Journal of Environmental Chemical Engineering 2 (2014) 1996–2004

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

nFe0/GAC-mediated advanced catalytic per-oxidation for

pharmaceutical wastewater treatment
Vijayalakshmi Gosu a , Bhola Ram Gurjar a, *, Rao Y. Surampalli b , Tian C. Zhang b
a
Department of Civil Engineering, Indian Institute of Technology Roorkee, Roorkee,Uttarakhand 247667, India
b
Department of Civil Engineering, University of Nebraska–Lincoln, 205D PKI, Omaha, NE 68182-0178, USA

A R T I C L E I N F O A B S T R A C T

Article history: In the present study, the treatment of pharmaceutical wastewater (PWW) in terms of organic content
Received 4 April 2014 (COD, TOC) has been investigated using advanced catalytic per-oxidation (ACPO) with granular activated
Received in revised form 27 July 2014 carbon supported nano zero valent iron (nFe0/GAC). The characteristics of PWW and optimization of
Accepted 25 August 2014
reaction parameters that influence the process efficiency have also been evaluated. The PWW contains a
Available online 27 August 2014
high amount of organic content of non-biodegradable nature. At optimum conditions,
81% COD and

76% TOC removal was attained. Moreover, ACPO process was more favorable to the complete oxidation.
Keywords:
The reaction kinetics follows the two-step pseudo first-order model. The activation energy (E) for the first
Pharmaceutical wastewater
Advanced catalytic per-oxidation
and second steps was calculated as
22 and
23 kJ/mol, respectively. The two-step kinetics can be
Advance Fenton’s reagent (nFe0/GAC + H2O2) attributed primarily to the oxidation of organic compound first to short chain molecular structures
Kinetic study (organic acids) followed by their complete oxidation to produce carbon dioxide and water. Moreover, the
Wastewater treatment average oxidation state (AOS) got raised from 1.8 to 2.1, which represents the strong mineralization and
the generation of highly oxidized intermediates. Thus, the treatment of PWW using nFe0/GAC + H2O2
could be considered to be an effective alternative treatment option.
ã 2014 Elsevier Ltd. All rights reserved.

Introduction effluents in per-oxidation process has recently emerged as an

The demand around the globe has necessitated the cost-
effective drugs with the world class manufacturing facilities.
Ironically, in many developing countries, up to half of the
pharmaceutical wastewater (PWW) from these industries is
released into the environment without any treatment [1],
making these manufacturing industries major contributors of
hazardous and toxic effluents. The PWW contains organic
solvents, organic compounds, catalysts, additives, intermediates,
raw materials and active pharmaceutical ingredients (APIs) [2].
These substances are resistant to biodegradation because of the
low BOD/COD values [3]. The conventional biological methods
may not be efficient for the removal of these recalcitrant
compounds present in PWW [4]. Therefore, advanced oxidation
processes (AOPs) have received considerable interest for PWW
abatement [5]. These AOPs generate reactive species that should
contain one unpaired electron for non-selectively oxidization of
a wide range of organic compounds [6]. Of all the AOPs, the use
of nFe0 for the degradation of organic compounds in industrial
active research area.
In the last decades, the homogenous Fenton process
encountered major drawbacks even though receiving much
attention with more emphasis on nFe0-based heterogeneous
catalysts [7]. In comparison with the conventional Fenton
process, the implementation of the heterogeneous Fenton
process in the treatment process results in reduction of leaching
of Fe2+ and Fe3+ and avoidance of unnecessary loading of
counter ions in the aquatic system [8]. The reduction of Fe3+ ion
to Fe2+ is much faster on the surface of Fe0 compared with the
conventional homogeneous Fenton process as given in Eqs.
(1–3). Due to above reasons, researchers are mainly focused on
nFe0/H2O2 using nFe0 as a heterogeneous catalyst to generate a
Fenton-like process such as advanced catalytic per-oxidation
(ACPO) [7–9]. The related reactions are as follows:
Fe0 + H2O2 ! Fe2+ + 2OH

Fe0 + 2H+ ! Fe2+ + H2

* Corresponding author. Tel.: +91 1332 285881/285882; fax: +91 1332 275568/
273560.
E-mail addresses: brgurjar@gmail.com, bholafce@iitr.ac.in (B.R. Gurjar). 2Fe3+ + Fe0 ! 3Fe2+

http://dx.doi.org/10.1016/j.jece.2014.08.020
2213-3437/ ã 2014 Elsevier Ltd. All rights reserved.
 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004 1997

Rankem, India. Mercuric sulfate (Hg2SO4) and silver sulfate (Ag2SO4)

Fe2+
+ H2O2 ! Fe 3+ 
+ HO + HO  were obtained from Himedia laboratories, Mumbai, India. The pH
value of the PWW wastewater was adjusted using 0.1 N HCl or 0.1 N
NaOH solution and regulated by the pH controller (Hach, India).
Millipore water (electrical conductivity = 18 MV cm) made by Milli Q
Fe2+ + H2O2 $ FeOOH2+ + H+
water purification system (Millipore, India) was used in this work.

