may be proposed for future drink-
ing water regulations due to their potential to disrupt the normal
endocrine function and affect the physiological status of animals
[5]. Attention has been therefore, focused in recent years on the
effective removal of these compounds from drinking water sources
(e.g. [4,7–11]).
⇑ Corresponding author. Tel.: +351 210924600x4200; fax: +351 217163636.
E-mail address: cristina.matos@lneg.pt (C.T. Matos).
water treatment facilities as a disinfection technique, although
chlorine is often employed for final disinfection, so that a persistent
residual is maintained in the water distribution system. The use of
UV radiation alone (direct photolysis) or in advanced oxidation pro-
cesses (AOP) – where UV may be used in combination with hydro-
gen peroxide (indirect photolysis) to produce highly reactive and
unselective hydroxyl radicals – has proved to be effective for the re-
moval of some organic pollutants (e.g. [12–14]), besides being ex-
tremely effective against a wide range of waterborne pathogens,
including Cryptosporidium and Giardia which are resistant to tradi-
tional disinfection techniques (e.g. [15]). The use of UV radiation
can therefore also lead to a reduction of the chlorine dose often
applied for final disinfection, decreasing the levels of disinfection
by-products (DBPs) formed. The use of UV radiation to achieve
the degradation of hormones has been also reported in the litera-
ture using different types of lamps (e.g. [8–11,16–19]). However,
UV radiation is not suitable for treatment of water with high levels
of suspended solids, turbidity, color, or soluble organic matter.
Appropriate membrane filtration prior to the UV system can reduce
turbidity, which improves UV transmittance and reduces shielding
of microbial pathogens and chemical compounds by particulate

1383-5866/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.04.013
90 V.J. Pereira et al. / Separation and Purification Technology 95 (2012) 89–96
matter before UV treatment. In addition, membrane materials with
defined surface chemical properties and highly controlled pore size
distribution, allows for the rejection of different micropollutants
and microorganisms. Nanofiltration is a process where the mem-
brane acts as a barrier depending on surface chemical interactions
(hydrophobic and electrostatic) as well as on size exclusion mech-
anisms, due to a high control of membrane morphology. Different
studies showed the possibility of using nanofiltration in the re-
moval of hormones, and demonstrated that the rejections achieved
for these compounds are largely controlled by adsorption of the
compounds to the membrane [20–29].
This work focused on the validation and comparison of inte-
grated nanofiltration and low pressure direct and indirect UV pho-
tolysis for drinking water treatment in order to guarantee effective
removal of hormones – mestranol, octylphenol, nonylphenol, pro-
gesterone, estrone, estriol, 17a-ethynylestradiol, and b-estradiol –
from real water sources. The rejection and adsorption obtained for
each compound using nanofiltration are determined and discussed.
In addition, the efficiency of the direct and indirect UV photolysis
processes using low pressure lamps – the most commonly used
lamps in drinking water treatment facilities – is evaluated in terms
of possible hormone competition effects, influence of the water
matrix composition on the degradation efficiency, and optimiza-
tion of the hydrogen peroxide concentrations used in the indirect
photolysis experiments. Finally, the performance of the integrated
process – combination of nanofiltration with the direct and indi-
rect photolysis process – is evaluated.
2. Experimental section
2.1. Chemical reagents and water characterization
The target hormones (mestranol, octylphenol, nonylphenol,
progesterone, estrone, estriol, 17a-ethynylestradiol, and b-estra-
diol) were selected due to their reported occurrence (e.g. [1–3,5])
as well as their different chemical structure, different molecular
weight and, consequently, different chemical properties (shown
in the Supplementary data).
All hormones selected (mestranol, octylphenol, nonylphenol,
progesterone, estrone, estriol, 17a-ethynylestradiol, and b-estra-
diol) were purchased as solids of the highest grade commercially
available (Sigma–Aldrich, St. Louis, MO). Stock solutions of the hor-
mones were prepared in high pressure liquid chromatography
(HPLC) grade methanol, stored at 20 °C and diluted in laboratory
grade water (LGW) or surface water as required. The stock solu-
tions used were as concentrated as possible to minimize the vol-
ume of methanol added to the samples. A maximum of 0.2% (v/v)
of methanol was present in the samples.
