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2.textile Dye Degradation Using Nano Zero Valent Iron - A Review
2.textile Dye Degradation Using Nano Zero Valent Iron - A Review
discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/301671266
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2 authors, including:
Chandra Devi Raman
Anna University, Chennai
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a b s t r a c t
Article history:
Received 18 December 2015
Received in revised form
9 April 2016
Accepted 12 April 2016
Water soluble unxed dyes and inorganic salts are the major pollutants in textile dyeing industry
wastewater. Existing treatment methods fail to degrade textile dyes and have limitations too. The
inadequate treatment of textile dyeing wastewater is a major concern when efuent is directly discharged into the nearby environment. Long term disposal threatens the environment, which needs
reclamation. This article reviews the current knowledge of nano zero valent iron (nZVI) technique in the
degradation of textile dyes. The application of nZVI on textile dye degradation is receiving great attention
in the recent years because nZVI particles are highly reactive towards the pollutant, less toxic, and
economical. The nZVI particles aggregate quickly with respect to time and the addition of supports such
as resin, nickel, zinc, bentonite, biopolymer, kaolin, rectorite, nickel-montmorillonite, bamboo, cellulose,
biochar, graphene, and clinoptilolite enhanced the stability of iron nanoparticles. Inclusion of supports
may in turn introduce additional toxic pollutants, hence green supports are recommended. The majority
of investigations concluded dye color removal as textile dye compound removal, which is not factual.
Very few studies monitored the removal of total organic carbon and observed the products formed. The
results revealed that partial mineralization of the textile dye compound was achieved. Instead of stand
alone technique, nZVI can be integrated with other suitable technique to achieve complete degradation
of textile dye and also to treat multiple pollutants in the real textile dyeing wastewater. It is highly
recommended to perform more bench-scale and pilot-scale studies to apply this technique to the textile
efuent contaminated sites.
2016 Elsevier Ltd. All rights reserved.
Keywords:
Nano zero valent iron
Textile dye degradation
Partial mineralization
Textile dyeing wastewater
Environmental remediation
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Treatment of textile dyeing industry wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2.1.
Textile dyeing industry wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2.2.
Conventional and advanced treatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
2.3.
Photocatalytic treatment using TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
Development of nZVI particles in environmental remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
3.1.
Permeable Reactive Barriers (PRBs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
3.2.
Iron PRBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
3.3.
Zero valent iron particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
3.4.
nZVI particles with supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
3.5.
nZVI integrated with other technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Nano zero valent iron (nZVI) on textile dye degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
4.1.
nZVI efficiency over other iron forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
4.2.
Textile dyes chemical structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
4.3.
Reaction between nZVI particles and textile dye . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
4.4.
Textile dye removal/degradation using nZVI particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
4.5.
Assessing textile dye degradation using nZVI particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
* Corresponding author.
E-mail address: skanmani@annauniv.edu (S. Kanmani).
http://dx.doi.org/10.1016/j.jenvman.2016.04.034
0301-4797/ 2016 Elsevier Ltd. All rights reserved.
342
5.
4.5.1.
Dye degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
4.5.2.
Influence of supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
4.5.3.
Integration with other treatment technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
4.5.4.
nZVI technique in presence of other pollutant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
4.5.5.
Fate of nZVI particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
1. Introduction
Environmental pollution due to industrial activities has been
increasing in the last four decades. One such industry is textile
dyeing. The textile dye industry efuents are complex; consisting of
dyes, alkalis, organic and inorganic salts, acids, and heavy metals
(Ghaly et al., 2014). The conventional physicochemical and biological treatment methods are inefcient to treat water soluble
reactive textile dyes. There is no adequate color removal (Juang and
Tseng, 1996) and organic compound mineralization (Robinson
et al., 2001). The emerging photocatalytic treatment of textile
dyes using TiO2 also has drawbacks (Bubacz et al., 2010; Rajeshwar
et al., 2008). The existing treatment technologies discharge the
partially treated textile dye industry efuent into nearby environment thereby causing degradation (Geetha et al., 2008; Imran et al.,
2015; Mathur et al., 2005; Odjegba and Bamgbose, 2012;
Sellamuthu et al., 2011). In particular, the textile dye industry
efuent alters the color and quality of waterbodies. As the efuent
makes its way into the watertable, groundwater quality also gets
deterioted (Gopal and Saranyadevi, 2014; Hossain et al., 2014;
Senthilnathan and Azeeza, 1999b). The toxic impacts of textile
Table 1
Review papers published in 2003e2015 on environmental nano remediation e a summary.
