Thai Environmental Engineering Journal : Special Vol.

January-April 2012 : 187-191

www.eeat.or.th

Treatment of Paracetamol in Bangkok’s Sewage by

Activated Sludge Process and Its Attenuation in Receiving Canal

Siriporn Poltam, Wilai Chiemchaisri* and Chart Chiemchaisri

Department of Environmental Engineering, Faculty of Engineering,

Kasetsart University, Chatuchak, Bangkok, 10900, Thailand
*
E-mail: fengwlc@ku.ac.th

Abstract

Paracetamol in Bangkok’s sewage and its fate in activated sludge process and the receiving
canal had been determined via GC-MS. The concentrations of Paracetamol in sewage, settled
sewage, effluent and disposal sludge were in ranges of 500-800 ng/L, 440-750 ng/L, and
170-288 ng/L and 15-20 ng/g dried sludge, respectively. The proximate Paracetamol levels as in the
discharge water were found in the receiving canal. Paracetamol eliminated rates by the AS process
were about 61-66% in which 41-51% by biodegradation and 13-23% by adsorption. Batch sorption
studies indicate that the sludge had high potentiality in Paracetamol adsorption in AS process in
which 15% of the adsorbed mass could desorb out into a clean environment.

Keywords: Paracetamol; activated sludge; sorption; sewage; treatment

Introduction liver failure [3]. In Thailand, the usage of

Pharmaceuticals are a set of compounds
which have obtained increasing attention over
the past decade. There are many different
compound classes which are intended to affect
a specific area of a disease. Recently, it has
become clear that the elimination of certain
pharmaceutical compounds during wastewater
treatment processes is rather low and as a
result, they are found in surface, ground and
drinking waters [1]. Analgesics are widely
used today and very often used as
acetaminophen or Paracetamol. The facts that
Paracetamol is qualified as both drugs in
relieve pain and drug fever. The main reasons
that led to a widely used Paracetamol are
because it is easy to buy without a prescription
from a doctor. Therefore, the usage of this drug
is rapidly increasing. Thus, the general public
is not aware of this drug because they do not
know too much about toxicity [2]. Mainly
causing liver injury, Paracetamol toxicity is one
of the most common causes of poisoning
worldwide. In the United States and the United
Kingdom it is the most common cause of acute
Paracetamol is on the rise with an estimated
increase between 2000 and 2009 [4]. For this
reason, Paracetamol may be able to cause the
same harmful exposure potential as persistent
pollutants, since their transformation and
removal rates can be compensated by their
continuous input into the environment. In this
study we aimed to determine the contamination
of wastewater and activated sludge with
Paracetamol in order to obtain more
information on its fate during sewage
wastewater treatment of Bangkok city. In
addition, this study suggests that more needs to
be known about the environmental fate of
Paracetamol so that we are able to provide a
comprehensive risk assessment.
Materials and Methods
Materials and Sampling Protocol
Water and disposal sludge were sampled
from Din Daeng Water Environment Control
Plant (UBA) during January to April 2011.
Besides, water samples from the receiving
canal were taken approximately far from the

