Journal of Hazardous Materials 260 (2013) 993–1000

Contents lists available at SciVerse ScienceDirect

Journal of Hazardous Materials

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

Pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater

using a combined zero-valent iron (ZVI) reduction and Fenton
oxidation process
Jinyou Shen a,1 , Changjin Ou a,1 , Zongyuan Zhou a , Jun Chen b , Kexiong Fang b , Xiuyun Sun a ,
Jiansheng Li a , Lin Zhou c , Lianjun Wang a,∗
a
Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of
Science and Technology, Nanjing 210094, Jiangsu Province, China
b
Hubei Dongfang Chemical Co. Ltd., Hubei 441404, China
c
School of Mechatronical Engineering, Beijing Institute of Technology, Beijing 100081, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• ZVI-Fenton process was conducted

for DNAN producing wastewater pre-
treatment.
• Transformation of nitro to amino
group by ZVI overcomes the oxidative
hindrance.
• Subsequent Fenton process is effi-
cient for the removal of aromatic
compounds.
• ABR-MBBR process is efficient for the
polishing of ZVI-Fenton effluent.

a r t i c l e i n f o a b s t r a c t

Article history: A combined zero-valent iron (ZVI) reduction and Fenton oxidation process was tested for the pretreat-
Received 25 December 2012 ment of 2,4-dinitroanisole (DNAN) producing wastewater. Operating conditions were optimized and
Received in revised form 2 July 2013 overall performance of the combined process was evaluated. For ZVI process, almost complete reduc-
Accepted 3 July 2013
tion of nitroaromatic compounds was observed at empty bed contact time (EBCT) of 8 h. For Fenton
Available online 10 July 2013
process, the optimal pH, H2 O2 to Fe(II) molar ratio, H2 O2 dosage and hydraulic retention time (HRT)
were found to be 3.0, 15, 0.216 mol/L and 5 h, respectively. After pretreatment by the combined ZVI-
Keywords:
Fenton process under the optimal conditions, aromatic organic compound removal was as high as 77.2%,
2,4-Dinitroanisole (DNAN)
Zero-valent iron (ZVI)
while the majority of COD remained to be further treated by sequent biological process. The combined
Fenton process anaerobic-aerobic process consisted of an anaerobic baffled reactor (ABR) and a moving-bed biofilm
Reduction reactor (MBBR) was operated for 3 months, fed with ZVI-Fenton effluent. The results revealed that the
Oxidation coupled ZVI-Fenton-ABR-MBBR system was significantly efficient in terms of correcting the effluent’s
main parameters of relevance, mainly aromatic compounds concentration, COD concentration, color and
acute toxicity. These results indicate that the combined ZVI-Fenton process offers bright prospects for
the pretreatment of wastewater containing nitroaromatic compounds.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction

2,4-Dinitroanisole (DNAN) is an important industrial chemical

∗ Corresponding author. Tel.: +86 258 431 5941; fax: +86 258 431 5941.
used extensively in the manufacture of explosives, dye intermedi-
E-mail addresses: shenjinyou-1981@163.com (J. Shen),
ates and pesticides. Currently, it is being considered to replace TNT
wanglj@mail.njust.edu.cn (L. Wang).
1
Both these authors contributed to the paper equally. (2,4,6-trinitrotoluene) in the production of munitions because of its

