International Journal of Environmental Science and Technology

https://doi.org/10.1007/s13762-020-02758-1

ORIGINAL PAPER

Feasibility of mercury (II) ion removal by nitrated polycarbonate

derived from waste optical discs
S. A. Abdallah1,2 · K. S. Tay1 · K. H. Low1 

Received: 23 December 2019 / Revised: 22 April 2020 / Accepted: 27 April 2020

© Islamic Azad University (IAU) 2020

Abstract
Advanced technology has led to the generation of the massive amount of electrical and electronic wastes, including compact
discs and digital versatile discs. These optical discs are often ended up in landfills and incinerators, resulting in severe envi-
ronmental degradation. This research aims to recover polycarbonate from waste optical discs and exploring its potential as a
sorbent for the removal of mercury in water. The recovered polycarbonate was nitrated to enhance its efficiency in removing
mercury (II) ion. The nitrated polycarbonate was characterized using Fourier-transform infrared spectroscopy, field emission
scanning electron microscopy, thermogravimetric analysis, energy-dispersive X-ray spectroscopy and Brunauer–Emmett–
Teller surface area analysis. Response surface methodology was employed to investigate the effects of agitation rate, contact
time, pH, initial concentration, sorbent dosage on the mercury (II) ion removal efficiency via a central composite design.
According to the quadratic model, an optimum response can be achieved at 188.6 rpm of agitation, 150 min of contact time,
pH 7.55 and 1.50 mg/L of initial mercury (II) ion concentration. The adsorption process was found to follow the Freundlich
isotherm model, and the adsorption mechanism was found to obey the pseudo-second-order kinetic model that indicates
the chemisorption process. The results of this study showed that the nitrated PC with a maximum adsorption capacity of
0.289 mg/g has the potential to be used as a sorbent in water treatment for the removal of mercury (II) ion in water.

Keywords  Adsorption · Design of experiments · E-waste · Heavy metal · Waste to wealth

Introduction constituted a significant fraction of e-waste in landfill (Noo-

Due to rapid advancement in technology, the amount of dis-
carded electrical and electronic devices or so-called e-waste
has increased rapidly around the world. Optical discs such
as compact discs (CDs) and digital versatile discs (DVDs)
Editorial responsibility: J. Aravind.
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1376​2-020-02758​-1) contains
supplementary material, which is available to authorized users.
* K. S. Tay
khengsoo@um.edu.my
* K. H. Low
lowkayin@um.edu.my
1
Department of Chemistry, Faculty of Science, University
of Malaya, 50603 Kuala Lumpur, Malaysia
2
Department of Science Laboratory Technology, College
of Science and Technology, Hussaini Adamu Federal
Polytechnic, P.M.B. 5004, Kazaure, Jigawa State, Nigeria
rimotlagh et al. 2019). These optical discs contain a large
portion of polycarbonate (PC, ~ 95%), and this has brought
about the concerns related to the release of bisphenol-A,
the monomer of polycarbonate which is known to be the
endocrine disruptor, into the environment through landfill
(Petrie et al. 2019). Incineration of CDs and DVDs is also
found to produce greenhouse gases and other noxious gases
(Weeden et al. 2015). As a result, numerous approaches
involving reduce, reuse or recycle CDs and DVDs have been
implemented (Leone et al. 2015) to circumvent the potential
environmental and health issues. In this context, one of the
significant challenges is converting the PC-based e-waste
into the material with useful applications.
According to previous reports, several surface modifica-
tion efforts have been carried out on PC to convert it into
the material with specific applications in various areas. For
example, PC was surface-modified with sulphochromic
acid, nitration reaction, oxidation, ammonia-radio frequency
glow discharge and corona discharge to produce substra-
tum for animal cell culture (Dewez et al. 1991). The surface

