Journal of Environmental Science and Engineering, 5 (2011) 121-137

Efficiency of Advanced Membrane Wastewater

Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol
M. Khamis1, R. Karaman2, F. Ayyash2, A. Qtait2, O. Deeb2 and A. Manssra1
1. Department of Chemistry and Chemical Technology, Faculty of Science and Technology, Al-Quds University, Jerusalem 20002,
Palestine
2. Faculty of Pharmacy, Al-Quds University, Jerusalem 20002, Palestine
Received: September 24, 2010 / Accepted: October 28, 2010 / Published: February 20, 2011.
Abstract: The efficiency of membrane separation technology for wastewater treatment was employed to check its efficiency in
removing pharmaceuticals, their degradation products and their metabolites from wastewater. Aspirin and paracetamol were found to
degrade in wastewater furnishing salicylic acid and p-aminophenol, respectively. The kinetics for the degradation reactions of both
drugs were investigated in wastewater environment and both have shown first order kinetics with rate constants 0.845 10-8 Ms-1 and
1.0 10-8 Ms-1 at room temperature, respectively. These values are an order of magnitude larger than those obtained in pure water under
the same conditions. The over all performance of the plant has shown complete removal of these compounds from spiked wastewater
within the detection limit of the analytical method. The most effective components for removing those drugs within the plant were
activated carbon and clay micelle filters. The adsorption isotherms for these compounds have been studied using both activated carbon
and newly developed adsober named clay-micelle complex. All studied isotherms were found to fit Langmuir isotherm. The Langmuir
constant and the adsorption capacity were evaluated and discussed.
Key words: Pharmaceuticals, wastewater, membrane technology, ultra-filtration, reverse osmoses, adsorption isotherms.

1. Introduction
Reclaimed (recycled) water is used in the
Mediterranean countries to irrigate plants in public
parks and municipal landscapes. Reclaimed water is a
wastewater that has been treated to remove solids and
certain pollutants, and then used in landscaping
irrigation. The recycling and recharging is often done
by using the treated wastewater for designated
municipal sustainable gardening irrigation applications.
In most locations, it is intended to be only used for
nonpotable uses [1].
The occurrence of pharmaceuticals and their
metabolites and transformation products in the
Corresponding author: R. Karaman (1958- ), male,
professor, main research field: pharmaceuticals, design and
stability. E-mail: dr_karaman@yahoo.com.

environment are increasingly become a matter of

concern, because these compounds which may have
adverse effects on living organisms, are extensively
and increasingly used in human and veterinary
medicine and are released continuously into the
environment. A variety of pharmaceuticals have been
detected in many environmental samples worldwide.
Their
occurrence
has
been
reported
in
sewage-treatment-plant effluents, surface water,
seawater, groundwater, soil, sediment and fish [2-5].
The utilities providing reclaimed water for nonpotable
uses do not treat the water with drinking water
standards.
Varying
amounts
of
pathogens,
pharmaceuticals and other trace chemicals are able to
pass through the treatment and filtering process,
potentially causing danger to humans. Modern

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Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

technologies such as reverse osmosis may help to

somewhat overcome this problem.
Pharmaceuticals are an important group of potential
endocrine disrupters (EDs) which have recently
attracted much attention of the international scientific
community. They are emerging environmental
contaminants, extensively and increasingly being used
in human and veterinary medicine. These compounds
are designed to have a specific mode of action, and
many are persistent in the body. They have been
detected with low concentrations in many countries in
many environmental samples, for example
sewage-treatment plant effluents, surface water,
seawater, and groundwater [2-5]. Non-steroidal
anti-inflammatory
drugs
including
aspirin
(acetylsalicylic acid) and paracetamol (acetaminophen)
are some examples of the most commonly used
pharmaceuticals [6]. Many pharmaceuticals undergo
transformations in the human body, resulting in release
of significant amounts of a variety of metabolites into
the aquatic environment. These metabolites can be
further transformed during sewage treatment.
Pharmaceutical substances may also be degraded by
biotic and/or abiotic processes, for example hydrolysis
and photolysis. The degradation by-products are also of
concern, because they may have toxicity similar to or
higher than the parent compounds [7-11].
Information about the fate of pharmaceuticals in the
environment is limited. The low volatility of
pharmaceutical products indicates that distribution in
the environment will occur primarily by aqueous
transport, but also by food-chain dispersal. Although
the persistence of pharmaceutical products is low, they
are ubiquitous in the environment because rates of
release are higher than their rates of transformation
[12]. The fate of pharmaceutical products and their
metabolites in wastewater treatment plants may be
mineralization to carbon dioxide and water, adsorption
on suspended solids (if the compound is lipophilic), or
released in the effluent either as the original compound
or as a degradation product. Adsorption of some