Characterization of pharmaceutical wastewater

FeOOH2+ ! Fe2+ + HO2 ! Fe3+ + HO2

The PWW collected from a pharmaceutical manufacturing

3+  2+ industry located in Roorkee, India was stored in the dark place at
Fe + HO2 ! Fe O2 + H2
temperature of
4 to 5  C to prevent the further degradation. As
The generated Fe2+ may react with oxidant (H2O2) to form shown in Table 1, the PWW contains a high amount of organic
hydroxyl radicals (OH) (Eq. (4)), which has powerful oxidative matter. The BOD/COD ratio of 0.28 indicates that the wastewater is
capacity in an aqueous phase. The rate of reaction in Eq. (5) is slower non-biodegradable. Furthermore, GC–MS confirms the presence of
than Eq. (6). Furthermore, various competitive reactions may also pharmaceutical and refractory organic compounds (Table 2). The
involve in the mineralization process (Eqs. (6) and (7)). The rate of wastewater in the present study was diluted as per test
reaction was found to be dependent on the concentration of Fe2+ in requirement (2–4 times), and the diluted water is taken as initial
overall process. Nowadays, ACPO is considered to be cost effective COD/TOC for the treatment purpose.
and of easy operation under atmospheric conditions (low tempera-
ture and atmospheric pressure) [7], and thus is used for the Synthesis of 10%-nFe0/GAC
treatment of many industrial wastewater such as coking, dye, textile
and pesticide wastewater, etc. [6,8–11]. ACPO can efficiently reduce The nanoscale zero valent iron supported granular activated
the chemical oxygen demand (COD) and total organic carbon (TOC) carbon (nFe0/GAC) was synthesized by the reduction method as
content of wastewater. per the method reported earlier [14]. Synthesis of nFe0/GAC is as
The nFe0 materials, however, have strong tendency to agglomer- follows: a required quantity of FeSO47H2O was dissolved in a 4/1
ate into larger particles because of its high surface energies and (v/v) ethanol/water mixture, which was then sonicated
intrinsic magnetic interactions. This may adversely influence the (Toshcon, India) for 10 min. Thereafter, GAC was added to the
catalytic performance, surface area, separation and recovery of nFe0. above-mentioned solution and the mixture was left in an
Moreover, the continuous loss of iron hinders its application. ultrasonic shaker for 15 min in order to disperse the iron species.
Enormous efforts have, therefore, been made to solve these problems In the meantime, sodium borohydride solution was dissolved in
through introducing support materials. Among various supports Millipore water. Excess of borohydride is necessary for better
such as granular activated carbon (GAC) received more attention due growth of nanoparticles. For that reason 20% excess BH4 was
to its excellent catalytic support characteristics for the wastewater added. The borohydride solution was added drop wise to the iron
treatment [12]. It is well known that activated carbon adsorb (II) solution along with continuous stirring of the solution
pollutants from aqueous phase, because of its, flexibility in catalysts (Remi laboratory stirrer at 500 rotations per minute (rpm)). Black
tailoring properties to specific application; high surface area, solid particles immediately appeared after the first drop of
different pore structure and chemical nature of the surface. During borohydride solution. After addition of the entire borohydride
last decade, synthesis of metal supported over activated carbon solution, the mixture was left for another 10 min of stirring. By
catalyst for wastewater treatment has gained more attention [12,13]. using vacuum filtration, black iron nanoparticles were separated
Moreover, activated carbon is stable in both acidic and alkaline from the liquid phase. At this stage, solid particles were washed at
environment and also less expensive material as operation costs are least three times with 25 ml ethanol to remove water content. The
considered. While considerable research has been conducted on final step of the synthesis was to dry the synthesized nFe0/GAC in
using GAC supported nFe0 (nFe0/GAC) for different applications, oven at 50  C overnight. Following the optimized 10% Fe weight on
information is not available on using nFe0/GAC-mediated advanced GAC, the synthesized composite had a Fe:GAC weight percentage
catalytic per-oxidation (ACPO) for PWW treatment. ratio of 10%, and was denoted as nFe0/GAC.
The purpose of the present study is to explore the feasibility of
using nFe0/GAC-mediated ACPO for PWW treatment. This paper
mainly focuses on the characterization and treatment of PWW
generated from a pharmaceuticals manufacturing plant in
Table 1
Roorkee, India. The treatability of PWW by the nFe0/GAC-mediated
Physico-chemical characteristics of PWW.
ACPO was determined with optimized operating conditions such
as pH, dose, stoichiometric ratio of H2O2:COD, initial COD, and Parameters Values
temperature (T). BOD(mg/l) 700
COD(mg/l) 2500
TOC(mg/l) 771.4
Materials and methods
pH 6.36
DO(mg/l) 2.16
Chemicals and materials Conductivity 1138
Na+2(mg/l) 110.33
All the chemicals used in this study were of analytical reagent Ca2+(mg/l) 114.67
Mg2+(mg/l) 16.03
grade, and solutions were prepared in ultra-pure deionized (DI) F(mg/l) 17.5
water (resistance =
18 MV cm). Ferrous sulfate heptahydrate, Cl(mg/l) 60.9
ethanol, and NaOH, were obtained from SD Fine Chemicals, India. NO3(mg/l) 3.74
Sodium borohydride, hydroxylamine hydrochloride, and 1,10- PO4(mg/l) 3.74
SO4(mg/l) 25.68
phenanthroline were purchased from Sigma–Aldrich. Dichloro-
BOD/COD 0.28
methane, acetic acid and 30% hydrogen peroxide were procured from
1998 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004