0304-3894/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2013.07.003
994 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000
insensitive properties [1]. The environmental risk associated with
the use of DNAN at large scale is still unclear, however, it is believed
to be metabolized to 2,4-dinitrophenol (2,4-DNP) in the body, a
chemical with high acute and chronic toxicity [2]. DNAN is usu-
ally produced using 2,4-dinitrochlorobenzene (DNCB), methanol
and sodium hydroxide as raw materials. In addition to DNAN, raw
materials such as DNCB and methanol, byproducts such as DNP, are
also the major constituents of DNAN producing wastewater. DNAN
producing wastewater is always characterized by intense color,
high toxicity, concentrated substrate and salt (usually exceeding
3 wt.%), poor decolorization. For the treatment of industrial efflu-
ent, biological treatment, which is environmental friendly and cost
effective, has turned out to be a favorable alternative. However, due
to the presence of nitro-aromatic compounds in DNAN producing
wastewater, conventional biological processes do not provide sat-
isfactory results. Some refractory organics still exist in the effluent,
resulting into intense color.
Advanced oxidation processes (AOPs) are interesting treatment
options for recalcitrant organic compounds removal from waste-
water, because of their great potential to oxidize, partially or totally,
numerous recalcitrant organic compounds [3]. One of the most
effective AOPs consists of the utilization of Fenton’s reagent, a
combination of H2 O2 and Fe2+ . In this process, H2 O2 decomposes
catalytically by means of Fe2+ at acid pH, giving rise to hydroxyl
radicals
H+
Fe2+ + H2 O2 −→ Fe3+ + HO• + OH−
The application of Fenton’s reagent as an oxidant for wastewater
treatment is attractive. However, due to the pronounced electron-
withdrawing character of the nitro group and chloro group, the
major constituents of DNAN producing wastewater, such as DNCB,
DNAN, DNP, harbor a highly electron deficient ␲-electron system
[4]. Electrophilic attack, which is usually the first step in oxida-
tion or aerobic biodegradation, becomes more difficult [5]. What is
more, with increasing numbers of nitro and chloro groups, aromatic
compounds become more resistant to mineralize through oxidative
pathways but are subject to initial reductive transformation [6,7].
In efforts to develop an effective wastewater treatment sys-
tem for chlorinated or nitroaromatic compounds, studies have
examined biological or chemical processes to reductively trans-
form the nitro functional groups or dechlorinate the compounds
to overcome the hindrance to oxidation [8]. Among the reductive
transformation processes, anaerobic reduction and zero-valent iron
reduction have turned out to be promising. However, anaerobic
reduction process is usually very slow [4,9], requiring an electron
donor (organic cosubstrate) to create the necessary reductive con-
ditions [10–12].
Zero-valent iron (ZVI), as an inexpensive, reliable and moder-
ately strong reducing agent, has been widely used to treat many
kinds of environmental contaminants, such as halogenated organic
compounds, azo dyes, and nitroaromatics [4,13–16]. For the reduc-
tive transformation of these environmental contaminants, the ZVI
process offers bright prospects, due to a number of advantages,
such as small footprint and excellent performance at much higher
loading rates than conventional anaerobic reductive processes. In
addition, the ZVI process is also very stable, with no specialized pH
and/or temperature requirements and no need for any nutrient and
alkalinity amendment [16]. However, a second treatment process,
such as oxidation/aerobic biodegradation, is necessary to further
degrade or mineralize the reduction products from ZVI effluent.
In recent years, attention has been focused on studies using
the combined ZVI and Fenton process for the treatment of
nitroaromatic compounds. Le et al. [12] described the effec-
tive degradation of para-chloronitrobenzene through a sequential
treatment using ZVI reduction and Fenton oxidation. The reductive
Table 1
Characteristics of DNAN producing industry wastewater.
Parameter Value
pH 7.2
COD (mg/L) 34000 ± 985
TOC (mg/L) 7151 ± 329
DNAN (mg/L) 123.1 ± 3.8
DNCB (mg/L) 249.3 ± 6.9
DNP (mg/L) 110.4 ± 4.2
Salinity (%) 3.3
Color (times) 700–1000
EC50, 48 h (v/v) (%) 0.67
product para-chloroaniline was more susceptible to oxidation by
Fenton agent than para-chloronitrobenzene itself. A continual sys-
tem consisting of ZVI and Fenton reaction was also proposed by
Barreto-Rodrigues et al. [8] for the treatment of TNT industrial
wastewater. It was suggested that the sequential treatment using
ZVI reduction followed by Fenton oxidation is a promising method
for nitroaromatic compounds degradation.
In this paper, the combination of reductive stage (ZVI) with
oxidative process (Fenton) was investigated for pretreatment of
DNAN producing wastewater. The main advantage of the combined
processes seemed to be associated with the primary conversion
of nitroaromatic compounds in DNAN producing wastewater into
chemical species with a greater susceptibility to oxidative degra-
dation, consecutively promoted for the Fenton reaction. In order
to provide useful information to help design and plan full-scale
technology implementation, bench-scale or pilot-scale treatability
studies aiming at real wastewater were necessary [17]. However,
no report has ever been published regarding treatment of real
DNAN producing wastewater. Thus, the objectives of this work
were (1) to assess the feasibility of combined ZVI-Fenton process for
the pretreatment of DNAN producing wastewater, (2) to optimize
the operating conditions of ZVI reduction and Fenton oxidation
process, and (3) to identify intermediate products of the coupled
process and to ascertain the degradation pathway.
2. Materials and methods
2.1. Materials
DNAN, DNCB and DNP were gift from Hubei Dongfang Chemical
Co. Ltd. in Hubei Province, China. Ferrous sulphate (FeSO4 ·7H2 O)
(Lianxing Chemicals, China), hydrogen peroxide (Huanghai Chem-
icals, China, 30%) was used as received. All other chemicals were of
the highest purity available and were purchased from Sinopharm
Chemical Reagent Co. Ltd. (Shanghai, China). Iron scrap, especially
turnings or shavings of 30CrMoSi steel was used in this study.