Purpose
Nanoparticles in environmental applications
Nanoscience in environmental remediation
Nanotechnologies for environmental clean up
Literatures
(Kamat and Meisel, 2003)
(Hoyt and Mason, 2008; Karn et al., 2009; Liu, 2006; Mueller and Nowack,
2010; Pandey and Fulekar, 2012; Stone et al., 2010; Tratnyek and Johnson,
2006)
(Riu et al., 2006; Zhang and Fang, 2010)
(Gottschalk and Nowack, 2011; Grillo et al., 2014; Ju-Nam and Lead, 2008;
Nowack and Bucheli, 2007)
(Bhattacharya et al., 2013; Brar et al., 2010; Chaturvedi et al., 2012; Pradeep
and Anshup, 2009; Qu et al., 2013)
mez-Pastora et al., 2014; Xu et al., 2012; Zhao et al., 2011)
(Go
(Crane and Scott, 2012; Cundy et al., 2008; Grieger et al., 2010; Kharisov et
al., 2012; Li et al., 2006; Mueller et al., 2012; O'Carroll et al., 2013;
Taghizadeh et al., 2013; Zhang, 2003)
(Liu et al., 2014)
(Shi et al., 2015; Tosco et al., 2014; Yan et al., 2013)
(Batool et al., 2014)
(Trujillo-Reyes et al., 2014)
(Fu et al., 2014; Raychoudhury and Scheytt, 2013)
(Tan et al., 2015)
343
more focus in the current decade (Fig. 1). The toxicity of nZVI particles are less compared to carbon nano tubes, nano diamond, nano
TiO2, nano ZnO on textile dye degradation and also no toxic effect is
reported on humans (Tan et al., 2015).
The application of nZVI particles to remove various contaminant
344
in Fig. 2. The textile dye is the main pollutant that needs effective
treatment to achieve complete mineralization, which is not
possible with available conventional and advanced treatment
methods (Ghaly et al., 2014; Robinson et al., 2001).
2.3. Photocatalytic treatment using TiO2
Photocatalytic oxidation is the latest treatment technique,
generates low waste and utilizes ultraviolet (UV) illumination as
well as titanium dioxide (TiO2) as catalyst to achieve textile dye
degradation. The UV light enhances TiO2 catalyst activity during
dye degradation (Bizani et al., 2006; Kanmani and Thanasekaran,
2003; Lachheb et al., 2002; Tang and An, 1995; Vautier et al.,
2001). Bubacz et al. (2010) achieved more than 90% dye decolorization using TiO2/UV system but only 3.99% of total organic carbon
(TOC) removal was observed in 6 h at pH 9. Although, there are
benets in utilizing TiO2, some limitations exist for the pure TiO2,
having bandgap larger than 3.2 eV (Linsebigler et al., 1995) and the
electron-hole recombination rate is too high, resulting in low
photocatalytic efciency (Ueda and Otsuka-Yao-Matsuo, 2004;
Wang et al., 2006; Zyoud et al., 2010). In addition, the photocatalytic activity of TiO2 catalyst degraded textile dyes partially and
produced toxic intermediates, and products (Akpan and Hameed,
2009; Chen, 2009; Konstantinou and Albanis, 2004; Rajeshwar
et al., 2008). Zn doped TiO2 decreased the bandgap energy and
showed better photocatalytic activity even in the visible light
(Singla et al., 2014). However, the dye degradation using metal
doped TiO2 (Karimi and Zohoori, 2013; Singla et al., 2014) or other
metal catalyst (Kansal et al., 2009; Mahmoodi et al., 2014; Manivel
et al., 2015; Rahman et al., 2013; Tolia et al., 2012; Vidhu and Philip,
2014) may generate toxic intermediates or introduce metal pollution. Also the photocatalytic degradation technique is efcient only
for pumping and treating strategies, and not suitable for eld
application in remediating contaminated sites.