Table 2
Characteristic peaks of identified compounds in PWW.

S. No. Compound (molecular formulae) M.W. R.T. R-M F-M

1 Pyridine(C5H5N) 79 4.32 772 763
2 Pentanoic acid(C5H10O2) 102 5.12 882 891
3 Benzoylcarbinol(C8H8O2) 136 5.67 832 879
4 1-Hydroxy-3-methylcholanthrene(C21H16O) 284 5.80 360 378
5 Crithmene(C10H16) 136 6.43 767 781
6 Isopropyltoluene(C10H14) 134 6.68 710 755
7 Phenol, 4-methyl-(C7H8O) 108 7.40 575 777
8 Indole(C8H7 N) 117 7.83 432 450
9 Phenylethyl alcohol(C8H10O) 122 8.13 733 805
10 Benzoic acid(C7H6O2) 122 8.92 825 895
11 Levomenthol(C10H20O) 156 9.17 845 856
12 Methyl salicylate(C8H8O3) 152 9.4 840 864
13 p-Toluylic acid(C8H8O2) 136 10.4 766 867
14 Benzene, 1-methoxy-4-(1-propenyl(C10H12O) 148 10.7 892 894
15 Benzenepropanoic acid(C9H10O2) 150 11.3 528 774
16 Methylparaben(C8H8O3) 152 12.9 871 906
17 Ibuprofen(C13H18O2) 206 14.9 659 836
18 Nipasol(C10H12O3) 180 15.0 828 864
19 Acetaminophen(C8H9NO2) 151 15.9 859 881
20 2,3-Dimethyl4-biphenyl amine(C14H15N) 197 16.9 585 789
21 Quinolin(C9H7N) 129 17.2 860 870
22 Dibutyl phthalate(C16H22O4) 278 17.4 840 876
23 Diphenyl sulfone(C12H10O2S) 218 18.2 739 777
24 Mefenamic acid(C15H15NO2) 241 20.6 608 812
25 2-Naphthalenol,1-[(2,4-dimethylphenyl)azo]-(C18H16N2O) 276 21.6 437 447
26 3,30 -Diaminobenzidine(C12H14N4) 214 22.0 411 589
27 Vincamine(C21H26N2O3) 354 23.4 346 369
28 Vitamin A aldehyde(C20H28O) 284 29.0 549 636

M.W.: molecular weight; R.T.: retention time (min); R-M: reverse match; F-M: forward match.