The iron shavings contained iron (>95%), carbon (0.30–0.35%), sil-
ica (0.2–0.35%), chromium (1.40–1.70%), manganese (0.40–0.60%),
Molybdenum (0.15–0.25%), aluminum (0.60–0.78%), and a few
other trace elements.
2.2. Characteristics of DNAN producing wastewater
During the experiment, raw wastewater taken from Hubei
Dongfang Chemical Co. Ltd. was used. Details of DNAN produc-
ing wastewater were included in Table 1. This wastewater was
characterized by its extremely high value of COD and salinity. The
toxic compounds included DNAN, DNCB, and DNP. In addition, high
concentration of methanol was the major constituents of DNAN
producing wastewater. EC50, 48 h (v/v) was as low as 0.67%, indicat-
ing the high toxic characteristic of DNAN producing wastewater.
It was probably due to the presence of highly toxic compounds,
 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000
such as DNCB, DNAN and DNP, which hamper a direct biological
treatment.
2.3. Experiment equipment and experimental procedure
Before the combined process of ZVI reduction and Fenton oxida-
tion in our study could be operated, it was necessary to investigate
the effectiveness of ZVI in DNAN producing wastewater pretreat-
ment. DNAN, DNCB, DNP, TOC, COD concentrations, and EC50, 48 h
(%, v/v) of the influent and effluent were monitored at empty
bed contact time (EBCT) of 2–8 h. To improve the performance of
the iron shavings, 0.2 wt.% of copper was applied to the iron sur-
face by reductive precipitation to form the so-called bimetallic ZVI
structures [16]. For the reduction of nitroaromatic compounds, the
Cu-doped iron shavings show good reactivity over a wide solu-
tion pH [16]. Excellent reduction performance of DNCB at neutral
pH condition by Cu-doped iron shavings was also observed in
our previous study [18]. In order to simplify the operation, DNAN
producing wastewater entered ZVI system at natural pH, without
acidification.
The optimization of Fenton oxidation process was emphasized
in this study. Operation parameters, such as pH, H2 O2 to Fe(II)
molar ratio, dosage of H2 O2 , and HRT were optimized. During pH
optimization, both H2 O2 and Fe(II) ions doses were kept constant
(FeSO4 ·7H2 O 0.014 mol/L, H2 O2 0.216 mol/L), with pH varied in
range of 0.5–4.5 and HRT of 6 h. The H2 O2 to Fe(II) molar ratio
optimization studies were carried out at HRT of 6 h, keeping the
FeSO4 ·7H2 O dosage constant at 0.014 mol/L, with the input H2 O2 to
Fe(II) molar ratio varied from 7.5:1 to 20:1. Doses of H2 O2 were var-
ied from 0.086 to 0.432 mol/L, under optimum H2 O2 to Fe(II) molar
ratio condition and HRT of 6 h. During HRT optimization, optimum
H2 O2 and Fe(II) ions dosages were adopted and HRT was varied in
range of 2–7 h. The effluents of Fenton process were all analyzed
after coagulation process.
After optimization of ZVI-Fenton process, a bench-scale experi-
ment was utilized to investigate the performance of the combined
ZVI-Fenton process (Fig. 1). The setup consisted of a reservoir,
a zero-valent iron (ZVI) reactor, a Fenton reactor, a coagulation-
sedimentation tank, an anaerobic baffled reactor (ABR), and an
aerobic moving-bed biofilm reactor (MBBR). The flow rate was
10 L/h, with approximately 8 h HRT for the ZVI reactor, 5 h for Fen-
ton reactor, 7 h for coagulation-sedimentation tank, 5 d for ABR
reactor and 3 d for MBBR reactor. The operation temperature during
the test period varied between 25 and 32 ◦ C.
Fig. 1. Experiment installation: (1) reservoir; (2) zero-valent iron (ZVI) bed; (3) Fenton reactor; (4) coagulation-sedimentation tank; (5) anaerobic baffled reactor (ABR); (6)
moving-bed biofilm reactor (MBBR); (7) peristaltic pump; (8) air pump.
995
The ZVI bed was a plug flow reactor with an empty bed volume
of 80 L, filled with 50 kg of iron shavings. 0.2 wt.% of copper was
applied to the iron surface by reductive precipitation. In order to
increase the flow velocity and improve the wastewater distribution
within the reactor, effluent was recirculated through a peristaltic
pump with effluent recirculation ratio of 100%. For the purpose of
ZVI bed washing, the patching was loosened by means of water and
air in cross-current flow.
The effluent of the ZVI bed was further treated in a column
shaped Fenton reactor. Solutions of H2 O2 and FeSO4 ·7H2 O were
pumped into the Fenton reactor using peristaltic pumps and the
solution was mixed in the reactor using a mechanical stirrer.
The pH of the reaction mixture was controlled using H2 SO4 and
NaOH solution (0.1 mol/L). The effluent of Fenton reactor entered
a coagulation-sedimentation tank by gravity. 1 mol/L of Na2 CO3
was received in the coagulation-sedimentation tank, reaching the
pH band of 7.5–8.0, for precipitation of Fe(II) and Fe(III) ions and
co-precipitation of by-product produced by the Fenton reaction.
10 mg/L of Polyacrylamide (PAM) was added to improve settling
characteristics. The sludge was separated through sedimentation
tank, with the supernatant followed for biotreatment.
The biotreatment processes were designed in two parts: an
anaerobic baffled reactor (ABR) and an aerobic moving-bed biofilm
reactor (MBBR). The ABR was a rectangular box with eight equal
compartments by vertical baffles with 45◦ slanted edges. Poly-
hedral hollow ball fillers with 25 mm diameter were added into
the MBBR as medium for biofilm development, occupying 50% of
the reactor volume. In order to avoid nutrient limitations, NH4 Cl
and Na2 HPO4 ·12H2 O, were added into the influent of ABR to give
COD:N:P of 100:5:1. CaCl2 and MgSO4 were also added as nutrient.
Effluent of the ABR entered the MBBR through a gravity drain. Efflu-
ent of ABR was recirculated to the influent of ABR with recirculation
ratio of 200%. Both ABR and MBBR were initially inoculated with
sludge taken from a secondary sedimentation tank of a municipal
wastewater treatment plant.
2.4. Analytical methods
Before analysis, water samples were passed through a 0.22 ␮m
filter. COD, TOC, acute toxicity were determined according to our
previous study [18]. Before COD analysis, samples were heated
on the water bath at 80 ◦ C for 40 min to eliminate the residual
H2 O2 . DNAN, DNCB, DNP, and their degradation products in the
supernatant were identified and quantified by HPLC (Waters 2996,
996 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000