3. Development of nZVI particles in environmental
remediation
3.1. Permeable Reactive Barriers (PRBs)
Environmental and geotechnical scientists explored PRB technology (Gavaskar, 1999; Starr and Cherry, 1994; Thomson et al.,
1991) to restore the subsurface environment by treating the
contaminant plumes movement in ground water and soils. PRB is a
Fig. 3. (a) Micrograph of oxidized nZVI particles (b) TEM image of aggregated nZVI particles.
345
the aggregated two months aged nZVI particles, chemically synthesized using sodium borohydride method and the behavior was
observed for this review.
3.4. nZVI particles with supports
The aggregation behavior can be inhibited by adding supports or
nanocomposites. Schrick et al. (2004) utilized carbon supported
nZVI in the presence of palladium for the removal of TCE in subsurface environment. This study showed that the supported nZVI
improved the reactivity, mobility of the particles in subsurface
remediation. Zhang et al. (2010) achieved the removal of Pb(II) in
60 min using 5 g/L of kaolin supported nZVI. Ali et al. (2015) added
porous cation exchange resin to nZVI particles to reduce Cr(VI) to
Cr(III) in aqueous solution. Currently, green supports using grape
leaf, green tea, eucalyptus leaf, and other tree leaf extracts are
under review for the stabilization of nZVI particles and also to
improve their reactivity (Hoag et al., 2009; Kharissova et al., 2013;
Machado et al., 2015; Prasad et al., 2014; Shahwan et al., 2011;
Wang et al., 2014a, 2014b; Weng et al., 2013).
Fig. 4. Evolution of Iron Permeable Reactive Barriers (PRBs) to nZVI technique on Environmental Remediation e past two decades (1995e2015).
346
In addition to nZVI, mZVI and iron oxides can also be opted for
textile dye degradation (Trujillo-Reyes et al., 2014; Xu et al., 2012).
However the efciency of mZVI and iron oxide are inferior, due to
the intrinsic passive layer of mZVI and inert surface of oxidized iron
(Guan et al., 2015). Chompuchan and Satapanajaru (2009) and Shih
et al. (2010) observed the specic surface area of nZVI particles
(29.67 m2/g, 29 m2/g) is larger than mZVI (2.55 m2/g, 0.2 m2/g). The
nZVI particles decolorized 90% dye molecules in 24 min but mZVI
particles achieved only 25% dye decolorization (Shih et al., 2010).
Also the achievement of nZVI particles on textile dye degradation
has been widely reported in recent years (Fig. 1.). The percentage of
research carried out on textile dye degradation using nZVI is higher
than mZVI and iron oxides, indicated in Fig. 5.
347
Table 2
Textile dye degradation/removal using nZVI particles.
Dyes
Orange II
Solvent Blue 36 (SB)
Reactive yellow (RY)
Methylene Blue (MLB)
Methyl Orange (MO)
Direct Fast Black G
Orange IV
Malachite Green (MG)
Congo Red (CR)
Remazol Black B 133
Methyl Orange
Methyl Orange (MO)
Methyl Blue (MB)
Methylene Blue (MLB)
Orange II (OR)
Direct Yellow 12
Rosso Zetanyl B-NG
Acid Orange 7
Malachite Green
Methylene Blue
Sunset Yellow (SY)
Acid Blue (AB)
Methyl Orange (MO)
Basic Magenta
Malachite Green
Vat Green 1
Orange II
Eriochrome Blue Black R
Supports/Nano
composites
Integrated
with other
techniques
nZVI
dose
e
e
Clinoptilolite
e
Microwave