Experimentation
The experiments were carried out in a three necked round
bottom glass reactor equipped with a reflux system to prevent the
evaporation of sample, and it immersed into the oil bath to
maintain uniform temperature. The reactor was kept inside the
oil bath in order to maintain constant desired temperature. The
temperature of the reaction mixture was increased using a
proportional–integral–derivative controller. The reaction mixture
was agitated with a magnetic stirrer at 300 rpm to keep the
solution homogenous. For each experimental run, a 100 ml
reaction mixture was charged into the reactor. Thereafter,
thermal equilibrium of the reaction mixture was attained with
the oil bath, and required quantities of catalyst dose (nFe0/GAC)
and oxidant (H2O2) were added to the reaction mixture for the
oxidation purpose. Batch studies were carried out by varying
operating parameters such as pH 2–9, dose = 0.5–6 g/l, the
stoichiometric ratio of H2O2:COD = 0.5–2, initial COD = 100–
2000 mg/l, and temperature = 303–333 K. Detailed test conditions
are described in each figure caption.
Analytical techniques and data analyses
The following analytical techniques were employed for various
experimental observations. Total organic carbon (TOC) was
measured with Shimadzu TOC-V analyzer by using non dispersive
infrared (NDIR) detector. Chemical oxygen demand (COD) was
analyzed by the potassium dichromate method [15]. The mixture
was incubated for 120 min at 120  C in a COD digester and
concentration was measured with UV/vis spectrophotometer
(DR500, USA). The compounds present in PWW were identified
by using gas chromatography–mass spectrometry (GC–MS)
(Varian450GC, 240 MS, USA) as per the method reported before
[2]. Briefly, the compounds were extracted from PWW with
n-hexane and thereafter concentrated in a water bath at 40–43  C.
The extracts were injected in the splitless mode, and column
temperature was maintained at 280  C. The flow rate of carrier gas
was maintained at 1.0 ml/min. The Fe2+, total Fe and hydrogen
peroxide (H2O2) concentrations were analyzed by the
1,10-phenanthroline and the titanium sulfate spectrophotometric
methods [16], respectively. The aromatic content (UV254) of PWW
was determined by UV/vis spectrophotometer (DR500, USA) [9].
The performance of the reaction was studied using the
following Eqs.:
½TOCo  ½TOCf
Removal ofTOCð%Þ ¼  100 (8)
½TOCo
½CODo  ½CODf
Removal ofCODð%Þ ¼  100 (9)
½CODo
½H2 O2 o  ½H2 O2 f
Oxidantconsumption ¼  100 (10)
½H2 O2 o
where [TOC]o and [TOC]f are the initial and final concentration of TOC
(mg/l), respectively, in each experiment; [COD]o and [COD]f are the
initial and final concentration of COD (mg/l), respectively; [H2O2]o
and [H2O2]f are the initial and final concentration of H2O2 (mM).
Results and discussion
Preliminary experiments
Preliminary experiments were carried out to investigate the
effect of individual parameters on the degradation efficiency. The
experiments with only nFe0/GAC were conducted to differentiate
the adsorption effect. The experiments with H2O2 and without
nFe0/GAC were carried out to examine the oxidation capability.
Volatilization effect was monitored without H2O2 and nFe0/GAC
(Table 1). Consequently, marginal removal (5–20%) was observed.
It was observed that maximum 20% COD and 13% TOC were
 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004 1999

Table 3 Effect of pH
Results of preliminary experiments of PWW.

Experiment Variables % COD removal % TOC removal The removal of COD, TOC and aromatic content increased with
0
nFe /GAC H2O2
an increase in pH until pH 4, depicted in Fig. 1(a). However,
further rise in pH (>4) leads to decrease in the percentage removal
1  + 15 9
2 +  20 13
of COD, TOC and the aromatic content. pH effects in Fe0/water
3   8 5 systems are complicated but well studied [17–23]. In the pH range
of 2–4, Fe(OH)+ dominates in contributing to high catalytic activity,
+: denotes presence; : denotes absence; dose: nFe0/GAC = 1 g/l; COD: H2O2 = 1.2;
reaction time = 5 h. which is formed due to decomposition of H2O2 to hydroxyl radicals
(OH). The obtained radicals are responsible for the degradation of
compounds present in PWW [17]. At pH range of 2–3, the
reduced. The observations of aforementioned experiments are regeneration of Fe2+ to Fe3+ with H2O2 may be inhibited [18].
summarized in Table 3. It is also found that nFe0/GAC or H2O2 Further, salvation of H2O2 in the presence of high concentration of
does not give desirable results when they are not used together. H+ ion forms stable oxonium ion (H3O2+). H+ ions may affect the
However, the substantial oxidation is accomplished when we use adsorption of contaminants onto reactive sites [23]. At pH of about
both of them together. 6 (effluent discharged condition), the organic compounds present