pharmaceuticals in digested sludge has been reported

to be relatively low. The easily adsorbed
pharmaceuticals can reach the terrestrial environment
when sludge is used as an agricultural fertilizer. They
can also enter agricultural land from manure,
medicated and in-house reared animals and from
animals raised on pastures. From the terrestrial
environment the pharmaceuticals can subsequently be
transported to surface water and groundwater. On the
other hand, pharmaceuticals used in aquaculture are
released directly into surface water [13].
Acidic pharmaceuticals, for example acetylsalicylic
acid, ibuprofen, fenoprofen, ketoprofen, naproxen,
diclofenac, and indomethacin, with pKa values from
4.1 to 4.9, and clofibric acid, bezafibrate (pKa 3.6) and
gemfibrozil occur as ions at neutral pH are, therefore,
not readily adsorbed by sludge, and remain in the
aqueous phase [14].
Some drugs may be released in a modified form,
either hydrolyzed or conjugated; for example, more
than 90% ibuprofen is removed by transformation into
hydroxyl and carboxyl derivatives. As a result, drug
residues or their transformation products are detected
in wastewater-treatment-plant effluents [14]. This is
important because conjugates may later be hydrolyzed,
yielding the parent compound; this is, therefore, an
additional indirect source of release of the drug into the
environment. Although some groups are not affected
by sewage treatment processes, others are amenable to
degradation, though incomplete. While water
purification techniques such as granular activated
carbon could potentially remove these pollutants from
wastewater streams, the high cost involved suggests
that more attention should be given to the potential for
the optimization of current treatment processes, and
reduction at source in order to reduce environmental
contamination [14].
Among the methods used for wastewater treatment
are the following: (1) Biodegradation: biological
degradation (aerobic/anaerobic by micro-organisms) of
drug substances leading to a reduction of the parent

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

compounds and/or their metabolites during wastewater

treatment. (2) Deconjugation: conjugates of organic
compounds such as steroid hormones have been shown
to be readily deconjugated in domestic wastewater and
within sewage treatment plants (STPs) due to the large
amounts of -glucuridase enzyme present (produced by
the fecal bacterium Escherichia coif). It seems probable
that gluconoride and sulfate conjugates of drug
compounds will be degraded by the same process. The
effect will increase the excreted contribution of the
active drugs to sewage and effluents. (3) Partitioning:
partitioning between the aqueous and organic biomass
phases is a key component in determining the ultimate
concentrations of organic pollutants. Compounds with
high log P (lipophylic molecules) values are known to
sorb to sludge, while substances with lower values are
more likely to stay in the aquatic phase, depending on
the individual compound, and substances sorbing to
solids may also be remobilized if they are not strongly
bound. (4) Removal during sludge treatment: drugs
may also be degraded during sewage treatment
processes. Many pharmaceuticals are not thermally
stable and so might be expected to break down during
processes such as composting due to heat (as well as
chemical and biodegradation). (5) Photodegradation:
several pharmaceutical compounds have been shown to
degrade due to the action of sunlight. The most
extensively studied of these compounds is the
analgesic/anti-inflammatory drug diclofenac, which
has been shown to degrade in the aquatic environment
due to ultraviolet (UV) light [14].
In this manuscript the authors report the first study
conducted in Palestine for the removal of some
pharmaceuticals by ultra filtration (hollow fiber and
spiral wound), sorption onto activated carbon,
micelle-clay complex and reverse osmosis membranes.
The authors have chosen to study the membranes
removal of aspirin and paracetamol since both
pharmaceuticals are widely consumed and were found
to be frequently used medicines in the region [15].

2. Experimental

123

2.1 Instrumentation
High Pressure Liquid Chromatography (HPLC-PDA)
system consists of an alliance 2695 HPLC from
(Waters: Israel), and a waters Micromass Masslynx
detector with Photo diode array (Waters 2996: Israel).
Data acquisition and control were carried out using
Empower software (Waters: Israel). Analytes were
separated on a 4.6 mm 150 mm C18 XBridge
column (5 m particle size) used in conjunction with a
4.6 mm 20 m XBridge C18 guard column.
Microfilter was used with 0.45 m (Acrodisc GHP,
Waters). pH were recorded on pH meter model
HM-30G: TOA electronics was used in this study to
measure the pH value for each sample. The Wastewater
treatment plant (WWTP) at Al-Quds University
collects mixture of black, gray and storm water. The
treatment plant consists of a primary treatment (two
stage primary settling basin), secondary (activated
sludge with a hydraulic retention time of 16-20 hours,
coagulation and chlorination) treatment. Then the
secondary effluent is introduced to the sand filter
before entering the ultra filtration membrane (Hollow
fiber and Spiral wound). After the ultra filtration
process, the effluent is subjected to activated carbon
adsorbers followed by a reverse osmosis (advanced
treatment). Then a blend of all effluents is used for
irrigation. The ultra filtration process is made of two
small scale membrane treatment plants with a capacity
of 12 m3/day. The first UF unit is equipped with 2 4
inch pressure vessels with pressure resistance up to 150
psi. Each vessel holds two separation membranes
(spiral wound with 20 kD cutoffs which are equivalent
to 0.01 micron separation rate). The designed permeate
capacity of the system is 0.5-0.8 m3/h. This membrane
can remove bacteria, suspended solids, turbidity agents,
oil and emulsions. The second unit is equipped with
two pressure vessels made from Vendor (AST
technologies, model number 8000 WW 1000-2M) that
houses the hollow fiber membranes with 100 kD cutoff
(Vendor, AST technologies, Model No. 8000WWOUT-IN-8080). The two units are designed to