radiation
e
0.01 g
0.2 g,
0.3 g
0.1 g
Kaolin
3D Graphene
Zinc
e
e
e
Ultrasonic
irradiation
e
e
Dye
pH
Dye degradation/
Removal efciency
Literatures
6
7
>92% in 30 min
SB: 93.8% in 5 min;
RY: 59.9% in 5 min
MLB: 90.9%, 95.1% in 7h;
MO: 91.0%, 90.5% in 7h
98.9% in 30 min
94.5% in 1h
MG: 90% in 50 min;
CR: 90% in 30 min
80% in 15 min
Volume
Initial
concentration
2 ml
250 ml
25 ml
10 mg/l
50 mg/l,
60 mg/l
100 mg/l
0.5 g
0.2 g/l
0.15 g
1000 ml
50 ml
50 ml
100 mg/l
200 mg/l
500 mg/l
e
7
7
0.3 g/l
1500 ml
200 mg/l
0.6 g/l
0.2 g/l
200 ml
100 ml
200 mg/l
100 mg/l
5
6
e
H2O2
oxidation
e
e
e
e
0.3 g
0.1 g
100 ml
25 ml
40 mg/l
100 mg/l
5.2
4.8
0.5 g/l
e
0.02 g/l
0.5 g
50 ml
8 ml
50 ml
10 ml
140 mg/l
50 mg/l
140 mg/l
100 mg/l
4
6
7.6
7
1 g/l
10 ml
100 mg/l
0.36 g
0.5 g
0.2 g
0.3 g
100 ml
50 ml
100 ml
100 ml
55 g
0.07 g
2 g/l
0.05 g
Biopolymer
Pd and TiO2
e
e
e
Ultrasonic
irradiation
UV light
e
e
H2O2
oxidation
e
UV light
Bentonite
e
e
e
Biochar
Cellulose
e
Bentonite
Persulfate
e
Bamboo
e
Nickelmontmorillonite
Bentonite
e
Rectorite
e
93% in 7 min
MO: 62.5e66.4% in 1h;
MB: 93.1e94.1% in 1h;
MLB: 74e80.9% in 1h;
OR: 82.5e88% in 1h
90.02% in 105.35 s
92.7% in 60 min
95% in 5 min
90.56% in 1h
79.6% in 120 min
SY: 98.9% in 30 min;
AB: 98.8% in 30 min;
MO: 79.9% in 30 min
85% in 12 min
162.62 mg/l
30 mg/l
70 mg/l
100 mg/l
3.03
5
e
3
95.16% in 33 min
67% in 60 s
100% within 10 min
100% in 20 min
1000 ml
30 ml
50 ml
50 ml
175 mg/l
100 mg/l
100 mg/l
50 mg/l
e
6.5
2
3
2 g/l
0.5 g/l
200 ml
100 ml
200 mg/l
100 mg/l
4
3
1000 ml
100 ml
100 mg/l
100 mg/l
6.5
5
1000 ml
100 mg/l
Acid Orange 7
Crystal Violet
Basic Yellow 28
Methylene Blue (MLB)
Methyl Orange (MO)
Acid Yellow 17
Reactive Black 5 (RB)
Reactive Red 198 (RR)
Methyl Orange
Phenol Red (PR)
Acridine Orange (AO)
Methyl Violet (MV)
Azo Carmine (AC)
Light Green (LG)
Orange II
ZnO-perlite
Kaolin
e
e
H2O2
oxidation
0.5 g/l
1 g/l,
0.5 g/l,
1 g/l,
1 g/l,
1 g/l
0.02 g/l
0.01 g/l
Methyl Orange
Acid Blue 113
Reactive Black (RB) 5
Reactive Red (RR) 198
Acid Black 24
e
Resin
e
e
e
e
3 g/l
20 g/l
0.05 g
10 ml
1000 ml
10 ml
25 mg/l
100 mg/l
100 mg/l
6
9
5
97% in 90 min
>97.23% in 7 min
98.2% in 15 min
MLB: > 80% in 5 min;
MO: 80% in 1h
97.8% in 35 min
(RB RR) mix: >70%
in 90 min
79.46% in 10 min
PR: 78.90% in 6h;
AO: 90.72% in 6h;
MV: 62.01% in 6h;
AC: 76.60% in 6h;
LG: 90.13% in 6h
Simultaneous and
sequential process:
39% and 53% in 1h
90% in 24 min
100% in 60 min
100% in 2h
0.3348
g/l
1000 ml
98.18 mg/l
100% in 10 min
Bromothymol Blue
H2O2
oxidationUV light
e
5 ml
500 mg/l
84% in 15 min
Methyl Orange
Orange G
Acid Orange 7
Acid Orange 8
Acid Orange 10
Sunset Yellow
Methyl Orange
Acid Black 24
Acid Black 24
e
Nickel
Resin
e
e
e
0.145
g/l
0.5 g/l
3 g/l
2g
1000 ml
e
50 ml
100 mg/l
150 mg/l
500 mg/l
6
6
6
100% in 10 min
100% in 10 min
70e85% in 6 min
e
e
e
e
500 ml
1000 ml
50 mg/l
100 mg/l
6
6.7
100% in 20 min
98.9% in 30 min
Acid Orange 7
Basic Orange 2
Acid Orange 6
200 ml
2500 mg/l
90% in 2h
(Chen, 2004)
0.3 g/l
0.3348
g/l
0.1 g
(Rakhshaee, 2011)
(Satapanajaru
et al., 2011)
(Chen et al., 2011)
(Prema et al., 2011)
348
Table 3
Evaluation of nZVI particles application on degradation of textile dyes.