Fig. 1. The % removal of COD, TOC and UV254 affected by (a) pH (dose = 1 g/l, H2O2:COD = 1:1.2, initial COD = 600 mg/l, initial TOC = 200 mg/l); (b) dose of nFe0/GAC (pH 4,
H2O2:COD = 1.2:1, initial COD = 600 mg/l, initial TOC = 200 mg/l); (c) stoichiometric ratio of H2O2:COD (pH 4, dose = 1.5 g/l, COD = 600 mg/l, initial TOC = 200 mg/l); and (d)
initial COD (pH 4, dose = 1.5 g/l, H2O2:COD = 1.5:1). For tests (a)–(d), reaction time = 6 h and T = 313 K.
2000 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004
in the wastewater with special groups such as  OH, COOH were
in the deprotonated form (with a higher negative charge). These
compounds have more neutral sites at the acidic condition (pH 2–
4). Their high interaction with catalyst surface might be resulting
in higher degradation efficiency [19]. The percentage removal in
terms of COD, TOC and aromatic contents decreased at higher pH.
This might be attributed to the formation of iron oxides
(e.g., magnetite or precipitation of Fe3+ to Fe(OH)3) that hindered
the reaction between iron species (i.e., Fe0, Fe2+, Fe3+) and H2O2
[20,23]. At low pH (2–4), even if the iron oxides are formed on the
Fe0 surface, they are likely poor crystalline, and do not inhibit the
reactivity of Fe0 [23]. Furthermore, self-decomposition of H2O2 to
O2 and H2O in the presence of active catalysts might also occur at
higher pH as stated by [24]. Consequently, reduction of hydroxyl
radicals (OH) generation could influence the degradation
efficiency. Therefore, further experiments were carried out in
the acidic medium (e.g., pH 4) in order to utilize the maximum
amount of generated hydroxyl radicals. The obtained optimal pH of
4 is in good agreement with the previous results [25].
Effect of nFe0/GAC dose
The dose of nFe0/GAC is an important parameter in the ACPO
process. Optimal dose would reduce the cost of the process.
Fig. 1(b) shows that the percentage removal of COD, TOC and
UV254 increased up to the dose of 1.5 g/l. Increase in removal was
driven by generation of more reactive species (OH) that leads to
acceleration of reaction in Eq. (4). The addition of nFe0/GAC above
the dose of
1.5 g/l did not influence the removal of COD, TOC, and (Fig. 1(d)), which was the reason why COD = 600 mg/l was used
UV254. Additional catalyst does not likely involve in the catalytic
activity, and thus the removal was insignificant with an increase in
the amount of dose beyond a certain limit. Moreover, as shown in
Eq. (8), in the reaction medium Fe3+ reacts with H2O2 and generate
Fe2+ and hydroperoxyl radicals (HOO). The oxidation capacity of