13
Vol.:(0123456789)

functionalization of PC with phenols and nitrophenols to
enhance the adhesion of the PC sheet to the metal layer for
electronic equipment also has been reported (Zarnoch 1994).
Furthermore, the modification of the surface of the PC with
proteins to produce open tubular enzymatic microreactors
was also established by Ogończyk et al. (2012). Jain et al.
(2012) managed to modify the surface of PC for immobi-
lization of antibodies to produce aminated polycarbonate
membrane as highly sensitive enzyme-linked immunosorb-
ent for the detection of Salmonella typhi.
Based on the chemical structure, PC, which is rich in the
aromatic ring, has the potential to uptake metal ions. To a
certain extent, part of these functional groups can be modi-
fied to enhance the adsorption capability of PC on metal
ions. For instance, the surface reactivity of the PC can be
manipulated by anchoring electron-rich functional groups to
enhance the adsorption of metal ions (Al-Ghouti et al. 2019).
This research aimed to convert the reclaimed PC from waste
CDs into sorbent for the removal of mercury (II) ion (­ Hg2+).
This study explored the potential of nitrated PC, synthesized
using PC that recovered from waste CDs, as sorbent for the
adsorption of ­Hg2+ in water.
Adsorption is a popular technique used in water treatment
for the removal of harmful substances due to its operational
and design simplicity (Herman et al. 2020; Kim et al. 2020).
The efficiency of adsorption processes in the removal of pol-
lutants is often influenced by operating parameters such as
pH, sorbent dosage, temperature, contact time, stirring speed
and initial concentration. Most of the studies optimized the
operating parameters of adsorption without considering the
simultaneous interactive impact of two or more operating
parameters on the performance of the adsorption process
(Al-Ghouti et al. 2019; Hong et al. 2020). Therefore, this
study optimized the operating parameters of the adsorption
of ­Hg2+ by nitrated PC, which include the initial concentra-
tion of ­Hg2+, pH of water, contact time, sorbent dosage, rate
of agitation via response surface methodology (RSM) based
on a central composite design (CCD). Through RSM, an
optimized adsorption method can be obtained by consider-
ing the interactive impact of operating parameters (Hong
et al. 2020). The adsorption mechanism of H ­ g2+ by nitrated
PC was also evaluated through isotherms and kinetic studies.
Date and location of the research
This research was carried out at the University of Malaya
during the period of 13 November 2018 to 27 September
2019.
13
International Journal of Environmental Science and Technology
Materials and methods
Chemical reagents
All reagents used were of analytical grade. Ultrapure water
was produced from an Elga Purelab UHQ (United Kingdom)
water purification system. Dichloromethane and hydrochlo-
ric acid were obtained from R&M. Methanol, nitric acid,
sulfuric acid, monosodium dihydrogen phosphate, disodium
hydrogen phosphate and mercury reference standard were
purchased from Merck. Pure PC (PPC) was obtained from
Sigma-Aldrich.
Preparation of nitrated recovered PC (NRPC)
The coating and label on the surface of the waste optical
discs were first removed mechanically. The optical discs
were then cut into small pellets. The pellets were washed
sequentially with 10% acetic acid solution, 5% sodium
hydroxide solution, ultrapure water and dried at 80 °C for
12 h. The obtained PC was purified as reported by Achilias
et al. (2009) with slight modification. In this experiment, 1 g
of the sample was first dissolved in 20 mL dichloromethane,
and the mixture was shaken for 1 h at room temperature
using an orbital shaker. The solution was then filtered into
30 mL of methanol to precipitate the PC. The collected pre-
cipitate was thoroughly washed with ultrapure water and
dried at 80 °C.
The NRPC was prepared from the recovered PC (RPC)
via the mixed acids technique (Vani et al. 2013). Briefly,
2 g of RPC was added into 40 mL of the mixture of nitric
acid and sulfuric acid (4:1 v/v), and the mixture was stirred
for 5 h at 50 °C. After cooling, the suspension was neutral-
ized with sodium hydroxide solution (5:12 w/v), followed by
washing with ultrapure water and methanol. The NRPC was
dried at 80 °C and subsequently was ground into a powder
and sieved into the particle sizes of 250, 600 and 1000 μm.
The NRPC was stored in a desiccator before use.
Method for the characterization of NRPC
The infrared (IR) spectra of the PPC, RPC and NRPC were
recorded using an attenuated total reflectance Fourier trans-
form infrared (ATR-FTIR) spectrophotometer (Perkin Elmer
400). A resolution of 2 cm−1 and a total of 16 scans were
applied to collect the IR spectra. Thermogravimetric anal-
ysis (TGA) was carried out using a simultaneous thermal
analyzer (Perkin Elmer STA 6000). The sample was heated
at the rate of 10 °C/min from 30 to 1000 °C. The morphol-
ogy of NRPC was recorded using field emission scanning
electron microscopy equipped with energy-dispersive
International Journal of Environmental Science and Technology