The concentration of the hormones used in these experiments
were higher (1 mg/L) than what is typically found in environmen-
tal samples in order to follow the degradation of the compounds by
direct injection using high pressure liquid chromatography (HPLC).
Bovine liver catalase was obtained from Sigma–Aldrich and
used to quench the hydrogen peroxide (one unit decomposed
1 lmol of H2O2). All the other reagents used were analytical grade.
The surface water used was supplied by the drinking water util-
ity Empresa Portuguesa das Águas Livres (located in the center of
Portugal) that treats and supplies drinking water to approximately
2.5 million people. The surface water matrix used was character-
ized (in a previous study [30]), in terms of temperature, pH [31],
total organic carbon (European Standard EN 1484:1997), turbidity
(ISO 7027:1990), alkalinity [31], and total hardness [31]. The aver-
age values and coefficient of variation (standard deviation divided
by the mean expressed as a percentage) of the different parameters
are described in Table 1.
Table 1
Characterization of the surface water matrix used
(parameters are characterized in terms of average values
and the coefficient of variation is given in parenthesis).
Temperature (°C) 17.4 (22.6%)
pH 7.83 (2.3%)
Total organic carbon (mg/L) 4 (15.7%)
Turbidity (NTU) 12.4 (70%)
Color (mg/L Pt–Co) 10.5 (N/A)a
Alkalinity (mg/L CaCO3) 69.2 (21.7%)
Total hardness (mg/L CaCO3) 131 (36.4%)
a
Only one measurement made for the sample used
in the studies.
The surface water samples were collected, filtered with a 5 lm
filter cartridge, transported to the laboratory in a cooler at 4 °C, and
kept refrigerated until used.
An Ultra-High-Speed Liquid Chromatography system (LaChrom-
Ultra System, VWR-Hitachi) [32–34], was used for the detection of
hormones, as detailed in the Supplementary data.
2.2. Nanofiltration
The nanofiltration trials were conducted in a stirred dead end
cell (Metcell, manufactured by MET, UK) coupled to an HPLC pump
that continuously feed the system (shown in Fig. 1) with surface
water spiked with 1 mg/L of the target hormones. The surface
water was pre-filtered with a 5 lm filter cartridge in order to re-
move particles. The membrane used in these trials was a Dow-
Filmthec NF 270 with an effective area of 63.6 cm2 and a molecular
weight cut-off (MWCO) of proximally 400 Da. This membrane was
chosen since it allows the rejection of several surface water chem-
ical pollutants, TOC, color, and turbidity with a significantly high
water permeability (11 L/(m2 h bar)). The trials were performed
under batch conditions at a transmembranar pressure of 8 bar
and by permeating 500 mL of the initial volume 750 mL.
The concentration of the selected hormones in the feed solu-
tion, permeate, and retentate were analyzed using the liquid
chromatography.
The apparent rejection (Rapp) degree of the selected compounds
after nanofiltration (referenced in the text as rejection) was deter-
mined using Eq. (1), with Cp and Cf referring to the concentrations
of each target hormone in the permeate and feed, respectively:
 
Cp
Rapp ð%Þ ¼ 100  1  ð1Þ
Cf
Several hormones analyzed were expected to adsorb at the
membrane surface. The hormones’ percent of adsorption (A) to
the membrane surface was therefore determined using Eq. (2),
where Cr is the concentration of each target hormone in the reten-
tate, whereas Vp, Vr, and Vf stand for the volumes of permeate,
retentate, and feed used in each nanofiltration experiment,
respectively.
 
CpV p þ CrV r
Að%Þ ¼ 100  1  ð2Þ
Cf V f
2.3. UV photolysis
2.3.1. Direct photolysis
Low pressure (LP) ultraviolet (UV) photolysis experiments were
conducted in a collimated beam laboratory-scale reactor (Trojan
Technologies Inc., Canada) using a low pressure Hg lamp that emits
mainly monochromatic light at 254 nm (Fig. 1).
Hundred milliliter of laboratory grade water or a natural water
matrix – surface water – were spiked with the appropriate volume
 V.J. Pereira et al. / Separation and Purification Technology 95 (2012) 89–96 91

Fig. 1. Nanofiltration and low pressure UV batch systems used; 1, nanofiltration module (metcell); 2, mixers; 3, nanofiltration permeate; 4, scale; 5, low pressure UV lamp
housing.