Fig. 3. Effect of pH on COD and TOC reduction during Fenton oxidation.

Fig. 2. Identification of intermediates in effluent of ZVI and Fenton by HPLC.

polymerization of 2,4-diaminoanisole occurred upon exposure to

Waters Incorporation, USA) through authentic standard and UV–vis
light analysis. The HPLC analysis was conducted at room tempera-
ture using a Waters RP18 column (5 ␮m, 4.6 mm × 250 mm) and a
UV–vis detector. The mobile phase was a mixture of 45% methanol
and 55% water pumped at a flow rate of 1.00 mL/min. The analysis
was performed at 254 nm, with column temperature at 35 ◦ C. Aro-
matic compounds in the wastewater were evaluated by UV254 [19].
Color was analyzed by dilution ratio method, according to China
NEPA standard methods (GB/T 11903-89).
3. Results and discussion
3.1. Characterization of ZVI reduction process
As shown in Table 2 and Fig. 2, in the effluent of the
ZVI bed (EBCT = 8 h), both DNAN and DNCB were almost com-
pletely removed, with removal efficiency of 99.8% and 99.9%,
respectively. Only low concentration of DNP (2.3 ± 1.5 mg/L) was
found in the effluent of ZVI, with removal efficiency of 97.9%.
According to our previous study, DNCB could be reduced to 2,4-
diaminochlorobenzene (DACB) completely by iron shavings [18].
Complete reduction of DNAN to 2,4-diaminoanisole (DAAN) in abi-
otic iron reduction study was also observed by Ahn et al. [20]. The
removal efficiency of DNP was not as high as DNAN and DNCB in
the ZVI bed, probably due to the electron donating character of
the hydroxy group, which resulted into a less electron deficient ␲-
electron system on DNP. Thus, the competition of DNP for electron
donors was weakened.
It can be inferred that, in ZVI reduction process, DNAN,
DNCB and DNP could be reduced to 2,4-diaminoanisole (DAAN),
2,4-diaminochlorobenzene (DACB) and 2,4-diaminophenol (DAP),
respectively. However, as was indicated by the results of HPLC
of ZVI effluent (Fig. 2b), among the three reductive products,
only DACB was observed. As Platten III et al. [1] suggested,
oxygen. 2,4-Diaminoanisole could be removed through polymer-
ization and subsequent capture in the floc. 2,4-Diaminophenol
could not be observed in the effluent of ZVI from HPLC as
well. Although no evidence could be found to link this phe-
nomenon to polymerization of 2,4-diaminophenol, polymerization
of amines with similar structure has been seen by other researchers.
Yang et al. [21] showed that diaminotoluene in aerobic sedi-
ment could form dimers and trimers. Another study showed a
non-electroactive polymeric material was formed on the elec-
trode surface when 2,3-diaminophenol was exposed to platinum
electrodes [22]. Electrochemical copolymerization of aniline with
2,4-diaminophenol was also observed by Mu et al. [23]. So,
polymerization of 2,4-diaminophenol might be the main reason
for the absence of 2,4-diaminophenol in HPLC. However, 2,4-
diaminochlorobenzene (DACB) was very stable in the effluent of
ZVI process, which was confirmed in our previous study [18].
Thus, to ensure high removal efficiency of DNCB, DNAN and DNP,
EBCT of 8 h was adopted for ZVI process.
3.2. Characterization and optimization of Fenton oxidation
process
3.2.1. Effect of pH
An essential characteristic of the Fenton process is that pH in
the acidic range. pH affects the activity of both the oxidant and the
substrate, the speciation of iron, and hydrogen peroxide decompo-
sition [24]. Fig. 3 showed the effect of pH on COD and TOC removal
efficiencies. It was apparent from Fig. 3 that COD removal increased
with pH increase, and maximum COD removal was observed at pH
of 3, after which the COD removal decreased. The effect of pH on
TOC removal efficiency was also obtained and it was observed to
be similar to COD removal. In addition, TOC removal efficiency was
a little lower than COD removal efficiency under the same operat-
ing conditions. The reduction in COD and TOC removal efficiency

Table 2
Performance of ZVI-Fenton-ABR-MBBR process under optimal conditions.

COD (mg/L) TOC (mg/L) DNAN (mg/L) DNCB (mg/L) DNP (mg/L) EC50, 48 h (v/v) Color (times) UV254 a

Influent 34,000 ± 985 7151 ± 329 123.1 ± 3.8 249.3 ± 6.9 110.4 ± 4.2 0.67% 700–1000 0.798
EffZVI 28,380 ± 645 6364 ± 195 0.3 ± 0.5 0.2 ± 0.3 2.3 ± 1.5 45.2% 300–500 0.232
EffFenton 15,638 ± 2870 4327 ± 134 – – – 17.3% 70–100 0.182
EffABR 1200 ± 235 351.6 ± 45.8 – – – 63.8% 60–90 0.053
EffMBBR 79.6 ± 25.9 35.3 ± 5.7 – – – Not toxic 30–50 0.012