OH is more in comparison to HOO [26]. Other possible reasons
could include self-scavenging effect of OH radicals and lower
utilization of H2O2 due to its self decomposition [24]. Kang and
Hwang [27] observed the similar trend at higher concentration of
iron species during the Fenton process. Thus, subsequent experi-
ments were conducted at the optimal dose of 1.5 g/l.
It should be pointed out that the dose of nFe0/GAC had no
specific effect on the amount of iron dissolved in the effluent after
reaction, which, according to the measurement during the study,
was always <1 mg/l, indicating that the main novelty of the
proposed process is realized, that is, development of
heterogeneous catalyst (nFe0/GAC) for the treatment of industrial
wastewater with minimum leaching.
Effect of stoichiometric ratio of H2O2:COD
The H2O2 concentration directly influence the production of
reactive species (OH) for the degradation of organic and
inorganic compounds in PWW. As shown in Fig. 1(c), there is
positive effect on the percentage removal of COD, TOC, and UV254
with an increase in the stoichiometric ratio till 1.5. It may be
ascribed to higher generation of reactive species (OH) that leads
to high degradation. Further rise in the H2O2:COD ratio does not
increase the percentage removal of COD, TOC, and
UV254 significantly, because the generated hydroxyl radicals
(OH) immediately react with H2O2 (see Eq. (11) below) [24],
leading the decreases in the available/residual H2O2 dose (Fig. 1c).
 rCOD ¼  COD ¼ kCOD C CODt orln CODt ¼ kCOD t
  þ OH
H2 O2 þ OH ! HOO ! O2 þ H2 O
H2 O
The hydroperoxyl radical (HOO) is an effective oxidant which
promotes the chain reactions. Furthermore, oxidation capacity of
(OH) is higher compared to (HOO) that may affect the
degradation as discussed before [26]. Many researchers also
observed the similar trends [28,29]. In this study, the residual
concentration of H2O2 was found to increase with an increase in
H2O2 and varied in the range of 0.0025–0.02 mM (0.085–0.64 mg/l)
(Fig. 1d); at the optimal stoichiometric ratio of H2O2:COD, the
residual concentration of H2O2 was found to be <0.5 mg/l
Therefore, the optimal stoichiometric ratio of H2O2:COD was used
in further tests in order to avoid excess residual H2O2 concentra-
tion, which is a valid consideration as the ACPO process is often
followed by biological treatment processes [30,31]. The reaction
was suspended by adding NaOH (6 M) followed by heating, so that
the remaining hydrogen peroxide decomposes completely, and the
NaOH treated solution was used for the measurement of COD.
Effect of initial COD
The concentration of COD plays significant role for selection of
the treatment process. The removal of COD, TOC and UV254 was
reduced with an increase in COD concentration for given hydrogen
peroxide. It has been reported that, at a lower COD concentration
(<300 mg/l), complete degradation of COD was achieved [32].
However, complete mineralization could not be attained in this
study. It may be ascribed to the compounds in PWW that are
rapidly oxidized to intermediate compounds (corresponding
carboxylic acids) but not further oxidized by hydroxyl radicals
[32]. Moreover, the utilization of hydrogen peroxide decreases as
the initial concentration of COD was higher than 600 mg/l
in many tests shown in Fig. 1(a)–(c).
Effect of temperature
Industrial wastewaters discharge at different temperatures.
Operating temperature is an important parameter that can
influence the rate of reaction. In this study, the COD and TOC
removal increases with the increase in temperature (Fig. 2(a)). At
303 K,
73% COD conversion and
59% TOC removal were
obtained, whereas at 333 K, 94% COD conversion and
83% TOC
reduction were observed. The residual TOC in the reaction mixture
may be attributed to the stable intermediates that are resistant to
further oxidation (such as short-chain organic acids and oligom-
ers). Even under extreme operating conditions the stable com-
pounds are resistant to total oxidation. Thus, TOC and COD remain
in reaction mixture at low temperature [33]. As temperature
increases the enhancement in generation of (OH) and reduction of
scavenging of hydroxyl radicals might occur [24]. This infers that
the organics and some relatively unstable intermediates present in
the PWW are either partially oxidized to form stable intermediates
(usually acetic acid) or directly oxidized to total oxidation
producing final end-products.
Kinetic study
It is essential to conduct kinetic study in any catalytic reaction
to identify the reaction pathway and the reaction rate and rate
limiting steps. In many reaction systems, due to the complexity of
the reactions, it is difficult to accomplish detail kinetic studies on
each of different individual reactions. In this study, the kinetics of
the PWW was evaluated using COD as a lumped parameter, and the
first-order kinetics was assumed:
dC C
(12)
dt C CODo
(11)
where, kCOD is first-order reaction rate constant; t is the reaction
time; CCODt is PWW concentration at any time (t), and CCODo is
initial COD concentration. According to Eq. (12), the two-stage first
 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004 2001

Fig. 2. (a) effect of temperature (K) on the % removal of COD and TOC at different time intervals (pH 4, dose = 1.5 g/l, H2O2:COD = 1.5:1, initial COD = 1000 mg/l, initial
TOC = 240 mg/l). (b) two stage kinetics for COD removal of PWW at different temperatures.

order reaction kinetics occurred in our systems, that is, initially the Assessment of oxidation process
degradation process was fast, and thereafter, the reaction was slow Because of heterogeneous composition and non-biodegradabil-
(Fig. 2(b)). As reported by several researchers [24,34–36], the ity of PWW, the assessment of the oxidation state and degree of
two-stage first order reaction kinetics might occur because initially oxidation were investigated. The reduction of COD in PWW is given
the organic compounds are oxidized to short chain molecular as follows:
structures and consequently these short chain molecular
COD + H2O2 + Fe2+ ! partially oxidized species
structures (organic acids) further get oxidized into carbon dioxide
and water [34]. The kCOD at different temperatures are tabulated in
Table 4 with the activation energy being calculated by using
partially oxidized species + H2O2 + Fe2+ ! CO2 + H2O + inorganics
Arrhenius equation for the two steps separately:
Average oxidation state (AOS) provides good information about the
kf ¼ ko expE=RT (13)
changes in the relative composition of dissolved organic matter
where, kf is the rate constant; E (kJ/mol) is the activation energy; ko during the reaction [39] and estimates the degree of oxidation in a
is the frequency factor; R is the molar gas constant; and T is the complex solution. AOS of PWW was calculated using the COD and
absolute temperature (K). The E for first and second steps is TOC (Eq. (16)). The AOS values of carbon can be in between 4 and

22 and
23 kJ/mol, respectively. This value is unexpectedly low +4 (CH4 to CO2).
as oxidation of organic compounds rarely gives activation energies