of the hormones stock solutions to achieve concentrations of 1 mg/ compounds were spiked in surface water with different hydrogen
L. This concentration was set in order to follow the degradation of peroxide concentrations (0, 20, 40, 60, 80, and 100 mg/L).
the compounds, spiked individually in different matrices (labora- At the determined exposure times, 200 lL of sample were taken
tory grade water and surface water) and as mixtures (in surface to vials containing catalase to quench the residual hydrogen perox-
water), by direct injection using the liquid chromatography system. ide. The residual H2O2 was determined at the beginning and end of
50 mL of sample were placed in a Petri dish and continuously stir- each experiment using the I 3 method described by Klassen et al.
red beneath the LP/UV source. The remaining 50 mL were used as [36].
control and kept in the dark, under identical experimental condi-
tions, in order to determine possible changes during the photolysis 2.4. Multi-barrier approach
reaction. All experiments were conducted at room temperature
(21 ± 2 °C). In order to study the efficiency of combining both nanofiltration
The lamp irradiance was measured using a calibrated radiome- and UV direct or UV indirect photolysis, as a multi-barrier system
ter (IL1700, International Light, Newburyport, MA) which was able to increase the removal of the target hormones, a nanofiltra-
placed at the same height of the water level in the Petri dish and tion permeate – obtained in the conditions described in Section
the solution transmittance was measured by a UV photometer 2.2 – was submitted to direct and indirect photolysis, using the
(P254C, Trojan Technologies Inc.). UV fluences of approximately experimental procedures described in Sections 2.3.1 and 2.3.2.
0, 40, 100, 500, 750, 1000, and 1500 mJ/cm2 were selected, taking
into account the radiometer reading as well as petri, reflection,
3. Results and discussion
water, and divergence factors as described by Bolton and Linden
[35]. These fluences were used to establish the corresponding
3.1. Nanofiltration
exposure times at which 200 lL of sample were taken to quantify
the concentration (C) of the target hormones.
In order to study the performance of a nanofiltration membrane
Fluence-based pseudo-first order rate constants (kf) were deter-
mined for the target pollutants using direct and indirect photolysis typically used in water treatment (NF270) for the rejection of the
target hormones, three experiments were conducted at 8 bar by
from the slope of a linear regression described by Eq. (3).
permeating 67% of the initial feed volume under batch conditions.
½hormone Table 2 depicts the rejections achieved for each hormone. Even
ln ¼ kf  UV fluence ð3Þ
½hormone0 
where [hormone0] is the initial concentration of the each hormone Table 2
spiked in solution and [hormone] is the concentration of each hor- Rejection degrees obtained for each hormone with nanofiltration.
mone at a given UV fluence. Hormones Rejection degree (%)
17a-Ethynylestradiol 92 ± 3
2.3.2. Indirect photolysis 17b-Estradiol 71 ± 8
The experiments conducted to address the efficiency of indirect Estriol 38 ± 1
low pressure photolysis to degrade hormones were conducted sim- Estrone 82 ± 3
ilarly to direct photolysis experiments, with the addition of 40 mg/ Progestrone >95 ± 0
Mestranol >95 ± 0
L hydrogen peroxide (H2O2) to the hormones spiked individually
4-Nonylphenol >91 ± 0
and as mixtures into laboratory grade water. In addition, to opti- 4-Octylphenol >89 ± 1
mize the removal of the selected hormones, mixtures of these
92 V.J. Pereira et al. / Separation and Purification Technology 95 (2012) 89–96

using a membrane with a MWCO (approximately 400 Da) higher
than the molecular weight of the selected compounds the rejection
degrees achieved were high (more than 71%) for all the selected
hormones except for estriol (38%). For the hormones progesterone
and mestranol (both with detection limits of 50 ppb by direct
injection) as well as 4-nonyphenol and 4-octyphenol (both with
detection limits of approximately 100 ppb by direct injection) the
minimum rejection was calculated according with their detection
limits. Their true rejection is therefore expected to be higher than
89%.
The rejection degrees obtained (Table 2) were a result of molec-
ular exclusion and adsorption of the hormones to the membrane
material.