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Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

deliver 1.5 m3/h. The reverse osmosis (RO) membranes

are made from thin film polyamide which consists of 1
4 inch pressure vessel made from composite material
with pressure resistance up to 400 psi. The vessel holds
two 4 inches special separation membranes
(manufactured in thin film polyamide with pH range
1-11 models BW30-4040 by Dow Film Tec.).
Membrane anti-scalent (Product NCS-106-FG, made
of phosphate in water with active ingredient of
phosphonic acid disodium salt) are continuously dosed
to the RO feed at concentration of 4 ppm in order to
prevent deposition of divalent ions. The system is
designed to remove major ions and heavy metals. The
designed RO permeate capacity of the system is 0.450.5 m3/h.
2.2 Chemicals and Reagents
Pure standards (> 99%) of aspirin, salicylic acid,
paracetamol and p-aminophenol are commercially
available. Methanol and water are both HPLC grade
and purchased from Sigma Aldrich. Magnesium sulfate
was purchased from Sigma Aldrich. High purity
diethyl ether (> 99%) was purchased from Biolab,
p-aminophenol and orthophosphoric acid (OPA) were
obtained from Riedel-De Haen.
2.3 Methods
Standard solution of salicylic acid:
(a) Stock solution: stock solution was prepared by
dissolving salicylic acid standard in a mixture of
methanol and water that adjusted to pH 3.45 in a ratio
(1:1) to a concentration of 200 ppm for the use in (b).
(b) Calibration curves: A 200 mL stock solution of
salicylic acid with a final concentration of 200 ppm
was prepared in the same manner as for (a). The
following diluted solutions were prepared from the
stock solution: 20 ppm, 60 ppm, 100 ppm, 160 ppm and
180 ppm. Then each diluted solution was extracted
three times with ether. The ether extracts were
combined, dried with anhydrous MgSO4, filtered and
evaporated. For HPLC-PDA analysis, the dried residue

after evaporated ether was dissolved with methanol:

water (adjusted to pH 3.45) (1:1) and was injected to
the HPLC apparatus.
Liquid-liquid extraction of salicylic acid:
Liquid-liquid extraction procedure was applied to
the diluted solutions (samples of calibration curve) and
wastewater samples using diethyl ether solvent. Each
sample was extracted three times with ether. The ether
extracts were combined, dried with anhydrous MgSO4,
filtered and evaporated. For HPLC-PDA analysis, the
dried residue was dissolved in a mixture of methanol:
water (adjusted to pH 3.45) (1:1) and was injected to
the HPLC apparatus.
Sample collection and preparation of salicylic acid:
Sample of 60 g of salicylic acid was dissolved in
minimum amount of methanol and was poured
immediately into the wastewater tank. Then eight
wastewater samples were collected from different
locations of wastewater treatment plant (WWTP).
Samples were kept on ice during transport to the
laboratory. Once received, conventional wastewater
parameters including total suspended solids (TSS),
temperature, and pH were measured then the samples
were filtered and adjusted to pH < 2 by the addition of
concentrated hydrochloric acid, and then stored at 4
until extraction.
Chromatographic conditions for the separation of
aspirin and salicylic acid:
All samples were analyzed using HPLC-PDA. The
optimal HPLC conditions that were found for the
analysis of salicylic acid are: a C-8 as the column, a
mixture of water: methanol (water pH adjusted to 3.4
using dilute o-phosphoric acid) (55:45 v/v) as a mobile
phase, a flow rate of 2 mL/minute and a UV detection
at a wavelength of 230 nm.
Sample and standard preparations of paracetamol:
(a) Stock solution: stock solution was prepared by
dissolving paracetamol standard and p-aminophenol
standard in acetonitrile and water that adjusted to pH
3.45 in a ratio (90:10) to a concentration 100 ppm that
used in (b).

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

(b) Calibration curves: a 500 mL stock solution of

paracetamol and p-aminophenol with a final
concentration of 100 ppm was prepared in the same
manner as for (a). The diluted solutions that were
prepared from the stock solution are: 10 ppm, 20 ppm,
40 ppm, 60 ppm, 80 ppm and 100 ppm. Then each
diluted solutions were extracted in the same manner as
before to plot calibration curve for paracetamol and
p-aminophenol with extraction.
(c) Stability study of paracetamol in pure water: for
the hydrolysis reaction of paracetamol in pure water, a
200 ppm solution was used. The reaction progress was
followed by HPLC method.
(d) Stability study of paracetamol in the presence of
sludge: the same procedure as described in (c) was used
for the hydrolysis of paracetamol in the presence of
sludge. However, in this case water was replaced with a
suspended sludge in plain water.
Samples at specific time intervals were taken. Then
the sample aqueous layer was extracted three times
with ether. The ether extracts were combined, dried
with anhydrous MgSO4, filtered and evaporated. For
HPLC-PDA analysis, the dried residue was dissolved
in a mixture of methanol: water (adjusted to pH 3.45)
(1:1) and was injected to the HPLC apparatus.
Chromatographic conditions for the separation of
paracetamol and p-aminophenol:
The optimal HPLC conditions that were efficient for
the separation of paracetamol and p-aminophenol are:
C-18 as the separation column, a mixture of water:
acetonitrile (water pH adjusted to 3.45 using dilute
o-phosphoric acid) (90:10 v/v) as a mobile phase, flow
rate of 1.0 mL/minute and a UV detection at a
wavelength of 247.0 nm.