– undetectable
a
25 times diluted.
 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000
Fig. 4. Effect of H2 O2 to Fe(II) molar ratio on COD and TOC removal.
below pH of 3.0 might be attributed to scavenging of hydroxyl rad-
ical with H+ ions [25,26]. Also above pH 3.0, the ferrous ion got
converted to ferric ion which then combined with hydroxyl radi-
cals to produce ferric hydroxide, which precipitated and settled
down, thereby reducing the ferrous availability in the solution [25].
In addition, above pH 3, more hydrogen peroxide was decomposed
without improving oxidation. The results agreed with other studies
on the oxidation of organic compounds in wastewaters that Fen-
ton reactions efficiently occurred between 2.9 and 3.5 pH range
[24,25,27,28].
3.2.2. Effect of H2 O2 to Fe(II) molar ratio
In Fenton process, iron and hydrogen peroxide are two major
chemicals determining operation costs as well as efficacy. Deter-
mination of the favorable amount of the Fenton’s reagent is highly
important. In order to investigate the optimum H2 O2 /Fe(II) molar
ratio, six different H2 O2 /Fe(II) molar ratios from 7.5:1 to 20:1
were tested (Fig. 4). It was shown that COD removal efficien-
cies increased with the increase of H2 O2 /Fe(II) molar ratio by the
H2 O2 /Fe(II) molar ratio of 15:1. COD removal efficiencies decreased
with further increase in H2 O2 /Fe(II) molar ratio over 15:1. The
effect of H2 O2 /Fe(II) molar ratio on TOC removal efficiency was
also obtained and it was observed to be similar to that on COD
removal efficiency. However, at H2 O2 /Fe(II) molar ratio over 15:1,
TOC removal efficiency decreased slightly.
Sludge settling characteristic was excellent at the H2 O2 /Fe(II)
molar ratio of 15:1, but became poor above the H2 O2 /Fe(II) molar
ratio of 17.5:1. It seemed that excessive hydrogen peroxide, when
decomposed, would produce oxygen bubbles that made sludge
settling difficult [24,29]. In addition, residual H2 O2 might inhibit
downstream biological treatment. When H2 O2 /Fe(II) molar ratio
was below 15:1, residual ferrous iron was observed, with the efflu-
ent bluish green. Also, excess iron salt contributed to an increase in
effluent TDS and electrical conductivity, as well as in the amount
of iron sludge that required further treatment [30,31].
Therefore, H2 O2 /Fe(II) molar ratio of 15:1 was chosen for further
experiments.
3.2.3. Effect of Fenton reagents dosage
Dosage of Fenton reagents determines not only the operation
costs but also the efficiency of organics removal for the Fenton
process [31]. The dosage differs depending on whether the Fenton
process has a role of pretreatment or ultimate pretreatment. Three
types of degradation of organic materials were described by Lyman
et al. [32] as: primary degradation, a structural change in the parent
compound where biodegradability might be improved; acceptable
997
Fig. 5. Effect of Fenton reagents dosage on UV254 (the samples were determined 5
times diluted) and color removal.
degradation, degradation to the extent that toxicity was reduced;
ultimate degradation, complete to carbon dioxide, water and other
inorganics. As Bowers et al. [33] indicated, a primary or acceptable
degradation might occur in a relatively low consumption and be
much more efficient than ultimate degradation. In this study, as
the influent COD was rather high, dosage of Fenton reagents would
be extremely high if ultimate degradation was achieved. Therefore,
primary or acceptable degradation was adopted, with the effect of
dosage on aromatic compounds removal and color removal empha-
sized. In addition, DACB, which was the main by-product from ZVI
process, was found to be very stable in biological process. Thus,
the effect of Fenton reagent dosage on DACB removal was also
investigated.
As was indicated by Fig. 5, at H2 O2 /Fe(II) molar ratio of 15:1,
the aromatic compounds (indicated by UV254 ) removal efficiency
increased rapidly with the increase of Fenton dosage. However,
further increase in H2 O2 dosage beyond 0.216 mol/L gave milder
increased removal efficiency of aromatic compounds. The color
removal followed the same trends. After Fenton-coagulation pro-
cess, the effluent changes into light yellow from reddish brown. At
H2 O2 dosage of 0.216 mol/L, the color value of Fenton effluent was
only 72.5 times. Removal of DACB was also closely related to Fen-
ton reagents dosage. As was shown in Fig. 6, with the increase of
Fenton reagent dosage, removal of DACB increased. At H2 O2 dosage
of 0.216 mol/L, 87.8% of influent DACB was removed in the Fenton
Fig. 6. Effect of Fenton reagents dosage on DACB removal.
998 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000
Fig. 7. Effect of HRT on COD and TOC removal during Fenton oxidation.
oxidation process. Further increase of dosage gave milder increased
removal efficiency for DACB.
Inferring these results, Fenton reagents dosage could be chosen
as follows: H2 O2 dosage of 0.216 mol/L (H2 O2 /Fe(II) molar ratio of
15:1). At this dosage, effluent of Fenton process mainly consisted of
methanol and formic acid, which were amenable for the biological
process.
3.2.4. Effect of HRTs
It is very important to determine the appropriate HRT for the
reactor because the performance of Fenton process is associated
with HRT obviously. The efficiency would decrease and the con-
struction cost would increase if HRT was too long. Thus, the effect
of HRTs on Fenton process was tested to determine an experi-
mental condition for further research. In Fig. 7, the variations of
the COD and TOC concentrations at different HRTs were shown.
The results demonstrated that organic materials removal increased