Estriol and estrone are less hydrophobic, present higher solubil-
ity and are therefore expected to adsorb to a lesser extent to the
membrane surface and natural organic matter [37] comparatively
to the other hormones, which explains the lower rejections ob-
served. The rejections achieved for hormones, such as 17b-estra-
diol and estrone, correlate well with values reported in the
literature with an NF200 [21] and an TFC-SR2 (from Koch Mem-
brane Systems) for estrone [37]. Comerton et al. [38] reported a
similar low value of rejection for estriol (48.1 ± 11.6) from filtered
Lake Ontario water using an NF270 membrane, while lower rejec-
tion percentages compared to the ones obtained in this study were
reported for 17b-estradiol, estrone, and 17a-ethynyl estradiol (that
ranged from 31.7% to 68.6%). Yoon et al. [39] reported high rejec-
tion percentages (44–93%) by using a ESNA membrane (from
Hydranautics) for 26 endocrine disrupting compounds (EDCs),
pharmaceutically active compounds and personal care products.
The rejection of the hormones was found to be largely depen-
dent on their adsorption to the membrane material. As demon-
strated in Fig. 2 the overall removal of hormones from water is
controlled by their adsorption. Fig. 2 shows the dependence of
the adsorption (calculated using Eq. (2)) and rejection degrees (cal-
culated using Eq. (1)) with the logarithmic value of the hormones
partition coefficient between octanol and water, which is a mea-
sure of the hydrophobicity of the compounds.
High adsorption values (which varied between 40% and 80%)
were obtained for all the selected hormones, except for 17b-estra-
diol. The observed dependence of adsorption with the octanol–
water partition coefficient of the selected hormones shown in
Fig. 2 is in agreement with the literature [38–40].
McCallum et al. [24], reported that the adsorption on an NF-270
membrane follows a Freundlich adsorption isotherm, and that
even though the equilibrium rejection after membrane saturation
of 17b-estradiol may decrease the overall value of rejection re-
mains high [28]. Additionally, Sanches et al. [29] reported high
nanofiltration rejections of pesticides and hormones under ex-
tended adsorption conditions.
3.2. Direct and indirect UV photolysis
The two main parameters that influence the direct photolysis of
a compound are the decadic molar absorption coefficient and the
quantum yield, shown in Table 3.
The decadic molar absorption coefficient (e(k)) measures the
probability that a compound will absorb light at a defined wave-
length (k) and was determined in this study by measuring the
absorbance (a), at 254 nm, of solutions spiked with each of the tar-
get compounds at concentrations ranging from 10 to 100 lM ([hor-
mones]) using a 1 cm path length (z) according to Eq. (4):
a ¼ eðkÞ  ½hormones  z ð4Þ
For a compound to be photolabile it needs to have the capacity to
absorb photons of the incident light. The decadic molar absorption
coefficient results presented in Table 3 therefore show that proges-
terone will absorb light at the 254 nm wavelength emitted by LP
lamps, and was therefore expected to show the highest direct pho-
tolysis degradation (as confirmed below in Fig. 3).The quantum
yield (U) for degradation of each target hormone represents the
ratio between the total number of molecules of the compound
transformed to the total number of photons absorbed by the solu-
tion due to the compound’s presence. This parameter is shown in
Table 3 and was experimentally determined as the ratio between
the pseudo-first-order rate constant (k0 d) and the specific rate of
light absorbed by the compound at 254 nm (Ks), as detailed in
Eqs. (5) and (6). The degradation kinetics of the hormones by LP di-
rect photolysis is a function of the parameters shown in Eqs. (5) and
(6) [12]:
!
d½hormone 0
X
 ¼ kd ½hormone ¼ K s ðkÞ /½hormone ð5Þ
dt k
with
Eop ðkÞeðkÞ½1  10aðkÞz 
K s ðkÞ ¼ ð6Þ
aðkÞz
Ks(k) represents the specific rate of light absorption by the com-
pound, Eop ðkÞ the incident photon irradiance, e(k) the decadic molar
absorption coefficient (described above), a(k) the solution absor-
bance, z the solution depth in the Petri dish, and U the quantum
yield. Since LP lamps emit mainly monochromatic light, all the
parameters described above were experimentally obtained at
254 nm.