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188 Thai Environmental Engineering Journal : Special Vol. January-April 2012
discharge point at 1, 2, and 3 kilometer(s).
These samples were collected in the same day
as the samples from the treatment plant.
Paracetamol Extraction and Determination
in Water Sample
Paracetamol (N-Acetyl-p-aminophenol,
standard grade, Sigma Aldrich) and
derivative reagent (N-methyl-N-
trimethylsilyltrifloroacetamide, MSTFA, Sigma
Aldrich) were employed for GC-MS analyses
(Shimadzu-2010). The SPE cartridges filled
with HCP-SA 100 mg Polyamide-Divinylbenzene
Copolymer Trimethylaminopropyl, PA-DVBT
(Vertical®) was used for Paracetamol extraction
from water samples. The Paracetamol extraction
and analysis were conducted as described
in [5].
Paracetamol Extraction and Determination
in Sludge Sample
A 100 g of the fresh sludge (78%MC
disposal sludge) sample were added into 250
ml of distilled water. The mixture was stirred
at 150 rpm for 1 hr, under 50ºC to allow the
Paracetamol leaching to the aqueous. After
centrifugation, the supernatant was filtered and
treated in similar procedure as a water sample.
Two times of leaching were conducted for each
solid sample. The remaining solids were added
into 200 ml methanol, and homogenized at
100 rpm for 1 hr. The mixer was centrifuged
for 15 min at 3,500 rpm. The methanol
supernatant was evaporated by N2 purging.
It was then carried out to the derivation process
as described in [5] before being made up to a
volume of 0.5 ml with hexane (99.9%) and
analyzed via GC-MS. For reference, it was
found that most of Paracetamol was in the
leaching water and the slight Paracetamol level
was detected in the methanol extract.
Batch Experiments of Adsorption/Desorption
of Paracetamol on Activated Sludge
The 22.7 g of sterile fresh sludge (121oC,
15 min) was stirred in a 100 mL of normal
saline (0.85%NaCl) at 50ºC for 5 min in order
to wash out the adsorbed Paracetamol on the
sludge after centrifugation. Two times of
elution were performed. Then, the sludge was
077-ACP
mixed with various concentrations of 1 L
Paracetamol solution (Co) of 2000, 4000, 6000,
8000, 10000 ng/L. Then the mixtures were
stirred at 150 rpm for 1 hr and then
subsequently centrifuged. An aliquot of
supernatant was filtered, extracted and
analyzed for Paracetamol content. The
remaining sludge was further carried out
for desorption experiment. In order to
simulate desorption in clean environment,
a 1 L distilled water was added in to the
sludge and the mixture was stirred at 50oC for
1 hr. The mixture was subsequently centrifuged
and an aliquot of supernatant solution was
analyzed as water sample described in above.
Then, we used the most popular adsorption
model for a single solute system, the
Freundlich model that is an empirical equation
based on the distribution of solute between
the solid phase and aqueous phase at
equilibrium [6]. The adsorption and desorption
data were analyzed using the Freundlich
equation (1):
qe = KFCen (1)
Where; qe is solid-phase equilibrium
concentration of Paracetamol adsorbed/
desorbed (ng/g), Ce is liquid-phase equilibrium
concentration of Paracetamol (ng/L), KF is the
Freundlich capacity factor, and n is the
Freundlich exponent. Eq. 1 can be linear by
taking logarithms to find out the parameters
KF and n.
Results and Discussion
Evaluation of Adsorption/Desorption
Potential of Paracetamol on the Activated
Sludge
The results of log of Paracetamol
dosages/remaining in water were plotted in
linear form as shown in Figures 1 and 2, the
adsorption and desorption equations are
obtained as follows:
Adsorption: log qad = 1.255 log Ce – 0.456 (2)
Desorption: log qdes = 1.000 log Ce – 0.699 (3)
Thai Environmental Engineering Journal : Special Vol. January-April 2012 189

As the result, summarized of adsorption adsorbed/desorbed (qe) at the equilibrium

and desorption isotherms are shown in Table 1.
KF value of adsorption in activated sludge
was higher than that in the desorption process,
which suggests that some fractions of
Paracetamol is reversibly bound to the activated
sludge. In this study we also used these
isotherms to calculate the adsorption potential of
Paracetamol on the studied activated sludge. By
an assumption that the amount of Paracetamol
when Ce of effluent = 201 ng/L, the total
adsorbed/desorbed mass was calculated on the
basis of the Freundlich constants (n and KF)
as shown in Table 1. As the result, it
indicates that the MLSS can adsorb Paracetamol
of 272 ng/g,dry. Besides, desorption of the
absorbed Paracetamol possibly occurs in clean
environment of 40.2 ng/g,dry or 15% of the total
absorbed mass daily (Table 1).