X-ray spectroscopy (EDX) (FESEM, Hitachi SU8220). concentration in the supernatant was determined using
Specific surface area measurements were conducted using mercury analyzer. The H­ g2+ removal efficiency (Y  ) and the
Brunauer–Emmett–Teller (BET) surface analysis on equilibrium adsorption capacity Qe (mg/g) of the NRPC are
micromeritics instrument. calculated using the following Eqs. 2 and 3, respectively
(Tran et al. 2015).
Mercury removal and adsorption studies
C0 − Ce
Y= × 100% (2)
To screen the performance of the NRPC against RPC, C0
70 mg of RPC and NRPC was shaken with 1.0 mg/L of
the ­Hg2+ at 150 rpm for 12 h at room temperature at vari- C0 − Ce
Qe = ×V (3)
ous pH conditions. The remaining ­Hg2+ in the supernatant m
was subsequently determined using mercury analyzer (NIC
where C0 (mg/L) is the initial concentration of ­Hg2+, Ce
RA-3). The effect of particle size was screened at 250, 600
(mg/L) is the equilibrium concentration of ­Hg2+, m is the
and 1000 μm.
mass of the NRPC, and V is the volume of the aqueous
solution.
Design of experiments

RSM was applied to study simultaneously the effects of

Adsorption isotherms study
operating parameters of the adsorption, which include
The isothermal adsorption was studied according to the
rate of agitation, contact time, pH, initial concentration of
batch adsorption method under the optimized experimental
­Hg2+ and NRPC dosage on the percentage of H ­ g2+ removal
condition. The adsorption equilibria were described by the
according to the study domain defined in Table 1 based on a
widely applied Langmuir and Freundlich models (Abas et al.
CCD. The following model was postulated for the response
2013) represented in Eqs. 4 and 5:
surface:
Ce 1 C
+ e
∑ ∑ ∑
Y = 𝛽0 + 𝛽i Xi + 𝛽ij Xi Xj + 𝛽ii Xi2 + 𝜀
(1)
= (4)
i i<j i
Qe qm kL qm

where Y is the predicted response, 𝛽0 is the intercept; 𝛽i, 𝛽ij , 1

and 𝛽ii are the linear, interaction and quadratic coefficients of log10 Qe = log10 kf + log10 Ce (5)
n
factor ith and jth. 𝜀 is the error term (Xu et al. 2013). Simi-
larly, Xi, and Xj represent the respective coded factor levels. where qm is the theoretical maximum adsorption capacity
(mg/g); kL is the Langmuir constant related to the energy of
Adsorption experiments ­ g2+
adsorption and the affinity of the binding sites for the H
(L/mg); kf and n are the Freundlich constants that indicate
The adsorption of ­Hg2+ on NRPC was performed at room adsorption capacity and adsorption intensity, respectively
temperature according to the design matrix shown in (Khor et al. 2017).
Table S1, where the treatments were carried out in tripli-
cates and in randomized order. For the experiment, NRPC Adsorption kinetics
­ g2+ solution with appropriate pH, and
was added into the H
the mixture was shaken on an orbital shaker for a defined The adsorption kinetic experiments were carried out using
time interval. The NRPC was then filtered, and the ­Hg2+ the optimized operating conditions where ­Hg2+ concen-
trations were measured at the defined time interval. The
adsorption capability (Qe) of NRPC at time t  , or equilib-
Table 1  Factor domain and the coded variables
rium, is expressed in Eq. 3. The kinetics of the adsorption of
­Hg2+ by NRPC was evaluated using the pseudo-first-order
Coded levels, Xi model, pseudo-second-order model and intra-particle dif-
 − 1 0  + 1 fusion model as described by Eqs. 6, 7 and 8, respectively
(Khor et al. 2017; Tran et al. 2015):
Agitation rate / rpm 100 150 200
Contact time / min 30 90 150 k
log Qe − Qt = − 1 t + log Qe (6)
( )
pH 4 6 8 2.303
Initial concentration / mg/g 0.5 1.0 1.5
Adsorbent dosage / mg 40 70 100