The highest quantum yield values were obtained for progester-
one and estrone (Table 3). Even though estrone exhibits a low dec-
adic molar absorption coefficient, its higher quantum yield

Table 3
Decadic molar absorption coefficient (e254 nm) and quantum yield (U) values of the
target hormones.

Compound e254 nm (M1 cm1) U (mol einstein1)

Estriol 1071 0.40
17b-Estradiol 2779 0.06
Estrone 2215 5.45
Octylphenol 3035 0.51
Nonylphenol 5900 0.27
17a-Ethynylestradiol 646 0.09
Progestrone 11265 2.82
Fig. 2. Dependence of hormones adsorption (to the nanofiltration membrane) and Mestranol 1255 1.45
their rejection degrees on the octanol–water partition coefficient (log Kow).
 V.J. Pereira et al. / Separation and Purification Technology 95 (2012) 89–96
Fig. 3. Direct (LP/UV) and indirect photolysis (LP/UV + 40 mg/L H2O2) fluence based degradation rate constants (kf) obtained for hormones spiked individually and as
mixtures in laboratory grade water (LGW) and surface water (SW).
explains why it can be removed by direct photolysis from surface
water to a greater extent than most of the other target hormones
(shown below in Fig. 3). The value of quantum yield obtained in
this study for 17b-estradiol (0.06 mol einstein1) agrees well with
the value reported by Rosenfeldt and Linden (0.04 mol einstein1)
[8]. Even though the quantum yield reported in this study for 17a-
ethynylestradiol is higher than what was reported in the literature
(0.026 mol einstein1) [8,18], our study corroborates the findings
that insignificant removal of both hormones (17b-estradiol and
17a-ethynylestradiol) is expected by low pressure direct
photolysis.
The performance of direct and indirect UV photolysis for the
degradation of the selected hormones was evaluated in terms of
competition effects, influence of water matrix composition, and
hydrogen peroxide concentrations.
Fig. 3 presents the direct and indirect photolysis fluence based
rate constants, calculated for the selected hormones spiked indi-
vidually and as mixtures in laboratory grade water. In the indirect
photolysis experiments, 40 mg/L of hydrogen peroxide was added
to the laboratory grade water spiked with the hormones. An exam-
ple of one of the fluence related degradation profiles obtained and
used to determine the degradation rate constant is presented in the
Supplementary data.
The results obtained show that higher degradation rate con-
stants of the selected hormones can be achieved by indirect pho-
tolysis, when 40 mg/L of hydrogen peroxide is used. Similar
degradation rate constants were obtained for the selected hor-
mones spiked individually and as mixtures in laboratory grade
water. Therefore, the competition for the UV light did not induce
a significant effect on photolysis, for the studied hormones concen-
trations and mixture combinations tested.
To understand the influence of the matrix compositions of real
waters on the UV degradation rate constants, direct photolysis
experiments were also conducted using surface water. Fig. 3 shows
a comparison between the direct photolysis degradation rate con-
stants obtained in laboratory grade water and surface water.
Very similar degradation rate constants were obtained for all
the selected hormones in laboratory grade water and surface
water, showing that the higher levels of total organic matter as
well as suspended and dissolved solids in surface water did not
93
contribute to a decrease in the direct photolysis of the hormones
due to the interference of these parameters as light scavengers,
for all the target hormones except estriol. On the contrary, we
could observe a slight increase of the fluence based rate constants
reported for mestranol, nonylphenol, progesterone, estrone, 17a-
ethynyl-estradiol, and b-estradiol that can be explained due to
the photolysis of natural organic matter that can be leading to
the production of hydroxyl radicals. These findings concur with
results obtained by Lin and Reinhard [11] when testing the photo-
degradation of 17b-estradiol, estriol, estrone, and 17a-ethinylest-
radiol using a very different photosimulator (with emitted
wavelengths in the range of 290–700 nm). In addition, Zhang
et al. [16] also reported an enhanced degradation of estrone and
17b-estradiol in the presence of humic acids, Caupos et al. [10]
reported an photodegradation enhancement of estrone in the
presence of fulvic acids, and Leech et al. [9] reported a significant
increase in the photodegradation of 17b-estradiol as a function of
the dissolved organic carbon derived from humic acids of the
Suwannee River with a threshold attained at approximately
5 mg/L.
