Desalination 162 (2004) 121–128

Application of membrane techniques to water purification.

Removal of phthalates

Michaá Bodzeka*, Mariusz Dudziaka, Krystyna Luks-Betlejb

a
Silesian University of Technology, Institute of Water and Wastewater Engineering,
Konarskiego 18, 44-100 Gliwice, Poland
Tel./Fax +48 (32) 2372368; email: bodzekm@polsl.gliwice.pl
b
Department of Chemistry, Silesian Medical Academy, Jordana 19, 41-808 Zabrze, Poland

Received 2 July 2003; accepted 3 September 2003

Abstract

Driving force membrane processes seem to be most useful for water treatment. Reverse osmosis, nanofiltration
and ultrafiltration have been applied to phthalate removal from water. In the experiment three membranes RO-DS3SE
were tested for reverse osmosis, membrane NF-DS5DK for nanofiltration and UF-DSGM for ultrafiltration, all of them
from Osmonics, Inc. (USA). All membranes were tested under specified conditions (for RO, NF – 2.0 MPa, UF –
0.3 MPa) and they showed a high degree of phthalate removal from water – from 97.6% to almost 99.9%. Microextraction
(solid phase extraction, SPME with CV/DVB-carbowax/divinylobenzene phase) was used for phthalate extraction
from the aquatic matrix, while gas chromatography (GC) with FID detector was used for their quantitative-qualitative
monitoring.

Keywords: Removal; Phthalates; Water treatment; Reverse osmosis; Nanofiltration, Ultrafiltration

1. Introduction Phthalates are used for plastics plastifying, mainly

for PVC; moreover, they are in some other
Phthalic acid diesters, commonly called
products such as solvents, plastics softeners, as
phthalates, are synthetic substances which con-
components of the materials for food product and
stitute potentially hazardous pollutants due to their
disposable medical equipment packages, toys,
widespread occurrence in the environment.
cosmetics, lubricants, epoxy resins used for water
*Corresponding author.
pipes inside, etc. [1].

Presented at PERMEA 2003, Membrane Science and Technology Conference of Visegrad Countries (Czech Republic, Hungary,
Poland and Slovakia), September 7–11, 2003, Tatranské Matliare, Slovakia.

0011-9164/04/$– See front matter © 2004 Elsevier B.V. All rights reserved
122 M. Bodzek et al. / Desalination 162 (2004) 121–128

There are many controversial opinions about [16,17], phthalates [17,18] and pesticides [19].
phthalate harmful influence on the organisms. Progress in the studies on the membrane tech-
Recent studies on phthalate biological activity niques makes their application for water treatment
show their negative influence on reproductive pro- technically possible and economically profitable.
cesses; thus, they can be classified as pollutants The membrane processes can be an alternative
which disturb endocrine system activity [1–5]. for the traditional treatment systems as they meet
Chemical substances that effect endocrine and high environmental standards [20].
immunological system of animals and people exert The aim of the present study was to check the
a particularly strong influence on a foetus, while possibility of application of the pressure driven
the results can be seen in an adult. membrane processes, i.e. RO, NF and UF, for
Phthalates migrate from plastic materials into phthalate removal from the waters prepared from
the environment and they can be found in water, drinking waters, under laboratory conditions. We
soil, air, food and human organism [6]. Such phtha- made an attempt to characterise the factors that
lates as diethyl (DEP), di-n-butyl (DBP), di(2- may influence permeation and retention of these
ethylhexyl) (DEHP) can be found in underground, compounds during the membrane filtration based
natural and drinking waters [7–9]. Surface waters on the literature data and our own studies.
may be polluted with phthalates coming from manu-
facturing waters from plastics plants, or phthalates
2. Experimental
may be washed out from the plastics (bottles,
packages etc.) gathered on waste dumps and 2.1. Apparatus and membranes
indirectly introduced into the environment.
Membrane filtration was carried out in the
Many countries have made special lists of
system presented in Fig. 1. The main element of
permissible concentrations of some phthalates [6].
the system — high pressure membrane module
Environment Protection Agency (EPA) allows the
made by Osmonics Inc., type SEPA CF-HP — is
concentration of di(2-ethylhexyl) (DEHP) to be
adapted for RO, NF and UF as well.
6 µg/l [10]. According to the Ministry of Health
The membranes by Osmonics Inc. (USA) were
Regulations of 19 November 2002 the permissible
used; some of their properties and parameters are
concentration of di-n-butyl in drinking water in
listed in Table 1.
Poland is 20 µg/l [11].
As the drinking water quality is getting worse
the methods of water treatment and the traditional
technological systems in water treatment plants
should be modernised, i.e. some new highly
effective processes have to be introduced. More
and more often the pressure driven membrane
processes such as reverse osmosis (RO), nano-
filtration (NF) and ultrafiltration (UF) are con-
sidered in water treatment [11,12]. The results of
the studies that have been carried out so far allow
accepting the membrane processes as an alter-
native method for treating waters containing large
amounts (over the standard) of organic micro-
pollutants, such as trihalomethanes (THM) [14–
16], polycyclic aromatic hydrocarbons (PAHs) Fig. 1. Diagram of the apparatus used.
 M. Bodzek et al. / Desalination 162 (2004) 121–128 123