13
 International Journal of Environmental Science and Technology

t t 1 NRPC
= + (7)

2974
Qt Qe k2 Q2e

558
1014
1503
75

26 1347
17

34
15
1157
RPC

1189
12
√
Qt = kipd t + C (8)

% Transmittance

2970
where k1, k2, and kipd are corresponding rate constants for the

558
1503
pseudo-first-order model, pseudo-second-order model and

1010
1766
intra-particle diffusion model, respectively. C is the bound- PPC

17
1157

1189
12
ary layer thickness.

2970

1503

558
The influence of matrix effect on the performance

1010
1766
of NRPC in the removal of ­Hg2+

17
12
1157

57
11
4500 4000 3500 3000 2500 2000 1500 1000 500

The performance of NRPC in the removal of H ­ g2+ from Wave number (cm-1)
water matrices was evaluated. Ultrapure water, mineral
water, lake water and tap water samples were spiked with Fig. 1  FTIR characteristic spectra of PPC, RPC and NRPC
1.5 mg/L of ­Hg2+ before being subjected to the adsorption
experiment under the optimized condition. The concentra-
tions of remaining ­Hg2+ were determined using a Mercury 110
Analyzer.

80.67%
90 (a)

83.27%
Statistical analysis 70

50
(b)
The design of experiments and statistical analyses were per-
formed using JMP 12.2 (SAS). Half normal plot was used to 30
screen the important effects based on the runs, and empiri-
cal models were approximated with regression (Grömping 10
2015). The postulated models were assessed with analysis 0 200 400 600 800 1000

of variance (ANOVA) and lack of fit test where p < 0.05 was

deemed as significant (Yilmaz et al. 2017). Fig. 2  TGA thermograms of (a) RPC and (b)NRPC

The TGA data provide quantitative information on

Results and discussion
Characterization of NRPC
The FTIR spectra (Fig. 1) of PPC, RPC and NRPC were
recorded to ensure the purity of RPC, and the nitration of
RPC was successful. The IR spectrum of RPC shows the
presence of all characteristic peaks of PPC, indicating high
purity PC was obtained using the selected method. For PC,
the characteristic peak at 1766 cm−1 is attributed to the
carbonyl (C = O) group. The peak at 2970 cm−1 shows the
presence of the aromatic rings in PC. The peaks at 1010 and
1217 cm−1 are attributed to the symmetrical and asymmetri-
cal stretching of the ester group of PC (Delpech et al. 2002).
The IR spectrum of NRPC also shows the presence of the
characteristic peaks of PC with additional peaks at 1347 and
1534 cm−1. These peaks are attributed to the asymmetrical
stretching of ­NO2, indicating the presence of ­NO2 on NRPC
(Vani et al. 2013).
the weight variation process as a function of temperature
(Larosa et al. 2017). The TGA thermograms of both the
RPC and NRPC (Fig. 2) exhibited a one-step degradation
process, which is the characteristic of PC and its derivatives
(Al‐Hamouz et al. 2006). NRPC and RPC showed a weight
loss of 83 and 81%, respectively. The higher weight loss of
NRPC was due to the loss of the ­NO2 group during heating.
This result indicated the success of the modification of RPC.
The FESEM micrographs of RPC and NRPC are pre-
sented in Fig. S1. The difference in morphological of RPC
and NRPC can be observed. The RPC surface is covered
by a non-uniform porous surface. On the other hand, the
NRPC showed rough surfaces as compared to the RPC.
The BET surface area of RPC and NRPC was 1.50 ± 0.01
and 1.53 ± 0.04 m2/g. This result showed that the surface
areas were not different significantly. The result EDX analy-
sis revealed the presence of nitrogen element on NRPC as
compared to RPC, further indicating the presence of ­NO2
groups (Table S2).