3. Results and Discussion

3.1 Aspirin
Aspirin (acetylsalicylic acid) is among the top
twenty medicines that have been found to be frequently
used in the West Bank and Jerusalem due to its activity
as a pain killer [15]. In addition, Aspirin is used as

125

antipyretic and is used once daily in low doses, 75 mg

and 100 mg, as prophylactic medicine for the
prevention of blood aggregation. The latter (blood
aggregation) is the most common cause for heart attack
among people over the age of 40.
Aspirin is a white powder that is stable in dry
conditions but is hydrolyzed to salicylic acid and acetic
acid under humid or mist condition (Scheme 1).
When aspirin is ingested, it is quickly and effectively
hydrolyzed to the major excretion product, salicylic
acid. Then salicylic acid is metabolized primarily to
two major inactive metabolites: salicyluric acid (75%)
arises from conjugation of salicylic acid with glycine,
and glucuronide ether and ester (15%) arises from
conjugation with glucuronic acid. In addition to these
metabolites, small amounts of gentisic acid (1%)
metabolites resulting from p-hydroxylation mediated
by cytochrome P450. These metabolites are then
excreted in the urine (Scheme 2) [16, 17].
Much scientific attention is being devoted to the
occurrence of pharmaceuticals in the environment.
This has resulted in increasing numbers of reports of
pharmaceuticals detected in a variety of environmental
samples, for example river water, seawater, and
wastewater. GC-MS and LC-MS or LC-MS-MS are the
techniques most commonly used for determination of
pharmaceuticals. The continuously increasing
sensitivity of these analytical techniques has resulted in
a large number of publications reporting the occurrence
of the compounds, especially in the aquatic
environment. Thirty-two pharmaceuticals from
different medicinal classes have been detected in
German municipal sewage treatment plant effluents
and river waters. Anti-inflammatory drugs (salicylic
acid, diclofenac, ibuprofen, indomethacin, naproxen,
and phenazone), lipid regulators (bezafibrate,
gemfibrozil, clofibric acid, fenofibric acid),
beta-blockers
(metoprolol,
propranolol),
and
carbamazepine were found to be ubiquitously present
in streams and river water in the low ngL-1 range [18].
The occurrence of aspirin was reported in treated

126

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

O
O

H
O

Hydrolysis

RT, pH = 7

H3C

OH

CH3
Aspirin

OH

Acetic acid

Salicylic Acid

Scheme 1 Hydrolysis of aspirin (acetylsalicylic acid) to salicylic acid and acetic acid.

O
O
OCH3
O
Aspirin

Hydrolysis

Ester and ether

glucuronides

Conjugation with
glucuronic acid

O
O
H3C

OH

Conjugation with
glycine

NH

OH
Acetic acid

OH

OH

Sodium Salicylate
Oxidation

Salicyluric acid

O
HO

OH

OH
Gentisic acid
Scheme 2 Major metabolism pathways for aspirin.

wastewater in other countries around the world.

Nakada and coworkers, reported that aspirin had the
highest concentrations among other pharmaceuticals,
ranging from 470 to 19,400 ngL-1 in the sewage
treatment plants (STP) influents in Tokyo, Japan, and
were removed efficiently during primary and
secondary treatments (> 90% efficiency) [19]. Terns

and coworkers, reported average concentrations of

salicylic acid in public owned wastewater treatment
plants (POTWs) which received influents from both
domestic, municipal, and industrial sewage system 54
gL-1 influents and in effluents of 0.5 gL-1 [20].
The need for treatment technologies that can provide
safe treated effluents led to the implementation of new

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

competing technologies for biological degradation of

organic matter like membrane bioreactor. In addition,
other technologies include oxidation processes alone or
combined with nanofiltration or reverse osmosis were
utilized to treat effluents as well. Ozone-based and
Advanced Oxidation Processes (AOPs) using
hydrogen peroxide or radiation have been repeatedly
proposed for the removal of organic compounds in
wastewater. Proper combinations of AOPs have also
been considered in order to treat the more refractory
pollutants. Fenton and Fenton-based systems,
heterogeneous photocatalysis, and ultraviolet or
ozone-based oxidation processes have been described
[21-22].
The removal of salicylic acid (hydrolytic product of
aspirin) has been studied by different research groups.
Gagnon and coworkers studied the disinfection
processes in terms of removing salicylic acid. They
found that salicylic acid was eliminated at a rate higher
than 50% at an ozone dose of 10 mg/L, and a higher
rate (70%) were observed when 20 mg/L of ozone was
used. The ozone technology is better than UV radiation
in removal salicylic acid [23]. A high biodegradation of
salicylic acid (> 94%) during biologically activated
sludge (BAC) process supported that salicylic acid was
removed efficiently by BAC [24].
3.1.1 Kinetic Studies on the Stability of Aspirin in
Pure Water and Wastewater
Since many pharmaceuticals might undergo
degradation upon their standing in aqueous medium
and sludge environment, kinetic studies on aspirin in
pure water and sludge conditions have be undertaken.
The kinetic experiments in pure water were carried out
at room temperature in different pH values. The kinetic
results which were monitored by HPLC revealed that
aspirin undergoes hydrolysis to salicylic and acetic
acids via a general base catalyzed process and the rate
of the hydrolysis is first order and pH-independent
(Scheme 1). Fig. 1 shows the HPLC chromatogram of
aspirin in pure water after 5 days incubation at room
temperature. The peak at retention time of 4.3 minutes