with the increase of HRT in the range of 2–5 h. At HRT of 5 h,
COD removal increased to 44.2%, while TOC removal increased to
32.0%. No insignificant improvement of COD and TOC removal was
observed with further increase in HRT beyond the range of 2–5 h.
In most literature for Fenton oxidation, contact time of 0.5–3 h has
been reported [24,27,34,35], however, the contact time of 5 h in
this study was a bit long, probably due to the high influent COD
and high dosage of iron and hydrogen peroxide. Therefore, in the
subsequent stage of the research, HRT of 5 h was chosen as the
optimal parameter for further investigation.
3.3. Performance of ZVI-Fenton-ABR-MBBR process
The coupled ZVI-Fenton-ABR-MBBR process was operated for 3
months. As was described previously, for ZVI process, EBCT of 8 h
was adopted. For Fenton process, pH of 3.0, H2 O2 to Fe(II) molar
ratio of 15:1, H2 O2 dosage of 0.216 mol/L, HRT of 5 h, were favor-
able for the organic removal. Under these optimal conditions, the
ZVI-Fenton pretreatment process was operated and the pretreated
effluent was fed into the ABR-MBBR process. Table 2 reveals the
performance of ZVI-Fenton-ABR-MBBR process under optimal con-
ditions, in terms of organic compounds, color, UV254 , acute toxicity.
Although COD removal and TOC removal was not high
(54.0 ± 8.4% and 39.5 ± 1.9% respectively), ZVI-Fenton coupled pro-
cess exhibited excellent performance on aromatic compounds
removal, toxicity and color reduction. DNAN, DNCB, DNP were
almost completely removed by ZVI process. In Fenton effluent, the
color decreased from 300–500 times in influent to 70–100 times,
while UV254 values, which indicated the concentration of aromatic
Fig. 8. Evolution of UV–vis spectra during ZVI-Fenton process.
compounds, decreased from 0.798 to 0.182, with the removal effi-
ciency of 77.2%. The high removal efficiency of aromatic compouds
also indicated excellent pretreatment performance of ZVI-Fenton
coupled process. The EC50, 48 h (v/v) values of ZVI influent was only
0.67%, which indicated that the DNAN producing wastewater was
highly toxic and was much resistant to mineralization by biological
process. After pretreatment by ZVI (EBCT = 8 h), the biological tox-
icity was greatly lowered as revealed by the EC50 value increasing
from 0.67% to 45.2%, probably due to almost complete conversion
of DNAN, DNCB and DNP into their corresponding aminoaromatic
compounds [6]. The reduction of biological toxicity reflected the
improvement of biodegradability [36], so that the results of the
reduced biological toxicity demonstrated the effectiveness of ZVI in
the biodegradability improvement of the tested DNAN producing
wastewater. However, EC50 value decreased to 17.3% after Fenton
process, probably due to the residual hydroxyl radicals produced
in Fenton process.
The spectrophotometric results also demonstrated effective
degradation of the chromophorous group. After pretreatment by
ZVI, the characteristic absorbance peak of aromatic compounds,
at approximately 260 nm and 360 nm, decreased. While simul-
taneously an absorbance peak at about 215 nm and 290 nm was
formed. The Fenton treatment promoted the removal of all the
absorbed species at 215 nm, 290 nm (Fig. 8), indicating complete
removal of the aromatic compounds. It was found that color of
ZVI influent turned from yellow to reddish brown after ZVI pro-
cess, while the color of reddish brown turned to light yellow after
Fenton process. The significant transformation of the color also
demonstrated the high removal of aromatic compounds by com-
bined ZVI-Fenton process. The HPLC analysis revealed the removal
of the aromatic compounds as well. After ZVI treatment, the inter-
mediate detectable by HPLC was DACB only (Fig. 2b). However,
concentration of DACB decreased significantly after Fenton oxida-
tion process (Fig. 2c), meanwhile the chromatographic peak shifted
to lower retention times, indicating the formation of less aromatic
and more polar compounds during the Fenton process.
Effluent of ZVI-Fenton process was fed into the ABR-MBBR
biological process for further treatment. After the acclimation
phase of the ABR-MBBR (about 40 d), steady state was achieved.
For biological treatment process, only results under steady state
were included in Table 2. As was indicated previously, aromatic
compounds, such as DNAN, DNCB, DNP, and their degradation by-
products, could be effectively removed in the ZVI-Fenton process.
Methanol, its oxidative product formic acid, and residual aromatic
compounds contributed to the COD of bioprocess influent. Thus
 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000
ABR-MBBR bioprocess was designed to degrade Methanol, formic
acid and residual aromatic compounds. The performance of the
ABR-MBBR process was investigated in terms of the effluent COD
and TOC, the effluent color, and acute toxicity in effluent.
Based on the data presented in Table 2, it could be inferred that
the ABR-MBBR coupled process used in this study exhibited excel-
lent polishing performance. The good quality of the effluent from
bioprocess was indicated by low residual COD and TOC concentra-
tions. Under steady state, the average effluent COD and TOC was
as low as 79.6 ± 25.9 mg/L, and 35.3 ± 5.7 mg/L, respectively. Color
value of MBBR effluent was as low as 30–50 times. Low UV254 value
in effluent of MBBR also revealed the high removal of aromatic
compounds.
Based on the EC50 data presented in Table 2, the ABR-MBBR
process used in this study was effective for detoxification of the
ZVI-Fenton effluent. After the ABR process, the EC50, 48 h (v/v) val-
ues increased from 17.3% to 63.8%, whereas the samples taken at
the end of the MBBR were not toxic, since all Zebrafish subjected to