COD
below 40 kJ/mol [36–38]. Therefore, this result suggests that the Average oxidation state ðAOSÞ ¼ 4  1:5  (16)
system is driven by mass transfer limitations. In fact, hydroxyl TOC
radicals are generated by decomposition of hydrogen peroxide in To differentiate between the extent of partial and total
the presence of active metal, and active metals are dispersed oxidation of PWW, the partial oxidation of COD (CODpartial) was
within the pore and released to the outside of GAC. The generated accomplished at various reaction times, which can be estimated by
radicals react non-selectively and diffuse into the bulk solution Eq. (17). The efficiency of COD removal through partial oxidation
(PWW) where the oxygen demanding pharmaceutical (e) can be defined by the ratio of COD removal by partial oxidation
contaminants get converted into the oxidized forms. and overall COD removal represented in Eq. (18) [40]


TOCt
CODpartial ¼ CODo  CODt (17)
TOCo
Table 4
Kinetic and thermodynamic parameters during the treatment of PWW.
CODpartial
Temperature Fast step Slow step e¼ (18)
ðCODo  CODt Þ
(K)
kCOD(1/ R2 E (kJ/ kCOD(1/ R2 E (kJ/mol) where CODt and TOCt are the concentration of COD and TOC at
min) mol) min) different reaction time t and CODo and TOCo the concentration of
303 0.0049 0.999 22.07 0.001 0.71 23.97 COD and TOC at zero reaction time. The variation of AOS and
313 0.0058 0.989 0.0018 0.86 efficiency of partial oxidation (e) with respect to time at different
323 0.0094 0.998 0.002 0.85
temperatures in the range of 303–333 K are shown in Fig. 3. The
333 0.010 0.998 0.0024 0.80
AOS of PWW was approximately 1.86 ascribed to the presence of
2002 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004

Fig. 3. (a) average oxidation state (AOS), and (b) partial oxidation (e) of PWW with time under test conditions: pH 4, dose = 1.5 g/l, H2O2:COD = 1.5:1, initial COD = 1000 mg/l,
initial TOC = 240 mg/l, reaction time = 6 h.

a smaller amount of oxidizable molecular structures in the reaction
mixture. The AOS increases gradually with time that may be
attributed to more numbers of oxidizable molecular structures in
the reaction. Moreover, AOS of PWW significantly improved when
temperature increased. With an increase in temperature from
323 to 333 K the AOS of PWW increased from 1.8 to 2.1. For a given
range of temperature the AOS was in the range of 0.8–2.1.
The e reaches the value of 0 when only total oxidation occurs
and 1 for the ideal case that only partial oxidation occurs. The
efficiency of COD removal through partial oxidation (e) is always
less than 0.5, which indicate that more than 50% of the overall COD
removal is due to total oxidation reactions as shown in Fig. 3(b).
However, partial oxidation seems to be more important than total
oxidation when e is always greater than 0.5 i.e., more than 50% of
the overall COD removal is due to partial oxidation reactions. This
signifies that in the present study the total oxidation appears to be
more predominant in PWW.
Monitoring of pharmaceutical compounds during the treatment
The pharmaceutical compounds identified in Table 2 were
analyzed by GC–MS under optimum conditions during the
treatment with different time intervals (pH 4; dose = 1.5 g/l;
H2O2:COD = 1.5:1; initial COD = 1000 mg/l; T = 333 K and reaction
time = 6 h). The disappearances of the identified compounds with
time (0–6 h) in the treated sample are listed in Table 5. The extent
of destruction of identified compounds in PWW was determined
by the arbitrary ratio given in Eq. (19):

Table 5
The disappearance of compounds in PWW during the treatment.