Since the results obtained in laboratory grade water (Fig. 3)
showed that an increase in the overall photolysis rate constants
could be expected using indirect photolysis, additional experi-
ments were conducted with the objective of understanding the ef-
fect of using different hydrogen peroxide concentrations: 0, 20, 40,
60, 80, and 100 mg/L (Fig. 4), on the degradation of the hormones
spiked to the surface water.
For all the selected hormones, except estrone and progesterone,
there is a clear advantage of adding hydrogen peroxide to increase
the degradation rate constants (Fig. 4). Indirect photolysis using
20 mg/L enhanced the degradation of nonylphenol and mestranol,
use of 80 mg/L enhanced the degradation of octylphenol, whereas
100 mg/L of hydrogen peroxide enhanced the degradation of es-
triol, 17b-estradiol, 17a-ethynylestradiol, progesterone, and mes-
tranol. The addition of 100 mg/L hydrogen peroxide seems to
optimize the overall removal of the group of hormones selected.
Previous studies also reported an increase in the degradation rates
obtained with increasing concentrations of hydrogen peroxide for
17a-ethynylestradiol and 17b-estradiol [8], as well as estrone
and 17b-estradiol [16]. These results are explained by the high
94 V.J. Pereira et al. / Separation and Purification Technology 95 (2012) 89–96

Fig. 4. Hydrogen peroxide concentration effect in the overall fluence based degradation rate constant (kf) obtained in surface water (SW).

second-order rate constant for 17a-ethynylestradiol and OH radi-
cals reported by Huber et al. [19] and by Rosenfeldt and Linden
[8] (9.8 ± 1.2  109 M1 s1 and 1.08 ± 0.23  1010 M1 s1, respec-
tively) and the high second-order rate constant reported for 17b-
estradiol and OH radicals (1.41 ± 0.33  1010 M1 s1) [8].
The percent degradation of the selected hormones using a UV
fluence of 1500 mJ/cm2 was therefore compared using direct and
indirect photolysis. Indirect photolysis was achieved by addition
of 100 mg/L of hydrogen peroxide to the surface water spiked with
the mixture of the selected hormones (Fig. 5).
The results obtained (Fig. 5), show that direct photolysis will
only be extremely efficient to degrade progesterone and estrone,
while percent degradations lower that 37% were obtained for all
the other selected hormones. Indirect photolysis with addition of
100 mg/L of hydrogen peroxide did not impact extensively the deg-
radation of progesterone and estrone but significantly increased
the percent degradation of all the other hormones. The advanced
oxidation process therefore proved to be more suitable to achieve
degradation of a broad range of hormones.
3.3. Multi-barrier approach
A multi-barrier treatment approach was tested by combining
nanofiltration with direct and indirect photolysis in order to

Fig. 5. Removal efficiency of the individual processes and the multi-barrier approach.
 V.J. Pereira et al. / Separation and Purification Technology 95 (2012) 89–96
evaluate the efficiency of the combined process for the removal of
the target hormones from surface water. In order to assess the
multi-barrier approach performance, the nanofiltration permeate
from the experiments described in Section 2.2 was subject to direct
UV photolysis and indirect photolysis. The results obtained are
summarized in Fig. 5.
As shown in Fig. 5 and described in Section 3.1, nanofiltration
showed lower rejection degrees for estriol (38%), 17b-estradiol
(71%) and estrone (82%) when compared with the other hormones
studied. Further treatment using direct and indirect photolysis in-
creased the removal of these hormones from surface water.
The comparison of the results achieved with the combined pro-
cesses with the ones achieved with the individual processes dem-
onstrates that the multi-barrier approach may increase the
efficiency of the water treatment for the removal of certain com-
pounds such as 17b-estradiol and estrone as well as other organic
contaminants with similar properties.
The use of nanofiltration prior to the UV photolysis potentiated
the increase of the UV degradation efficiency, which was more pro-
nounced for the case of estriol. After nanofiltration, UV photolysis
allowed a higher degradation of estriol when compared to the
experiments where only UV photolysis was used. This can be ex-
plained due to the removal of color and turbidity by nanofiltration,
which improves UV transmittance and reduces shielding of chem-
ical compounds by particulate matter. The nanofiltration perme-
ates presented levels of color and turbidity below the detection
limits (<1 mg/L Pt–Co and <0.2NTU, respectively) and 90% UV
transmittance.