127

belongs to aspirin and that at 5.5 minutes to the

hydrolysis product, salicylic acid. The kinetic data
were examined for linear relationship. A linear
correlation with a correlation coefficient (R) of 0.99
was found between ln [aspirin] (logarithms of aspirin
concentration) and time.
The correlation results obtained are illustrated
graphically in Fig. 2. The rate constant for the
hydrolysis of aspirin in pure water obtained from the
slope of the plot in Fig. 2 is 0.357 10-8 Ms-1 [25].
Similarly, kinetic study on the stability (hydrolysis)
of aspirin in wastewater was conducted. The HPLC
monitoring results for the hydrolysis of aspirin after
incubation in wastewater for 10 days were examined
for correlation-ship. The linear correlation of ln
[aspirin] vs. time gave a straight line with a correlation
coefficient (R) of 0.98 as shown in Fig. 2 (pink points).
The first order rate calculated from the slope of the
curve gave a value of 0.845 10-8 Ms-1.
Comparison of the hydrolysis reaction rate values in
pure water and in wastewater solution (0.357 10-8
Ms-1 vs. 0.845 10-8 Ms-1) revealed that the hydrolysis
in wastewater proceeds at faster rate than in pure water.
The accelerations in rate can be attributed to the
content nature of the wastewater (consisting of variety
of enzymes, bacteria and heavy metals) which can act
as a catalyst for such reactions.
3.1.2 Removal Efficiency of Salicylic Acid
(Hydrolysis Product of Aspirin) during Membrane
Separation and Adsorption by Activated Carbon and
Clay-micelle Complex
In eastern Mediterranean countries including
Palestine, the demand on water is growing rapidly due
to fast growth of population, urbanization and
socioeconomic development. Both the West Bank and
Gaza Strip are facing a series of wastewater and
sanitation-related problems: large-scale discharge of
untreated wastewater, leaking of collected wastewater
from sewer systems and cesspits, water treatment
plants that do not function or function only poorly
and uncontrolled reuse of untreated wastewater by the

128

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

Fig. 1 Chromatogram shows the hydrolysis of aspirin after 5 days.

Fig. 2 Plot of ln [Aspirin] vs. time (days) is for the hydrolysis of aspirin in pure water and is for the hydrolysis of aspirin
in the presence of wastewater.

irrigation sector. Those combined problems causing

many diseases related to contaminated drinking water.
Statistics from the Center for Disease Control and
Prevention (CDC) revealed that more than 17,000
cases of water-related illnesses have been spotted in
Gaza during the past two years. However, since many
symptoms are often confused with other sicknesses,
some researchers feel as many as 25 outbreaks go
unreported for every one reported, since many people
are exposed to potentially harmful microbes, pesticides
and chemicals [26].
One of the most widely used wastewater treatment
processes is the activated sludge process. It is a cost

effective treatment method under optimal conditions,

but bulking can be a chronic problem in some plants
[27]. The use of membranes for wastewater treatment
was limited in particular situations due to their high
costs (management and plant costs), and suspected to
microbial fouling [28]. After passing through the UF
units, the water can be disinfected by chlorination with
its health and environmental consequences[29].
Reverse osmosis (RO) membranes are capable of
rejecting bacteria, pharmaceuticals, salts, sugars,
proteins, dyes and other constituents that have a
molecular weight greater than 150-250 Daltons. RO
membranes, like all membranes, are subjected to

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

fouling by cake layer formation [30], but coupling

the membrane systems with other technologies such as
pretreatment using activated sludge process followed
by the use of reverse osmosis technologies could be the
most efficient method in treating wastewater
efficiently.
This research project was designed to evaluate the
performance of ultra filtration membranes (hollow
fiber and spiral wound), activated carbon adsorbers,
clay micelle complex and reverse osmosis in terms of
the removal of salicylic acid from synthetic wastewater
sample. The experiment took place in the WWTP
facility at Al-Quds University, Palestine. Fig. 3
illustrates a flow diagram of a wastewater treatment
plant consists of HF-UF filters (hollow fiber) and
SW-UF (spiral wound), activated carbon and RO
filters.
3.1.3 Salicylic Acid Wastewater Spiking and
Sampling
Sixty g salicylic acid standard was dissolved in
methanol then poured into the wastewater treatment
plant. Eight wastewater samples were collected from
different locations of the wastewater treatment plant

Wastewater
inlet from site
(Grey, black,
and storm
water)

Primary
settling
basin
(Screening)

Pumped
to
aeration tank

located in main campus of Al-Quds University at

Abu-Dies using pre-cleaned 500 mL glass containers.
Fig. 3 illustrates the sampling points (s.p.) which are as
follows: HF ultra filtration (hollow fiber) influent (s.p.
2) and Effluent (s.p. 4), SW-ultra filtration (spiral
wound) effluent (s.p. 6), activated carbon adsorber
effluent (s.p. 7) and reverse osmosis membrane (s.p. 8).
The eight samples were kept in ice bath during
transportion to the laboratory. Conventional
wastewater parameters for the eight samples including
total suspended solids (TSS), temperature, and pH
were measured then the samples were filtered and
adjusted to pH < 2 by the addition of concentrated
hydrochloric acid, and then stored at 4 . The samples
solutions were extracted by ether and after evaporation
were analyzed by HPLC (see diagram in Fig. 4). The
results obtained are summarized in Table 1.
3.1.4 The Efficiency of HF-UF (hollow fiber) and
SW-UF (spiral wound), Activated Carbon and RO
Membranes at the Removal of Salicylic Acid. Table 1
shows the efficiency of the removal of salicylic acid
during ultra filtration by hollow fiber (HF-UF),
spiral wound (SW-UF) and activated carbon filters.