13
International Journal of Environmental Science and Technology

The preliminary screen on ­Hg2+ removal efficiency
In this initial screening, the performance of NRPC and
RPC in the removal of ­Hg2+ in water was evaluated. The
result showed that NRPC yielded a higher percentage of
­Hg2+ removal as compared to RPC (Fig. 3a). The improved
performance of NRPC can be attributed to the additional
lone-pair electron-bearing oxygen and nitrogen on the nitro-
group (–NO2) to complex with H ­ g2+. For the effect of par-
ticle size of NRPC on the removal of ­Hg2+, the synthesized
NRPC was ground and sieved into different sizes (Fig. 3b).
The NRPC with the particle size of 250 μm was found to be
­ g2+ removal because smaller
the most efficient sorbent for H
particles have a higher specific surface area, which could
provide more adsorption sites as compared to sorbent with
larger particle sizes. Therefore, 250 μm NRPC was chosen
as the candidate for further adsorption studies.
Response surface methodology
In RSM, screening helps to eliminate components that do
no influence the response (Ravindran et al. 2019). By using
the half-normal plot, the significant factors affecting the
response can be determined. The half-normal plot is a plot
(a) 90 RPC NRC
80
70
% Removal
of the absolute values of effects against their cumulative
normal probability (Krishnaiah and Shahabudeen 2012).
Graphically, these factors are represented by the data points
that deviate far to the right-side from the linear line in the
plot (Ravindran et al. 2019) and that the effects that are small
are considered as error terms which normally distributed
with mean zero (Grömping 2015). Based on this assump-
tion, the resulted half-normal plot (Fig. S2) indicated that
the effect of agitation rate ( X1 ), contact time ( X2 ), pH ( X3 )
and the interaction between pH and initial concentration
( X3 X4 ) were not due to random noise and can be deemed
important. In other words, the effect of sorbent dosage ( X5 )
was not significant under the current experimental settings.
Table 2 shows the outputs of multiple regression based on
the revised model without taking sorbent dosage ( X5 ) into
consideration. The empirical relationship between H ­ g2+
removal efficiency and the operating parameters can be
expressed as follows (Eq. 9):
Ŷ = 42.508 + 9.785X1 + 8.908X2 + 7.162X3 − 3.368X4 + 0.682X1 X2
+ 0.385X1 X3 − 4.163X1 X4 + 3.158X2 X3 + 4.890X2 X4
+ 8.013X3 X4 − 4.472X12 + 7.033X22 − 12.007X32 + 6.288X42
(9)
Also, based on the statistics in Table S3, both analy-
sis of variance (ANOVA) ( P < 0.0008 ) and lack of fit
( P = 0.2381 ) suggested that the second-order polynomial
model could perform adequately within the study domain
(Yilmaz et al. 2017). Likewise, the coefficient of determinant
( R2 = 0.8857) was within desirability range and in fairly

60 good agreement with the adjusted ( R2 = 0.8072) indicating

50 that the total variation was ascribed to the retained variables
40 to a great extent. Thus, the model could reasonably capture
30 the empirical relationship between mercury removal and the
20
10
Table 2  Regression results of the revised model
0
3 4 5 6 7 8 Coefficients Estimate Standard error t-ratio P > |t|
pH
𝛽0 42.508 2.927 14.52  < 0.0001*
(b) 90 𝛽1 9.785 1.995 4.90 0.0003*
80 𝛽2 8.908 1.995 4.46 0.0006*
70 𝛽3 7.162 1.995 3.59 0.0033*
% Removal