Even though the higher removal of the different hormones was
obtained by the combined nanofiltration and indirect photolysis
using hydrogen peroxide, the combination of nanofiltration and di-
rect photolysis proved to be sufficient for achieving high hormone
removals (close to the ones obtained for the combined process
with the H2O2 addition). Therefore, the combination of nanofiltra-
tion and low pressure direct photolysis will prevent the addition of
H2O2, contributing to the overall economic efficiency and sustain-
ability of the treatment process and preventing secondary water
chemical contamination by possible by-product formation due to
reactions of the highly reactive OH radicals produced during indi-
rect photolysis.
4. Conclusions
Nanofiltration allowed for the rejection of the selected hor-
mones with efficiencies higher than 71% (except estriol 38%) from
surface water, even using a membrane (NF270) with a molecular
weight cut-off higher than the molecular weight of the target com-
pounds (mestranol, octylphenol, nonylphenol, progesterone, es-
trone, estriol, 17a-ethynylestradiol, and b-estradiol), which
allows for a significant high water treatment rate (approximately
90 l/(m2 h) for a transmembrane pressure of 8 bar), when com-
pared with nanofiltration membranes with lower molecular
weight cut-off. Hydrophobic interactions were found to be impor-
tant mechanisms governing the rejection of these hormones. High-
er rejection efficiencies of estriol could probably be obtained using
a different membrane with a lower molecular weight cut-off. How-
ever, the use of such membrane will result in lower water treat-
ment rates.
Low pressure direct photolysis with an ultraviolet fluence of
1500 mJ/cm2 proved to be extremely effective to degrade only
two of the selected hormones – progesterone and estrone. To
achieve higher removal efficiencies of all the other selected hor-
mones, indirect photolysis should be used with the addition of
100 mg/L of hydrogen peroxide, to produce the highly reactive
and unselective hydroxyl radicals that were found to profoundly
95
impact the degradation of most of the target hormones. A slight in-
crease of the direct photolysis rate constants were obtained in sur-
face water compared to laboratory grade water probably due to
reaction of the LP UV light with natural organic matter present in
the water and the consequent production of hydroxyl radicals. Ex-
tremely similar direct and indirect photolysis rate constants were
also obtained in surface water for individual compounds when com-
pared to mixtures, showing that competition for the ultraviolet light
does not seem to impact the photolysis of hormones significantly.
Both treatment processes tested – nanofiltration or low pres-
sure advanced oxidation processes – could be used individually
and are expected to provide a high removal degree of the target
hormones. However, as demonstrated, the multi-barrier approach
(integration of nanofiltration with direct or indirect UV photolysis)
can increase the overall hormone removal efficiency. The integra-
tion of nanofiltration with direct UV photolysis is considered the
most efficient solution since it prevents the addition of hydrogen
peroxide. The use of these treatment processes prior to the com-
mon final disinfection has an additional advantage of lowering
the chlorine dose needed to achieve final disinfection due to the
proven disinfection efficiency of photolysis needed and thus the le-
vel of disinfection by-products in the water that form by reaction
of chlorine with the natural organic matter and have been linked
to adverse health effects. In addition, nanofiltration highly de-
creases the natural organic matter present in the water and other
particulate matter that may interfere with photolysis.
This multi-barrier approach, the combination of nanofiltration
with LP/UV photolysis, guarantees the production of water with
extremely high chemical quality able to cope with drinking water
microbial outbreaks (e.g. Cryptosporidium outbreaks) and future
more stringent regulations in terms of both chemical pollutants
and microbiological agents.
Acknowledgments
The authors thank Filipa Santos for technical assistance. We also
thank Trojan Technologies Inc. through Linha d’Água for providing
the collimated beam bench-scale reactor and VWR for the
LaChromUltra system. Vanessa J. Pereira thanks Fundação para a
Ciência e a Tecnologia for the grant BPD/26990/2006. Financial
support from the EEA Financial Mechanism, Empresa Portuguesa
das Águas Livres (EPAL), Município de Almada, and IBET (through
project PT0012), is gratefully acknowledged. This work was sup-
ported by Fundação para a Ciência e a Tecnologia through the grant
PEst-OE/EQB/LA0004/2011.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.seppur.
2012.04.013.
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