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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.
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
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
Table 6
Comparison of the retention coefficients (R) of phthalates removed during filtration depending on the compound molar
mass
Solid-phase microextraction of phtalates from water, Industrial Water Production, 22–26 September 2002,
J. Chromat. A, 983 (2001) 93–101. Mülheim an der Ruhr, Germany, 37a (2002) 323–331.
[24] Y. Kiso, Y. Sugiura, T. Kitao and K. Nishimura, [26] K. Konieczny, Ultrafiltracja i mikrofiltracja w
Effects of hydrophobicity and molecular size on uzdatnianiu wód do celów komunalnych, Zeszyty
rejection of aromatic pesticides with nanofiltration Naukowe Politechniki Slaskiej, Seria: Inzynieria
membranes, J. Membr. Sci., 192 (2001) 1–10. Srodowiska, z.42, Gliwice 2002.
[25] K.O. Agenson, J.I. Oh, T. Kikuta and T. Urase, Rejec- [27] M. Bodzek, A. Waniek and K. Konieczny, Pressure
tion mechanisms of plastic additives and natural driven membrane techniques in the treatment of
hormones in drinking water treatment by nano- water containing THMs, Desalination, 147 (2002)
filtration, Proc. Membranes in Drinking and 101–108.