60 𝛽4 −3.368 1.995 −1.69 0.1152

50
𝛽12 0.628 2.116 0.30 0.7715
𝛽13 0.385 2.116 0.18 0.8584
40
𝛽14 −4.163 2.116 −1.97 0.0709
30
𝛽23 3.158 2.116 1.49 0.1595
20
𝛽24 4.89 2.116 2.31 0.0379*
10 𝛽34 8.013 2.116 3.79 0.0023*
250 μm 600 μm 1000 μm 𝛽11 −4.472 5.270 −0.85 0.4115
𝛽22 7.033 5.270 1.33 0.2050
­ g2+ removal efficiency by RPC and
Fig. 3  a Comparison of the H 𝛽33 −12.007 5.270 −2.28 0.0402*
NRPC b effect of different particle sizes of NRPC in the removal of
𝛽44 6.288 5.270 1.19 0.2541
­Hg2+

13

operational variables. According to the t-statistics (Table 2),
the most significant effects were the rate of agitation ( 𝛽1 ),
contact time ( 𝛽2 ), pH ( 𝛽3 ), contact time-initial concentra-
tion ( 𝛽24 ), pH-initial concentration interaction ( 𝛽34 ) and the
quadratic effect of pH ( 𝛽33 ) . Coefficients with positive signs
imply that increase in their levels enhances the removal effi-
ciency. In contrast, coefficients with negative signs have a
reverse influence on the response with an increase in that
particular factor (Alimohammady et al. 2017).
Effect of agitation rate (β1)
The degree of mixing of sorbent with the adsorbate depends
on the rate of agitation. Therefore, the mass transfer of ­Hg2+
Fig. 4  Interactive effect between a initial concentration and agitation rate b initial ­Hg2+ concentration and contact time c initial ­Hg2+ concentra-
tion and pH
13
International Journal of Environmental Science and Technology
from the solution onto the surface of the NRPC is influenced
by the agitation rate (Verma et al. 2006). In this study, the
­Hg2+ removal percentage was significantly increased as the
agitation rate shifted from 100 to 200 rpm (Fig. 4a). This
observation implied that by increasing the rate of agitation,
the homogeneity of the mixture was enhanced, thereby
increasing the removal efficiency.
Effect of contact time (β2)
The increase in contact time could significantly improve the
­ g2+ removal (Khor et al. 2017). The adsorp-
percentage of H
2+
tion of H
­ g at the initial stage appeared rapidly due to the
available active binding sites, which facilitated a higher
International Journal of Environmental Science and Technology
frequency of interaction between the places and the ­Hg2+
ions until equilibrium is reached. After that, the adsorption
slightly declined (Fig. 4b). The adsorption process can pro-
ceed in two stages, namely the initial fast stage due to the
availability of active sites followed by a second slower stage
where the ­Hg2+ competitively attacked the remaining avail-
able vacant sites.
Effect of pH (β3)
The pH of the solution is a substantial factor in any adsorp-
tion process (Khor et al. 2017). Based on the distribution of
mercury species in water (Anbia and Amirmahmoodi 2016),
­Hg2+ and Hg(OH)+ are the predominant species at pH lower
than 3. Above pH 3 to 4, neutral Hg(OH)2 is the predomi-
nant species of mercury. At pH higher than 4.5, mercury
exists as neutral Hg(OH)2. According to the response surface
(Fig. 4c), the ­Hg2+ removal efficiency is less prominent at
pH lower than 5. This may due to the competition between
­H+ with H­ g2+ and Hg(OH)+ for the active sites. By raising
the pH value beyond 5, the adsorption efficiency of NRPC
on ­Hg2+ was found to increase. Unlike other metal oxides,
Hg(OH)2 does not precipitate from water and this allows it
to interact favorably with NRPC (Jeon et al. 2020).
Effect of initial ­Hg2+ concentration (β4)
The initial concentration of adsorbate is yet another sig-
nificant factor in the adsorption process. At the low level
of sorbate concentration, there is a low mass ratio between
­Hg2+ and NRPC, which offers relatively more accessible
sites, thus favoring higher removal efficiency, and vice versa.
This result corroborates the negative sign of the regression
coefficient, 𝛽4 . Based on Table 2, the main effect of the ini-
tial concentration of ­Hg2+ was not noteworthy. However, this
parameter significantly governs the effect of contact time
and the effect of pH.
Interactive effect of contact time and initial ­Hg2+
concentration (β24)
The impact of mutual interaction between contact time and
initial ­Hg2+ concentration on the removal efficiency is shown
in Fig. 4b. At low H­ g2+ concentration, the percent removal
was high within the first 30 min, which can be explained
based on the accessibility of active binding sites that favored
the rapid adsorption process. The initial increase in adsorp-
tion efficiency was due to the availability of more adsorp-
­ g2+ concentration, which
tion sites coupled with low initial H
provided a concentration gradient between the H ­ g2+ and the
surface of NRPC. The percent removal efficiency gradually
decreased after reaching about 80 min of the experiment, as
observed by the slope on the response plot. This result may
imply that the ­Hg2+ removal reached equilibrium over this
duration. The declined percent removal might also be due
to less available binding sites as the contact time increased
or might be due to initial saturation of the active site caused
by monolayer coverage on the outer surface of the NRPC
as reported elsewhere (Alimohammady et al. 2017). The
simultaneous increase in ­Hg2+concentration and contact
time, however, resulted in a significant increase in removal
efficiency, as evident from the statistical analysis P > │t│,
0.0379 (Table 2).
­ g2+ concentration (β34)
Effect of pH and initial H
The response surface plot in Fig. 4c shows that the simulta-
neous interactive effect of pH and initial concentration exerts
a significant influence on the NRPC H ­ g2+ removal efficiency
(p < 0.0023). Figure 4c shows that a lower percent removal
was depicted at lower pH due to the competitive effect of
­H3O+. However, by simultaneously increasing the H ­ g2+ con-
centration from 0.5 to 1.5 mg/L, and the pH values from 4
to 7, the percent H­ g2+ removal was found to increase from
40 to 55%. An increase in the initial ­Hg2+ concentration
enhanced the collision probability between the ­Hg2+ spe-
cies and the sorbent, thereby increasing the chances of inter-
action with sorbent and resulted in higher removal efficiency.
Increasing the pH from 4 to 7 also implies the increasing
interaction between ­Hg2+ species and NRPC.
Optimization of the removal efficiency
One of the fundamental aims of establishing the optimal
conditions for the process variables is to maximize the
removal efficiency of the H­ g2+ from wastewater. To achieve
a reasonable removal efficiency, the optimum adsorp-
tion points were explored via point prediction method and
response surface plots using the software desirability func-
tion (Xu et al. 2013). According to the quadratic model, the
optimum response can be achieved at 188.6 rpm of agitation
rate, 150 min of contact time, pH 7.55 and 1.5 mg/L of ini-
tial ­Hg2+ concentration regardless of the sorbent dosage. The
model prediction was subsequently validated by conducting
independent adsorption experiments using the established
optimal conditions. The observed removal efficiency was
within the model prediction, which demonstrated that the
RSM was adequate and can be applied to optimize the H ­ g2+
removal efficiency.
Adsorption isotherm
Langmuir model (Eq. 4) and the Freundlich model (Eq. 5)
were employed to study the adsorption mechanism. The
Langmuir model describes a monolayer or homogenous
adsorption, which implies that the sorbates are adsorbed
13
 International Journal of Environmental Science and Technology