Sand
filter

(Activated
carbon)
product
storage tank

Activate
d carbon
adsorber

(Concentrate)

RO product
storage tank

RO
membrane

Aeration Tank
(16-20 HRT)
Continuous circulation with
pump, adding coagulating
agent i.e. Aluminum sulfate
and chlorination

129

UF-SW
permeate tank
(Activated carbon and
reverse osmosis feed)

UF
filters
(Spiral
wound)

Storage tank

3
UF filters
(Hollow UF (brine)
fiber)

4
Hollow
fiber
(HF)
Permeate tank
(UF feed)

Fig. 3 Flow diagram shows the process of wastewater treatment plant which consists of HF-UF filters (hollow fiber) and
SW-UF (spiral wound), activated carbon and RO filters. The sampling locations in the plant are indicated by red printed
Arabic numbers.

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Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

500 ml wastewater sample

Filtration sample or Centrifuge

To avoid extraction inefficiencies
due to presence of suspended solids

Storage
Return the rest sample at 4 C
Acidification
Acidified
the
sample
with
concentrated HCl to pH 2 or less

Liquid- liquid Extraction

The extracted with diethyl ether

Drying and dissolve the target drug

before injection to HPLC
The dried residue (extracts) was
diluted with mobile phase

Reverse phase (HPLC-PDA)

Sample ready for injection into
HPLC-PDA
Fig. 4 Schematic representation for the analysis process of salicylic acid.
Table 1 Performances of hollow fiber ultra filtration (HF), spiral wound ultra filtration (SW), activated carbon adsorber and
reverse osmosis in terms of removal of salicylic acid from wastewater.
Sample location number (see Fig. 3)

Name of sample location

Sample No. 1

Sample No. 3

Blank (before addition 60 g of Salicylic acid)

Initial concentration of salicylic acid before running
wastewater treatment plant
Brine of HF-ultrafiltration-hollow fiber

Sample No. 4

Product of HF-ultrafiltration-hollow fiber

Sample No. 5

SW-ultrafiltration (spiral wound fiber) concentrate

6.776

Sample No. 6

Permeate of SW-ultrafiltration (spiral wound fiber)

5.6806

Sample No. 7

Product of activated carbon adsorber

Sample No. 2

Examination of the results listed in Table 1 reveal that

the efficiency of the ultra filtration process is more than
85% (samples No. 4 and 5) at the removal of salicylic

Concentration of salicylic acid (mg/L)

0
56.686
45.415
7.548

acid in the effluent sample. On the other hand, the

efficiency during activated carbon adsorber is 100%
(Sample No. 7). Therefore, there was no need to pass

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

the salicylic acid through the reverse osmosis

membrane.
3.1.5 The Efficiency of a Clay Micelle Membrane at
the Removal of Salicylic Acid
3.1.5.1 Clay Micelle Complex
Clay micelle complex is prepared by mixing certain
type of clay mineral (montmorillonite) with cationic
surfactant. In this study octadecyltrimethylammonium
(ODTMA) with a critical micelle concentration (CMC)
value of 0.3 mm was employed for a complex
formation. A certain mass of clay was introduced into a
solution of ODTMA until reaching a concentration of 1
10-2 m then stirred for 24 hours. The complex was
filtered and dried then mixed with excess sand. This
complex by virtue of its positive charge with
hydrophobic region is capable of binding negatively
charged organic molecules and bacteria as well [31].
H3C
N
H3C

CH3
(CH2)17CH3

Octadecyltrimethylammonium (ODTMA)

Equilibrium relationships between adsorbent and

adsorbate are described by adsorption isotherms. The
most common model for adsorption process is
Langmuir adsorption isotherm. The latter is the most
widely used for modeling equilibrium data and
determination of the adsorption capacity [32].
Its linear form is represented by Eq. (1):
Ce/Qe = 1/(k Qmax) + Ce/Qmax . (1)
Where, Ce is the equilibrium concentration of a
pharmaceutical (salicylic acid), Qe is the equilibrium
mass of adsorbed pharmaceutical (salicylic acid) per
gram of complex, k is the Langmuir constant, and Qmax
is the maximum mass of pharmaceutical (salicylic acid)
removed per gram of complex.
Fig. 5 shows a linear correlation between the terms
Ce/Qe and Ce which indicate that the adsorption of
salicylic acid on the clay micelle complex following
the Langmuir isotherm model. Qmax and k values for
the removal of salicylic acid by the clay micelle complex were determined from the slope and the intercept

131

of plot 1 shown in Fig. 5.