Table 1
Properties of the membranes tested and the parameters used during the experiments

Membrane process Reverse osmosis Nanofiltration Ultrafiltration

Producer’s symbol DS3SE DS5DK DSGM
Membrane material polyamide polyamide polyamide
Parameters
Pressure, MPa 2.0 2.0 0.3
Flow rate, m/s 0.75 0.75 0.75
Temperature, °C 20±2 20±2 20±2
RNaCl, % 96.7 40.6 —
RMgSO4, % 98.8 96.3 —
Cut-off, Da — 150–300 8000
Redistilled water flux, m3/m2s.10–6 2–3 about 5.5 about 3.5

2.2. Methodology of the experiments V

J= m 3 /m 2 ⋅ s
We investigated the following: F ×t
• Tap water samples collected from consumers where V – permeate volume, m3; F – membrane
(Zabrze – Upper Silesia) for phthalate determ- area, m2; t – time, s.
ination,
• Simulated waters prepared from tap water and Cp
R =1− × 100%
phthalate standards used for membrane filtra- Cn
tion tests. where Cp – concentration in the permeate, Cn –
Concentrations of individual phthalates in tap concentration in the tap water.
water are given in Table 2. The following phthalates Methodology of xenobiotics determination
were used for the experiments: dietyl (DEP), di- included two steps:
n-butyl (DBP), di-2-ethylohexyle(DEHP) – Dr • Step I – extraction of phthalates from water
Ehrendorfer standards (Germany). by micro-extraction technique SPME (solid
For particular processes the retention coeffi- phase microextraction) with the use of a micro-
cients (R) were determined on the basis of the extractor equipped with a fibre with CV/DVB
concentrations of xenobiotics in raw water and phase (carbowax–divinylobenzene), by Supelco.
permeate stream, and the filtration efficiency was • Step II – qualitative-quantitative analysis of the
defined as follows: isolated compounds by capillary gas chromato-
graphy (GC) technique with the use of gas
Table 2 chromatograph A-14 Shimadzu equipped with
Concentration of individual phthalates in the mixture FID detector, capillary column PTETM–5 (30 m
× 0.25 mm × 0.25 µm) by Supelco.
Tested solutes Concentration of individual
phthalates in the mixture, µg/dm3 Methodological details on phthalate determina-
tion had been described in previous publications
I II III
[22,23].
Diethyl phthalate 40 200 600
Di-n-butyl phthalate 40 200 600
Di-(2-ethylhexyl) 40 120 200
2.3. Phthalate characteristics
phthalate Molecular structure of phthalates is presented
124 M. Bodzek et al. / Desalination 162 (2004) 121–128

A B C
O O
O O O
O O O
O
O
O
O

Fig. 2. Molecular structure of (A) diethyl phthalate (B) di-n-butyl phthalate (C) di-(2-ethylhexyl) phthalate.