Supports/Nano
composites
Integrated nZVI
with other particles
techniques surface area
measured
Degradation Intermediates or
mechanism nal products
discussed or identied
proposed
Presence of inorganic
salts
Green
synthesis
of nZVI
Applied to
textile dyeing
wastewater efciency
Literatures
Orange II
Solvent Blue 36
Reactive yellow
Microwave e
radiation
Methylene Blue
Methyl Orange
Direct Fast Black G
Orange IV
Clinoptilolite
21.8 m2/g
Kaolin
3D Graphene
e
e
e
e
e
e
Malachite Green
Congo Red
Remazol Black B 133
Zinc
73.08 m2/g
Methyl Orange
Biochar
Ultrasonic
irradiation
e
Methyl Orange
Methyl Blue
Methylene Blue
Orange II
Direct Yellow 12
Cellulose
Grape leaf
extract
(Luo et al.,
2015)
1-Diazo-2naphthol, 2Naphthol,
Benzenesulfonate
e
(Mao et al.,
2015)
e
e
e
e
e
e
>99.84% in 1h
e
20.89 m2/g
(Nairat et al.,
2015)
(Jin et al., 2015)
(Wang et al.,
2015a)
(Gautam et al.,
2015)
(Dutta et al.,
2015)
(Han et al.,
2015)
(Wang et al.,
2015b)
Bentonite
57.8% in 1h
81.3% in 1h
28.637 m /g e
e
e
e
e
e
e
e
e
Acid Orange 7
Malachite Green
Persulfate
e
H2O2
oxidation
e
e
Methylene Blue
Bamboo
e
Green tea
extract
e
Sunset Yellow
Acid Blue
Methyl Orange
Basic Magenta
Nickel-montmorillonite e
13.9 m2/g
Malachite Green
Bentonite
Vat Green 1
Orange II
Rectorite
47.8 m /g
Ultrasonic
irradiation
UV light
NaCl, Na2CO3
(Sohrabi et al.,
2014)
(Kerkez et al.,
2014)
(Li et al., 2014)
(Huang et al.,
2014)
(Shaibu et al.,
2014)
(Rahman et al.,
2014)
(Kadu and
Chikate, 2013)
(Abbassi et al.,
2013)
(Arabi et al.,
2013)
(Luo et al.,
2013)
(Khaloo and
Fattahi, 2013)
(Khani et al.,
2013)
Dyes
349
350
Table 3 (continued )
Degradation Intermediates or
mechanism nal products
discussed or identied
proposed
Presence of inorganic
salts
Green
synthesis
of nZVI
Applied to
textile dyeing
wastewater efciency
Literatures
35.16 m2/g
Green tea
extract
e
Biopolymer
H2O2
oxidation
e
Pd and TiO2
UV light
13.97 m2/g
NaCl
100% in 3h
Bentonite
54.04 m2/g
Na2SO4
99.75% in 6h
(Chen et al.,
2012)
(Poursaberi
et al., 2012)
(Shahwan et al.,
2011)
(Rakhshaee,
2011)
(Satapanajaru
et al., 2011)
(Chen et al.,
2011)
(Prema et al.,
2011)
H2O2
oxidation
e
27.9 m2/g
16% in 1h
Supports/Nano
composites
Integrated nZVI
with other particles
techniques surface area
measured
Crystal Violet
Kaolin
Basic Yellow 28
Methylene Blue
Methyl Orange
Acid Yellow 17
Reactive Black 5
Reactive Red 198
Methyl Orange
Phenol Red
Acridine Orange
Methyl Violet
Azo Carmine
Light Green
Orange II
Methyl Orange
29 m /g
2
Resin
25.96 m /g
12.6% in 1h
Reactive Black 5
Reactive Red 198
29.67 m2/g
Acid Black 24
H2O2
oxidationUV light
140.8 m2/g
Bromothymol Blue
Methyl Orange
Na2SO4
Green tea
extract
e
Orange G
Nickel
90 m /g
Aromatic amines
Acid Orange 7
Acid Orange 8
Acid Orange 10
Sunset Yellow
Methyl Orange
Acid Black 24
Acid Black 24
Resin
e
e
e
e
e
140.8 m2/g
e
e
e
e
e
e
e
e
Acid Orange 7
Basic Orange 2
Acid Orange 6
33.5 m2/g
e
53.8% in
10 min
e
(Moon et al.,
2011)
(Shih et al.,
2010)
(Shu et al.,
2010)
(Chompuchan
and
Satapanajaru,
2009)
(Shu et al.,
2009)
(Hoag et al.,
2009)
(Jing et al.,
2009)
(Bokare et al.,
2008)
(Zhao et al.,
2008)
Dyes
et al., 2015b) and persulfate (Li et al., 2014) supported nZVI particles
maintained the dispersion of nZVI particles and protected the
surface from air and increased more contact area for nZVI particles.