Slope= 1/Qmax = 0.0174; Qmax=57.47 mg/g.
Intercept = 1/k Qmax = 0.1163; k = 0.15.
Langmuir isotherm for the removal of salicylic acid
by charcoal adsorber was done in order to compare it
with the efficiency for the removal by a clay micelle
complex. Plot 2 shown in Fig. 5 describes the
Langmuir isotherm for the removal of salicylic acid by
charcoal. The calculated values of Qmax and k are
shown in the following equations: Slope= 1/Qmax =
0.0162; Qmax= 61.73 mg/g.
Intercept = 1/k Qmax = 0.1646; k = 0.098.
Comparison between the calculated values of Qmax
for the adsorption of salicylic acid on the clay micelle
complex and charcoal reveals that both have
comparable efficiency. However, since the quantity of
the cationic surfactant in the clay micelle is about 3
times smaller than the quantity of activated carbon in
charcoal, the effective absorption efficiency of the clay
micelle is much superior than charcoal.
3.2 Paracetamol
Paracetamol (acetaminophen) is one of the most
popular over-the-counter analgesic and antipyretic
drugs. Paracetamol is available in different dosage
forms: tablet, capsules, drops, elixirs, suspensions and
suppositories. Its saturated aqueous solution has a pH
of about 6 and is stable (half-life over 20 years) but
stability decreases in acid or alkaline condition due to
being slowly broken down, via a base or acid
hydrolyzed hydrolysis of the amide bond, into acetic
acid and p-aminophenol (Scheme 3) [33-34].
Paracetamol is metabolized primarily in the liver,
into non-toxic products. Three metabolic pathways are
notable as shown in Scheme 4. Glucuronidation is
believed to account for 40% to two-thirds of the
metabolism of paracetamol [35]. Sulfation (sulfate
conjugation) may account for 20-40% [35].
N-hydroxylation and rearrangement, then GSH
conjugation, accounts for less than 15%. The
hepatic cytochrome P450 enzyme system metabolizes

132

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

Fig. 5 Langmuir isotherms for the removal of aspirin by a clay micelle (plot 1) and by charcoal (plot 2) and for removing
paracetamol and p-aminophenol by a clay micelle complex (plots 3 and 4, respectively).

O
HN

C
CH3
O

HN

H
O

Hydrolysis

H or OH

OH
Paracetamol

H3C

OH

OH
p-Aminophenol

Acetic acid

Scheme 3 Hydrolysis pathway for paracetamol.

paracetamol, forming a minor yet significant alkylating

metabolite known as NAPQI (N-acetyl-p-benzoquinone imine). NAPQI is then irreversibly conjugated
with the sulfhydryl groups of glutathione [36]. All
three pathways yield final products that are inactive,
non-toxic, and eventually excreted by the kidneys. In
the third pathway, however, the intermediate product
NAPQI is toxic. NAPQI is primarily responsible for
the toxic effects of paracetamol [36].
Paracetamol is widely used all over the world. In a
study conducted in 2000 [37], paracetamol was ranked
as one of the top three drugs prescribed in England, and
the mass of paracetamol through prescription alone
totaled more than 400 tons in that year. Paracetamol has
been found with a concentration of up to 6 mgL-1 in
European STP effluents [38], up to 10 mgL-1 in natural
waters in USA [39] and even more than 65 mgL-1 in the

Tyne River, UK. Furthermore, according to a

reconnaissance study of organic wastewater
contaminants in USA waters, paracetamol was
determined to occur at a frequency of 23.8% in surface
water at a maximum concentration of 10 gL-1 [38].
Paracetamol was chosen for this study because it is
widely used as an over-the-counter and prescribed
medication in Israel and Palestine [15] and therefore,
was anticipated to occur in wastewater influent. It is
among the top twenty medicines that have been found
to be frequently used in the West Bank and Jerusalem
[15].
3.2.1 Kinetic Studies on the Stability of Paracetamol
in Pure Water and Wastewater
Under abnormal conditions (heat, pH, temperature,
etc.) paracetamol degrades slowly forming a mixture of

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol
O
C

HN

CH3

Glucoronidation
O
HN

O
CH3

GlcA
O

Sulfation

HN

N-Hydroxylation and
rearrangement

CH3

OH
Paracetamol

OH

O
N

O
S

HN
CH3

CH3

GSH Conjugation

GSH
O

OH

Toxic reactions with

protiens and nucleic acids

Scheme 4 Metabolic pathways for paracetamol.

contaminants, such as 4-aminophenol and acetic acid.

This reaction (Scheme 3) could also be carried out by
enzymatic cleavage or by microwave assisted alkaline
hydrolysis.
In a similar manner to that of aspirin, kinetic studies
on paracetamol in pure water have been carried out at a
room temperature in a wide pH range. The kinetic
results which were monitored by HPLC revealed that
paracetamol was completely stable under these
conditions due to the high activation energy needed to
break down the amide bond. No degradation products
were observed after incubation for more than two
weeks.
On the other hand, HPLC monitoring of a solution of
paracetamol in the presence of wastewater gave a
gradual disappearance of a peak characterized as the
reactant at a retention time of 3.93 minutes and a

133

gradual appearance of a new peak at a retention time of

1.97 minutes characterized as a product. Fig. 6 shows a
representative chromatogram for the hydrolysis of
paracetamol to products. Characterization of the
compound that showed a peak at 3.93 minutes revealed
that the hydrolyzed product of paracetamol is
p-aminophenol. This result was supported by the fact
that when a standard solution of p-aminophenol was
injected to HPLC at the same conditions of the kinetic
experiments only one peak at a retention time of 3.93
minutes was obtained.
The kinetic data obtained from the HPLC
monitoring (7 days) were examined for linear
correlation. The correlation results indicate a linear
correlation between ln [paracetamol] and time with a
correlation coefficient R = 0.94 (Fig. 7). The rate
constant for the hydrolysis of paracetamol obtained
from the slope of the plot in Fig. 7 is 1.0 10-8 Ms-1.
3.2.2 Paracetamol and Its Hydrolyzed Product
(p-aminophenol) Wastewater Spiking and Sampling
Samples of 60 g of paracetamol and 60 g of its
hydrolyzed product (p-aminophenol) were dissolved in
methanol and were introduced to WWTP. Then eight
wastewater samples were collected from different
locations of WWTP located in Al-Quds University
main campus at Abu-Dies using pre-cleaned 500 mL
amber glass bottles. Samples from the sampling points
2, 4, 6, 7 and 8 (Fig. 3) were collected for observing the
removal membranes efficiency: ultra filtration (hollow
fiber and spiral wound), then followed by activated
carbon and reverse osmosis membrane.
3.2.3 The Efficiency of HF-UF (hollow fiber),
SW-UF (spiral wound), Activated Carbon and RO
Membranes at the Removal of Paracetamol and
p-aminophenol
Since paracetamol was found to undergo hydrolysis
to p-aminophenol when kept standing for some time in
sludge we sought to study the efficiency of the different
membranes on the removal of both paracetamol and
p-aminophenol. Table 2 summarizes the results of
the efficiency of HF-UF (hollow fiber), SW-UF (spiral