the undiluted effluents of the MBBR survived. Thus, an EC50 value
for the MBBR effluent could not be ascertained. These results con-
firmed the complete elimination of acute toxicity in the coupled
ABR and MBBR process.
3.4. Implication
Since conventional biological treatment is not effective in
polishing high strength wastewater containing nitroaromatic com-
pounds, such as DNAN producing wastewater. The goal of this
research is to look into the effectiveness of ZVI-Fenton cou-
pled process as a pretreatment method for DNAN producing
wastewater.
The first step in the coupled ZVI-Fenton process involving the
reduction of nitroaromatic compounds into their corresponding
aminoaromatic compounds using ZVI was necessary. Nitro group
was an electron-withdrawing group, while amino group was an
electron-donating group [9]. The reduction of nitro group into
amino group reduced the toxicity of nitroaromatic compounds
[37], creating favorable conditions for degradation of the target
pollutant in the subsequent biological or oxidation process. An
interesting phenomenon was observed by Barreto-Rodrigues et al.
[8] that when the effluent was submitted to the Fenton treatment
(H2 O2 /Fe(II) molar ratio of 5:1) without passing through the col-
umn of metallic iron, there were no significant removals of TNT or
COD, suggesting that the transformations that occur inside the ZVI
column were very important for the success of the oxidative treat-
ment. For Fenton oxidation process, significance of ZVI reduction
was also proved by our studies.
Compared with anaerobic reductive process, the ZVI reactor in
this study was much smaller, with EBCT of only 8 h. Three-month
operation of this system proved that the need for maintenance was
minimal. The ZVI reactor was stopped only briefly for backwash and
inspection, leading to easy maintenance and low operating cost.
The reductive products of DNAN, DNCB and DNP could be effec-
tively removed in the sequent process through polymerization and
subsequent capture in the floc or oxidative cleavage of benzene
ring. Although Fenton process had the drawback of high cost, the
combination of ZVI with Fenton process was significantly efficient
for the treatment of explosive industry effluents [8]. Low cost of ZVI
process and optimization of the operation parameters could ease
the problem of high cost during Fenton stage.
Thus, the coupled ZVI-Fenton process gave excellent per-
formance when pretreating DNAN producing wastewater. This
technology could be considered as a potential process for the pre-
treatment of high strength wastewater containing nitroaromatic
compounds.
999
4. Conclusions
The purpose of this study was to evaluate the effectiveness of
coupled ZVI-Fenton system for the pretreatment of DNAN produc-
ing wastewater. The following conclusions were derived:
(1) For ZVI process, almost complete reduction of nitroaromatic
compounds was observed at EBCT of 8 h. For Fenton process,
the optimal pH, H2 O2 to Fe2+ molar ratio, H2 O2 dosage, HRT
were found to be 3.0, 15, 0.216 mol/L and 5 h, respectively.
(2) The combined process of ZVI reduction and Fenton oxida-
tion was significantly efficient for the pretreatment of DNAN
producing wastewater. Reductive transformation of the nitro
functional groups by ZVI overcame the hindrance to subsequent
Fenton oxidation.
(3) After ZVI-Fenton pretreatment, the effluent could be well
polished by ABR-MBBR coupled bioprocess. The present find-
ings indicate that the coupled ZVI-Fenton-ABR-MBBR system
offers bright prospects for the treatment of nitroaromatic
compounds-containing wastewater.
Acknowledgements
This research is financed by Innovation Program of Foun-
dation Product, Major Project of Water Pollution Control and
Management Technology of P. R. China (No. 2012ZX07101-003-
001), National Natural Science Foundation of China (No. 50978136
and 51208258), Natural Science Foundation of Jiangsu Province
(No. BK2011717), China Postdoctoral Science Foundation (No.
2011M500927), Jiangsu Planned Projects for Postdoctoral Research
Funds (No. 1101014C), Fundamental Research Funds for the Central
Universities (No. 30920130122007) and Zijing Intelligent Program
(No. 2013-ZJ-02-19).
References
[1] W.E. Platten III, D. Bailey, M.T. Suidan, S.W. Maloney, Biological transformation
pathways of 2,4-dinitro anisole and N-methyl paranitro aniline in anaerobic
fluidized-bed bioreactors, Chemosphere 81 (2010) 1131–1136.
[2] N.N. Perreault, D. Manno, A. Halasz, S. Thiboutot, G. Ampleman, J. Hawari,
Aerobic biotransformation of 2,4-dinitroanisole in soil and soil Bacillus sp.,
Biodegradation 23 (2012) 287–295.
[3] J.A. Zazo, J.A. Casas, A.F. Mohedano, M.A. Gilarranz, J.J. Rodriguez, Chemical
pathway and kinetics of phenol oxidation by Fenton’s reagent, Environ. Sci.
Technol. 39 (2005) 9295–9302.
[4] H. Lin, L. Zhu, X. Xu, L. Zang, Y. Kong, Reductive transformation and dechlori-
nation of chloronitrobenzenes in UASB reactor enhanced with zero-valent iron
addition, J. Chem. Technol. Biotechnol. 86 (2011) 290–298.
[5] J. Zhang, Z. Sun, Y. Li, X. Peng, W. Li, Y. Yan, Biodegradation of p-nitrophenol
by Rhodococcus sp. CN6 with high cell surface hydrophobicity, J. Hazard. Mater.
163 (2009) 723–728.
[6] J. Shen, R. He, H. Yu, L. Wang, J. Zhang, X. Sun, J. Li, W. Han, L. Xu, Biodegra-
dation of 2,4,6-trinitrophenol (picric acid) in a biological aerated filter (BAF),
Bioresour. Technol. 100 (2009) 1922–1930.
[7] S. Susarla, Y. Yonezawa, S. Masunaga, Reductive transformations of halogenated
aromatics in anaerobic estuarine sediment: kinetics, products and pathways,
Water Res. 32 (1998) 639–648.
[8] M. Barreto-Rodrigues, F.T. Silva, T.C.B. Paiva, Combined zero-valent iron and