S. No. Compound (molecular formulae) Duration of treatment

0 1h 3h 6h
1 Pyridine(C5H5N) 0.19 – – –
2 Pentanoic acid(C5H10O2) 26.89 – – –
3 Benzoylcarbinol(C8H8O2) 0.28 – – –
4 1-Hydroxy-3-methylcholanthrene(C21H16O) 2.85 – – –
5 Crithmene(C10H16) 0.17 – – –
6 Isopropyltoluene(C10H14) 0.22 – – –
7 Phenol, 4-methyl-(C7H8O) 0.11 – – –
8 Indole(C8H7N) 0.28 0.05 – –
9 Phenylethyl alcohol(C8H10O) 0.15 0.65 – –
10 Benzoic acid(C7H6O2) 4.06 1.05 0.13 –
11 Levomenthol(C10H20O) 14.62 0.235 – –
12 Methyl salicylate(C8H8O3) 11.68 – – –
13 p-Toluylic acid(C8H8O2) 0.36 0.56 – –
14 Benzene, 1-methoxy-4-(1-propenyl)(C10H12O) 3.45 – – –
15 Benzenepropanoic acid(C9H10O2) 0.05 0.96 0.009 –
16 Methylparaben(C8H8O3) 2.40 0.053 – –
17 Ibuprofen(C13H18O2) 0.66 – – –
18 Nipasol(C10H12O3) 5.86 0.95 0.001 –
19 Acetaminophen(C8H9NO2) 2.14 – – –
20 2,3-Dimethyl4-biphenyl amine(C14H15N) 0.25 0.43 – –
21 Quinoline(C9H7N) 3.05 0.056 – –
22 Dibutyl phthalate(C16H22O4) 4.39 5.63 0.569 –
23 Diphenyl sulfone (C12H10O2S) 10.67 – – –
24 Mefenamic acid(C15H15NO2) 0.48 – – –
25 2-Naphthalenol, 1-[(2,4-dimethyl phenyl)azo]-(C18H16N2O) 0.91 0.098 – –
26 3,30 -Diaminobenzidine(C12H14N4) 1.74 – – –
27 Vincamine(C21H26N2O3) 1.76 – – –
28 Vitamin A aldehyde(C20H28O) 0.76 – – –
Total compounds (%) 100 10.772 0.709 0
 V. Gosu et al. / Journal of Environmental Chemical Engineering 2 (2014) 1996–2004
SiðtÞ
PiðtÞ ¼ P  100 (19)
Sið0Þ
where, Pi(t) is the fraction of a remaining compounds (i) in
the PWW after a treatment period (t), Si(t) is the peak surface
area of a compounds (i) after a treatment period (t), Si(0) is
the sum of the surface areas of all identified compound peaks
from the raw PWW. Table 5 shows that variations of these
percentages with different time intervals during the treatment.
The 28 compounds are identified in PWW. After 3 h reaction,
95% compounds disappeared, presumably due to the formation
of intermediate compounds caused by the ACPO process. Later
on, complete disappearance of compounds in PWW was
observed.
Implications and limitations
Combining the results of this study (e.g., Table 5 and Fig. 3), one
can understand that the nFe0/GAC-mediated ACPO process is a
powerful and straightforward process for PPW removal. Most of
the contaminants in PWW were mineralized via oxidation
reactions as the partial oxidation (e) is always <0.5 at reaction
time of 6 h. While this study did not evaluate the biodegradability
of the remaining residuals in the PWW, previous report [34]
indicates that the Fenton process treated wastewater is biode-
gradable with a stable performance. Moreover, results of this study
show that the leaching of dissolved iron is not an issue, indicating
the feasibility of using heterogeneous catalyst (nFe0/GAC) for the
treatment of industrial wastewater with minimum leaching of
dissolved iron. However, the results of kinetic studies and
temperature effects indicate that the proposed nFe0/GAC-mediat-
ed ACPO process may be mass transfer limited. Furthermore, while
the two-step pseudo-first-order reaction kinetics was used in this
study as previous ACPO studies did [24,28,34–36], the kinetic
analysis conducted via Eqs. (14) and (15) may provide more
insights or be more straightforward for elucidation of the reactions
mechanisms. Thus, further studies are needed to fully demonstrate
the feasibility of the process.
Conclusion
The overall results obtained from this study present a feasible
method for removal of non-biodegradable organic compounds
from PWW. The degree of removal of such compounds depends on
the pH, dose, stoichiometric ratio of (H2O2:COD), initial COD, and
temperature. The optimum condition for this process was
observed at pH 4; catalyst dose = 1.5 g/l; stoichiometric ratio of
H2O2:COD = 1.5:1; initial COD = 1000 mg/l; temperature = 333 K
and reaction time of 6 h. The kinetic study reveals that the
treatment process can be fitted with two-step pseudo first-order
reaction. The activation energy (E) for the first and second steps
was calculated as
22 and
23 kJ/mol, respectively. From GC–MS
analysis, 28 major compounds were identified in PWW, and these
identified compounds completely disappeared when treated with
nFe0/GAC + H2O2 for 6 h. The partial oxidation (e) was always less
than 0.5 indicating that the total oxidation or complete oxidation
was more predominant. Due to the treatment of PWW using
nFe0/GAC + H2O2 the AOS values got raised from 1.86 to 2.1, which
attributed to strong mineralization and the generation of highly
oxidized intermediates.
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