Table 1 Freundlich isotherms of adsorption and desorption of Paracetamol on the sludge

qe(ng/g) at
Regress equation log KF KF n R2
Ce=200 ng/L
Adsorption - 0.456 0.35 1.255 0.98 272
Desorption - 0.699 0.2 1.000 1.00 40.2

Figure 1. Adsorption isotherm of Paracetamol Figure 2. Desorption isotherm of Paracetamol

on activated sludge on activated sludge

Removal Mechanism of Paracetamol in was 64.69% on average. By calculation of a

the Activated Sludge Process and Its
Attenuation in Receiving Canal
The concentrations of Paracetamol
in sewage, settled sewage, effluent and
disposal sludge varied insignificantly during
investigation period with in ranges of
500-800 ng/L, 440-750 ng/L, and 170-288 ng/L
and 15-20 ng/g dried sludge, respectively
(Figure 3). It was found that the removal from
aqueous-phase (Raq-phase) referring to the loss of
Paracetamol between the influent and effluent
missing part in mass balance equation,
the biodegraded Paracetamol in the
activated sludge process was 45.33% on
average (Table 2). This result is different from
many researchers who reported that over 99%
removal of Paracetamol in AS process is by
biodegradation [1, 7, and 8]. In this study,
we found that not only biodegradation,
adsorption of Paracetamol (13-23%) in the AS
process is a significant removal mechanism.
And because 15% of the adsorbed Paracetamol

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190 Thai Environmental Engineering Journal : Special Vol. January-April 2012

could desorb, it suggests that the sludge should
be carefully handled/treated further to avoid
fate of Paracetamol into the environment.
Although the concentrations of Paracetamol
in the effluent existed in nano levels, however
the large volumes of the discharge treated
water were about 200,000-300,000 cu.m/d, and
the calculated discharged Paracetamol into the
receiving canal was 40.67 g/d on average. We
found the concentrations of Paracetamol in
the receiving canal were proximate levels
to those in the effluents (Figure 4) which
indicates that slight degradation of Paracetamol
was found in the receiving canal during
3 kilometers from the discharged point.
Therefore, it is more necessary to be known
about its persistence in the environment
for further risk evaluation.

Figure 3. Distribution of Paracetamol in the Figure 4. Concentrations of Paracetamol in the

activated sludge process receiving canal compared to the effluent

Table 2 Fates of Paracetamol in the activated sludge process

Mass of Paracetamol (g/d)

Sample avg sd
28-1-11 25-2-11 18-3-11 25-3-11 8-4-11 22-4-11
1. Sewage 144 107 103 100 92 144 115.0 23
2. Settled sewage 143 103 101 79 92 139 109.5 25.86
%R (1-2) 0.99 3.74 1.94 21.00 0.00 3.47 5.19 7.88
3. Effluent 49 41 35 35 31 53 40.67 8.71
%Raq (1-3) 65.97 61.68 66.02 65.00 66.30 63.19 64.69 3.88
4. Disposal sludge nd nd 0.025 0.027 0.021 0.019 0.023 0.004
5. MLSScal - - 21.45 23.10 20.69 18.35 20.90 1.97
% Rad - - 20.83 23.10 22.49 12.74 19.79 2.01
%Rcal biodeg. - - 45.19 41.9 43.81 50.45 45.33 1.87
Note: nd: not determined; aq: aqueous phase; cal biodeg: calculated biodegradation, avg: average, sd:
standard deviation; %R: removal percentage; MLSScal: calculated adsorbed paracetamol in MLSS

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Thai Environmental Engineering Journal : Special Vol. January-April 2012
Conclusions
Determinations of Paracetamol in the AS
discharge water/sludge and receiving canal
samples indicate high persistence in
biodegradation by exhibiting several hundred
nanograms of concentrations. The existing AS
process is moderate efficient to remove
Paracetamol from Bangkok’s sewage by only
61-66% in which 41-51% by biodegradation
and 13-23% by adsorption. Desorption of
Paracetamol from the sludge into clean water
was 15% of the total adsorbed one. The
proximate Paracetamol levels as in the
discharge water were found in the receiving
canal.
Acknowledgements
The authors would like to acknowledge
the WateR-InTro Project: “Research and
Development for Water Reuse Technology in
Tropical Regions” for the financial support.
We appreciate the Bangkok Metropolitan
Authority (BMA) for collaboration and thank
the National Research Council of Thailand
(NRCT) for networking fund.
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