fenton processes for the treatment of Brazilian TNT industry wastewater, J.
Hazard. Mater. 165 (2009) 1224–1228.
[9] Y. Mu, R.A. Rozendal, K. Rabaey, J. Keller, Nitrobenzene removal in bioelectro-
chemical systems, Environ. Sci. Technol. 43 (2009) 8690–8695.
[10] M.M. Häggblom, V.K. Knight, L.J. Kerkhof, Anaerobic decomposition of halo-
genated aromatic compounds, Environ. Pollut. 107 (2000) 199–207.
[11] L.H. Li, J. Wang, J. Zhou, F.L. Yang, C.Y. Jin, Y.Y. Qu, Enhancement of nitroaromatic
compounds anaerobic biotransformation using a novel immobilized redox
mediator prepared by electropolymerization, Bioresour. Technol. 99 (2008)
6908–6916.
[12] C. Le, J. Liang, J. Wu, P. Li, X. Wang, N. Zhu, P. Wu, B. Yang, Effective degradation
of para-chloronitrobenzene through a sequential treatment using zero-valent
iron reduction and Fenton oxidation, Water Sci. Technol. 64 (2011) 2126–2131.
[13] J.-H. Fan, H.-W. Wang, D.-L. Wu, L.-M. Ma, Effects of electrolytes on the reduc-
tion of 2,4-dinitrotoluene by zero-valent iron, J. Chem. Technol. Biotechnol. 85
(2010) 1117–1121.
1000 J. Shen et al. / Journal of Hazardous Materials 260 (2013) 993–1000
[14] W.A. Arnold, A.L. Roberts, Inter- and intraspecies competitive effects in
reactions of chlorinated ethylenes with zero-valent iron incolumn reactors,
Environ. Eng. Sci. 17 (2000) 291–302.
[15] H.-Y. Shu, M.-C. Chang, C.-C. Chen, P.-E. Chen, Using resin supported nano
zero-valent iron particles for decoloration of Acid Blue 113 azo dye solution, J.
Hazard. Mater. 184 (2010) 499–505.
[16] L.M. Ma, W.X. Zhang, Enhanced biological treatment of industrial wastewater
with bimetallic zero-valent iron, Environ. Sci. Technol. 42 (2008) 5384–5389.
[17] C.A. Somensi, E.L. Simionatto, S.L.A.W. Bertoli Jr., C.M. Radetski, Use of ozone
in a pilot-scale plant for textile wastewater pre-treatment: physico-chemical
efficiency, degradation by-products identification and environmental toxicity
of treated wastewater, J. Hazard. Mater. 175 (2010) 235–240.
[18] J. Shen, Z. Zhou, C. Ou, X. Sun, J. Li, W. Han, L. Zhou, L. Wang, Reductive
transformation and detoxification mechanism of 2,4-dinitrochlorobenzene in
combined zero valent iron and anaerobic-aerobic process, J. Environ. Sci. 11
(2012) 1900–1907.
[19] J.X. Ravikumar, M.D. Gurol, Chemical oxidation of chlorinated organics by
hydrogen peroxide in the presence of sand, Environ. Sci. Technol. 28 (1994)
394–400.
[20] S.C. Ahn, D.K. Cha, B.J. Kim, S.-Y. Oh, Detoxification of PAX-21 ammunitions
wastewater by zero-valent iron for microbial reduction of perchlorate, J. Haz-
ard. Mater. 192 (2011) 909–914.
[21] H. Yang, A. Halasz, J. Zhao, F. Monteil-Rivera, J. Hawari, Experimental evidence
for in situ natural attenuation of 2,4- and 2,6-dinitrotoluene in marine sedi-
ment, Chemosphere 70 (2008) 791–799.
[22] H.J. Salavagione, J. Arias-Pardilla, J.L. Vázquez, M.C. Miras, E. Morallón, C. Bar-
bero, Spectroelectrochemical study of the oxidation of diaminophenols on
platinum electrodes in acidic medium, Electrochim. Acta 50 (2005) 5414–
5422.
[23] S. Mu, Y. Zhang, J. Zhai, The electrochemical copolymerization of aniline with
2,4-diaminophenol and the electric properties of the resulting copolymer, Elec-
trochim. Acta 54 (2009) 3923–3929.
[24] H. Zhang, H.J. Choi, C.-P. Huang, Optimization of Fenton process for the treat-
ment of landfill leachate, J. Hazard. Mater. B 125 (2005) 166–174.
[25] K.V. Padoley, S.N. Mudliar, S.K. Banerjee, S.C. Deshmukh, R.A. Pandey, Fenton
oxidation: a pretreatment option for improved biological treatment of pyridine
and 3-cyanopyridine plant wastewater, Chem. Eng. J. 166 (2011) 1–9.
[26] E. Neyens, J. Baeyens, A review of classic Fenton’s peroxidation as an advanced
oxidation technique, J. Hazard. Mater. 98 (2003) 35–50.
[27] B. Lodha, S. Chaudhari, Optimization of Fenton-biological treatment scheme for
the treatment of aqueous dye solutions, J. Hazard. Mater. 148 (2007) 459–466.
[28] H. Kušić, A.L. Božić, N. Koprivanac, Fenton type processes for minimization of
organic content in coloured wastewaters. Part I: processes optimization, Dyes
Pigm. 74 (2007) 380–387.
[29] I.W.C. Lau, P. Wang, H.H.P. Fang, Organic removal of anaerobically treated
leachate by Fenton coagulation, J. Environ. Eng. 27 (2001) 666–669.
[30] P.R. Gogate, A.B. Pandit, A review of imperative technologies for wastewater
treatment I: oxidation technologies at ambient conditions, Adv. Environ. Res.
8 (2004) 501–551.
[31] Y. Deng, J.D. Englehardt, Treatment of landfill leachate by the Fenton process,
Water Res. 40 (2006) 3683–3694.
[32] W.J. Lyman, W.F. Reehl, D.H. Rosenblatt, Handbook of Chemical Property
Estimation Methods, in: Environmental Behavior of Organic Compounds,
McGraw-Hill, New York, 1982.
[33] A.R. Bowers, P.W.W.E. Gaddipati Jr., R.M. Monsen, Treatment of toxic or refrac-
tory wastewaters with hydrogen peroxide, Water Sci. Technol. 21 (1989)
477–486.
[34] J. Blanco, F. Torrades, M. De la Varga, J. García-Montaño, Fenton and
biological-Fenton coupled processes for textile wastewater treatment and
reuse, Desalination 286 (2012) 394–399.
[35] J.A. Zimbron, K.F. Reardon, Continuous combined Fenton’s oxidation and
biodegradation for the treatment of pentachlorophenol-contaminated water,
Water Res. 45 (2011) 5705–5714.
[36] Z. Xiong, X. Cheng, D. Sun, Pretreatment of heterocyclic pesticide wastewater
using ultrasonic/ozone combined process, J. Environ. Sci. 23 (2011) 725–730.
[37] X. Xu, H. Lin, L. Zhu, Y. Yang, J. Feng, Enhanced biodegradation of 2-
chloronitrobenzene using a coupled zero-valent iron column and sequencing
batch reactor system, J. Chem. Technol. Biotechnol. 86 (2011) 993–1000.