onto active sites that are of identical energy situated at Table 3  Comparing adsorption capacities of different adsorbents on
the surface of sorbent (Abas et al. 2013). The Freundlich ­Hg2+
model, on the other hand, describes the adsorption process Adsorbents qm (mg/g) References
on the heterogeneous surface with the non-uniform active
Dried biomass of Vibrio 0.164 (Jafari and Cheraghi 2014)
sites, which is also known as multilayer adsorption process
parahaemolyticus
(Abas et al. 2013). In many experiments (Abas et al. 2013;
VER 0.099 (Tran et al. 2015)
Khor et al. 2017), the Langmuir and Freundlich isotherm
NRPC 0.289 This work
models are used to describe the same set of sorbate-sorb-
ent adsorption, but the preferred model is chosen based on
the magnitude of the regression correlation coefficient, R2 .
In this study, the Freundlich model showed higher ­R2 value Adsorption kinetics and mechanism
as compared to the Langmuir model (Fig. 5). Therefore,
the adsorption of ­Hg2+ by NRPC was found to follow the The study of adsorption kinetics helps to elucidate the
Freundlich process. This result indicated that the adsorp- sorbate uptake behavior as a function of contact time
tion of H­ g2+ onto NRPC involved a complex multi-layer for the sorption process and at the same time, provides
adsorption process. necessary information for the design of an appropriate
The qm value obtained for NRPC was 0.289 mg/g. Con- wastewater treatment plan (Khor et al. 2017). The popular
sidering that the raw material (i.e., CD and DVD waste) pseudo-first-order and pseudo-second-order kinetic mod-
is widely available, the modified PC can be employed as a els are used to assess the kinetic behavior of adsorption
sustainable sorbent for wastewater treatment. Based on qm, processes. Theoretically, the pseudo-second-order equa-
the ­Hg2+ adsorption efficiency of the NRPC is relatively tion is associated with adsorption or desorption processes
higher than the dried biomass of Vibrio parahaemolyticus that are chemisorption by nature (Guo et al. 2016). From
(Jafari and Cheraghi 2014) and mercaptoethylamine/mer- the experimental data, the data fitted to pseudo-first-order
captopropyltrimethoxysilane functionalized vermiculite model shows the R2 of 0.6556 as compared to the pseudo-
(Tran et al. 2015) (Table 3). second-order model with the R 2 of 0.9903 (Fig. 6a, b).
Based on the value of R2, the adsorption of H­ g2+ by NRPC
was found to follow the pseudo-second-order model that
indicates the presence of chemisorption process (Guo
et al. 2016). The adsorption behavior of ­Hg2+ on NRPC
was further assessed using intraparticle diffusion. The
4.00
(a) R² = 0.9545
plot of intraparticle diffusion shows two linear portions
3.50
3.00
(Fig. 6c). The first portion is representing the macropore
Ce/Qe (g/L)