Table 3
Properties of phthalate esters [18,21]

Characteristic Value
Diethyl phthalate Di-n-butyl phthalate Di-(2-ethylhexyl) phthalate
Formula C12H14O4 C16H22O4 C24H38O4
Molecular weight, g/mol 222.24 278.35 390.56
Molecular width, nm 0.405 0.409 0.525
Molecular length, nm 1.190 1.451 1.658
log Kow 2.47 4.72 7.45

in Fig. 2, and some chemical properties are given Table 4

in Table 3. The phthalates being analysed are
hydrophobic compounds of small water solubility.
The components were soluble in the range
4.0×102 mg/l for DEP to 2.6×10–3 mg/l for DEHP,
their molar mass was from 222.24 for DEP to
390.56 for DEHP. Kiso in his work [18] gives full
characteristics of the particle morphology, and thus,
besides molar mass he gives two additional
parameters typical for phthalate particle —
molecular width, nm, and molecular length, nm,
Table 3. Hydrophobic character of phthalates is
expressed by the index log Kow defined as:
log Kow = log (Co/Cw)
where Kow is a partition coefficient, Co and Cw is
concentration in n-octanol and in water.
3. Results and discussion
3.1. Determination of xenobiotic concentra-
tions in waters
Quantitative determination of tap water
collected in Zabrze is given in Table 4.
Phthalate content in tap water collected in Zabrze
Phthalate esters Zabrze RSD
µg/l %
Diethyl phthalate (DEP) — —
Di-n-butyl phthalate (DBP) 0.17 13.68
Di-(2-ethylhexyl) phthalate (DEHP) <0.5 12.57
*
RSD – relative standard deviation (%) for n (3–4)
Two phthalates (di-n-butyl and di-2-etylhexyl)
were found in the sample under test, but their
concentrations were low. The concentration of di-
n-butyl did not exceed the permissible concentra-
tion defined by the Ministry of Health Regulations.
Relative standard deviation (RSD) for such low
concentrations was about 13%, and it means that
SPME-GC determinations are of good precision.
Retention coefficients of the membranes at the
parameters used during phthalate removal from
water (Table 1) were in the range of 97.6–99.9%
(Table 5), when the concentrations of phthalate
three-component mixture were 120 µg/l–1400 µg/l.
 M. Bodzek et al. / Desalination 162 (2004) 121–128 125

Table 5 correlate to one another proportionally, i.e. the

Influence of phthalate concentration on the separation bigger particle size and higher log Kow, the higher
properties of the membranes in the range of mixture con- retention coefficient values are predicted. The
centrations 120 µg/l–1400 µg/l morphology of phthalate particles investigated in
the present work was similar: width from 0.405 nm
Membranes Retention coefficient R, % (DEP) to 0.525 nm (DEHP), length from 1.190 nm
120 µg/l 520 µg/l 1400 µg/l (DEP) to 1.658 nm (DEHP). But no correlation
RO-DS3SE 99.9 99.9 99.9 was found between the retention coefficient (R)
NF-DS5DK 99.9 99.9 99.9 and log Kow. The values log Kow for the phthalates
UF-DSGM 97.6 99.4 99.9 were different in the range 2.47 (DEP)–7.45
(DEHP), and the retention obtained was high for
Such a high degree of the removal was obtained all the compounds. Due to this fact log Kow cannot
also by the authors of the work [18]. be accepted as an effective parameter in modelling
The values of R (%) showed that the separation the compound retention [25]. Similarly to the authors
properties of membranes did not depend on the [25] we conclude that the compound retention
increase of phthalate mixture concentration in tap modelling cannot be based on the single properties
water. The membrane processes that had been of the compounds.
used appeared to be of great effectiveness in Redistilled water flux (Jw) and permeate flux
phthalate separation from water. (Jv) received under the same conditions are com-
Table 6 presents the retention coefficients pared in Table 7.
obtained for particular components of the phthalate
mixture for the filtration of water, in which these
Table 7
compounds have the same concentrations depend-
Comparison of flux Jw and Jv received during phthalate
ing on their molar mass. removal from water
For the phthalate mixture concentration 40 µg/l
no differences between the retention coefficients Membrane Jw·106, Jv·106, m3/m2.s, (Jv/Jw)
were observed. The membranes under test were [m3/m2.s] 120µg/l 520µg/l 1400µg/l
able to remove the xenobiotiocs successfully inde-
pendent of their molar mass. Kiso emphasises in RO-DS3SE 2.29 1.87 1.87 1.74
(2.0 MPa) (0.82) (0.82) (0.76)
his works [18] and [24] that the values of phthalate
retention coefficients may have connection with NF-DS5DK 5.48 4.35 4.09 3.63
(2.0 MPa) (0.79) (0,75) (0.66)
the morphology of the particles removed from the
compounds, including phthalates, and with log Kow UF-DSGM 3.19 2.84 2.66 2.60
values of these compounds. All these values should (0.3 MPa) (0.89) (0.83) (0.81)