134

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

Fig. 6 Chromatogram shows the hydrolysis of paracetamol after 2 days.

Fig. 7 Plot of ln [Paracetamol] vs. time (days) for the hydrolysis of paracetamol in the presence of wastewater at room
temperature.

wound), activated carbon and reverse osmosis

membranes
in
removing
paracetamol
and
p-aminophenol.
Inspection of the results listed in Table 2 indicates
that the efficiency of the ultra filtration process is about
40% (samples No. 4 and 5) at the removal of
paracetamol and about 70% at that of p-aminophenol in
the effluent samples. On the other hand, both the
activated carbon adsorber and the reverse osmosis
membranes were significantly superior in the removal
of paracetamol and p-aminophenol. In the case of
acetaminophen a removal of 99% was observed by

both membranes whereas, a 100% removal was

achieved when 4-aminophenol was tested (Sample No.
7 and 8).
3.1.3 The Efficiency of a Clay Micelle Membrane at
the Removal of the Hydrolysis Product of Paracetamol
(p-aminophenol)
In a similar to that conducted for salicylic acid,
Langmuir isotherms for the removal of paracetamol
and its hydrolysis product p-aminophenol by a clay
micelle complex were established. Plots 3 and 4 shown
in Fig. 5 describe the Langmuir isotherms for the
removal of both chemicals. The calculated Qmax and k

Efficiency of Advanced Membrane Wastewater Treatment Plant towards Removal of Aspirin, Salicylic
Acid, Paracetamol and p-Aminophenol

135

Table 2 Performance of hollow fiber ultra-filtration (HF), spiral wound ultra-filtration (SW), activated carbon adsorber and
reverse osmosis in terms of removal of paracetamol and p-aminophenol from wastewater.
Sample location No.( Fig. 3)
Sample No. 1
Sample No. 2
Sample No. 3
Sample No. 4

Concentration
of Concentration
of
paracetamol (mg/L)
p-aminophenol (mg/L)

Sample location name

Blank (before addition of 25 g paracetamol and

0
p-aminophenol)
Initial concentration of paracetamol and
p-aminophenol before running wastewater 20.95
treatment plant
Brine of HF-Ultra filtration-Hollow fiber
20.92

Sample No. 7

Product of HF-Ultra filtration-Hollow fiber

SW-Ultra filtration (spiral wound fiber)
concentrate
Permeate of SW-Ultra filtration (spiral wound
fiber)
Product of activated carbon adsorber

Sample No. 8

Product of reverse osmosis

Sample No. 5
Sample No. 6

values for paracetamol are 178.6 mg/g, 0.0377,

respectively and that for p-aminophenol are 29.4 mg/g
and 0.2, respectively. The Langmuir isotherms for the
removal of both chemicals by charcoal gave Qmax
values 129.9 mg/g for paracetamol and 11.12 mg/g for
p-aminophenol and the calculated k values were 0.39
for paracetamol and 8.25 for p-aminophenol.
Comparison of the calculated Qmax values of both
chemicals using the clay micelle complex and charcoal
reveals that the former is more efficient than the latter
in removing paracetamol and p-aminophenol.

4. Conclusions
The combined results revealed the following: (1)
both aspirin and paracetamol are not stable in
wastewater conditions and they undergo a relatively
fast hydrolysis to the corresponding hydrolysis
products. Therefore, efforts should be concentrated on
finding suitable methods for the removal of salicylic
acid (aspirin product) and p-aminophenol (paracetamol
product) rather than to be focused on the parental
drugs.
(2) The efficiency of hollow fiber and spiral wound
membranes at the removal of the pharmaceutical
studied herein (paracetamol and aspirin) is not
satisfactory (40-70%), whereas, the activated carbon,
clay micelle complex and the reverse osmosis
membranes were completely efficient in removing both

0
24.3
20.4

12.47

6.87

11.84

5.22

10.73

2.82

0.223

0.11

pharmaceuticals (about 100%). Hence, the authors

conclude that a clay micelle complex and activated
carbon filters can effectively remove pharmaceuticals
of the kind described herein and there is no need to use
more expensive methods such as the removal by
reverse osmosis membrane.

Acknowledgements
Beir-Zeit Pharmaceutical Co. is thanked for the
supply of paracetamol and aspirin. Special thanks are
given to Dr. Saleh Abu-Lafi for technical assistance.
This work was supported by a generous grant from
United States Agency for International Development
(USAID), Middle East Regional Cooperation (MERC)
program.

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