2.50 and mesopore diffusion, and the second portion is describ-

2.00 ing the micropore diffusion (Fierro et al. 2008). Therefore,
1.50 the mechanism of adsorption is proposed to start from
1.00
the physical diffusion of ­Hg2+ species into the macropore,
0.50
0.00
mesopore and micropore of NRPC and reaching the active
0.00 0.20 0.40 0.60 0.80 1.00 sites. At the active sites, the chemisorption is proposed to
Ce mg/L happen via the donation of lone electron of the oxygen of
the nitro group of NRPC to the ­Hg2+ species.
0.00
-1.40 -1.20 -1.00 -0.80 -0.60 -0.40 -0.20 0.00

(b) -0.20 NRPC performance on real samples

-0.40
Log Qe

R² = 0.9952
-0.60
Based on the results of sorbent performance on real sam-
ples, NRPC managed to remove 72, 73, 75 and 72% of
-0.80
­ g2+ from ultrapure water, mineral water, lake
the spiked H
-1.00 water and tap water samples, respectively (Fig. 7). The
-1.20 result showed that the matrix effect does not significantly
Log Ce influence the performance of NRPC in removing ­Hg 2+.
Consequently, NRPC can be a potential sorbent for the
Fig. 5  Adsorption isotherm models (a) Langmuir and (b) Freundlich removal of ­Hg2+ from real water samples.
for ­Hg2+ adsorption onto NRPC

13
International Journal of Environmental Science and Technology

Conclusion

In this research, RPC was obtained from waste optical discs

and further converted into NRPC for removal of H ­ g2+ from
various aqueous matrices. Based on RSM, the optimized
operating conditions for H ­ g2+ removal were found at the
188.60 rpm of agitation rate, 150 min of contact time, pH
7.55, 1.5 mg/L initial ­Hg2+ concentration, and 100 mg sorb-
ent dosage. Under the optimized condition, the adsorption
process was well approximated by the Freundlich model as
compared to the Langmuir model; and the kinetic of ­Hg2+
uptake by NRPC was found to follow the pseudo-second-
order model. The results demonstrated the potential of the
waste-derived NRPC as an sorbent.

Acknowledgement  The authors gratefully thank Ministry of Education

Malaysia (FRGS FP074-2018A) and University of Malaya (PG206-
2016A) for financial supports.

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