Table 6
Comparison of the retention coefficients (R) of phthalates removed during filtration depending on the compound molar
mass

Molar mass, g/mol Concentration in water, µg/l Retention coefficient R, %

RO-DS3SE NF-DS5DK UF-DSGM
222.24 DEP 40 95.1 99.9 99.9
278.35 DBP 40 95.1 99.9 89.7
390.56 DEHP 40 99.9 99.9 99.6
126 M. Bodzek et al. / Desalination 162 (2004) 121–128
The permeate flux (Jv) was smaller than the
redistilled water stream (Jw) for the membranes
being rested. The higher concentration of the
phthalate mixture, the lower value of Jv/Jw ratio; it
resulted from the membrane blocking — a nega-
tive phenomena often accompanying the mem-
brane filtration [26].
In the filtration efficiency modelling, at small-
particle organic compound removal described
previously in the work [27], the membrane
blocking was total for RO and NF, and ‘in places’
for UF. A mathematical model based on the
changes in time resistance of mass transport and
a filtration model under constant pressure con-
ditions (model by J. Hermia) were used for the
modelling. The membranes which were applied
appeared to be highly efficient in the removal
process. The work [17] suggests that an adsorp-
tion fouling may be a probable cause of such high
values of the retention coefficients, especially for
nanofiltration. In our opinion it is a result of attrac-
tion of negatively charged organic foulants by
positively charged surfaces of the membranes.
During the filtration of such foulants by the
membranes made of polyamide, these compounds
begin to build in into the polymer structure via
hydrogen bonds which are likely to form. Such an
adsorption may initiate the membrane blocking,
either total or ‘in places’. Fig. 3 shows a diagram
of this process.
4. Conclusions
1. The investigations showed a high effective-
ness of pressure driven membrane techniques in
phthalate removal from water. The compounds
were removed in the range of 97.6–99.9%.
2. The membranes were able to remove xeno-
biotics independent of their concentration in the
filtered water, their molar masses and log Kow of
particular components. Similar values of the
retention coefficients for the phthalates being
investigated were received probably due to similar
morphology of the particles.
Polyamide
+
N (CH2)5 C
n
H O
Hydrogen bond
O
C OR1
C OR2
O
Phthalate molecule
Fig. 3. Diagram of a hydrogen bond between a membrane
polymer and a phthalate particle.
3. The result of the removal was probably
influenced by the membrane blocking — total for
RO and NF and ‘in places’ for UF, according to
the work [27] — caused by the adsorption of the
compounds under retention, and the formation of
hydrogen bonds with membrane polymer (poly-
amide).
4. Permeate and retention modelling basing on
a single parameter is not complete. Characteri-
sation of the membrane separation both on the
level of molecular interaction (particle removed –
membrane polymer) based on chemical-physical
properties of the components, and by the deter-
mination of the process parameters (model by
Hermia) seems to be proper and correct.
Acknowledgements
This work was performed with the financial
support from the Polish State Committee of Scien-
tific Research (KBN) under grant 3 T09 047 19.
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