However, the reactivity of nZVI particles gets reduced.
The supports like biochar, kaolin, rectorite, and clinoptilolite
instead of degrading the textile dye pollutant, adsorb and transfer it
to the environments to which they come in contact. Hence, it is
highly recommended to degrade textile dyes rather than transferring them under the adsorption process. The addition of supports such as heavy metals, resins, and polymers may introduce
toxic substances to the environment. The green supported nZVI
particles were synthesized using green tea extracts and grape leaf
extracts and its application on textile dye degradation were also
reported (Abbassi et al., 2013; Hoag et al., 2009; Luo et al., 2015;
Shahwan et al., 2011). There is no report available on bench-scale
and pilot-scale studies of nZVI particles application towards
textile dye degradation. The efciency of bare and green supported
nZVI particles on textile dye degradation have to be evaluated. The
application of bare or green supported nZVI particles to the real
textile dyeing wastewater and contaminated sites, needs more
investigations.
4.5.3. Integration with other treatment technique
The efciency of nZVI reactivity may be improved, if the nZVI
technique is integrated with other treatments like microwave radiation, ultrasonic irradiation, H2O2 oxidation, and UV illumination
(Dutta et al., 2015; Kerkez et al., 2014; Khaloo and Fattahi, 2013;
Khani et al., 2013; Mao et al., 2015; Moon et al., 2011;
Satapanajaru et al., 2011; Shahwan et al., 2011; Shu et al., 2009).
Mao et al. (2015) utilized microwave radiation with nZVI particles
to degrade reactive yellow, solvent blue 36 dyes and achieved
59.9%, 93.8% dye decolorization within 5 min respectively; the
corresponding total organic carbon removal was observed as 41.5%,
60.2% in 5 min. However the reaction mechanism between the dye
molecules and nZVI under microwave radiation was not explained
and its still on research. All other integrated studies observed only
dye decolorization. Very few research were reported in integrated
treatment with nZVI technique on textile dye degradation and it is
an emerging area. Recently, the electrochemical technique (Brillas
and Martnez-Huitle, 2015) is receiving extensive attention on
textile dye degradation and this technique can be integrated with
nZVI to achieve complete mineralization of the textile dye organic
compound.
4.5.4. nZVI technique in presence of other pollutant
The application of nZVI technique to textile dyeing wastewater
(Bokare et al., 2008; Chen et al., 2011; Jin et al., 2015; Kerkez et al.,
2014; Satapanajaru et al., 2011) at laboratory scale was reported.
The studies conrmed that the dye degradation using nZVI particles is possible in presence of other inorganic pollutants (Table 3).
The presence of Na2SO4 salts slowed down (Jing et al., 2009) and
reduced the efciency of degradation process because SO2
4 ions
(Chen et al., 2011) compete with dye molecules and occupy the
reactive sites on nZVI surface. Satapanajaru et al. (2011) identied
the pitting corrosion of NaCl on nZVI that improved the degradation rate. Khaloo and Fattahi (2013) observed the degradation efciency maintained even in the presence of Na2CO3 and also NaCl
increased kinetic dye removal rate. The efciency of nZVI on textile
dye degradation in presence of multiple pollutants needs more
research.
4.5.5. Fate of nZVI particles
Abbassi et al. (2013) explored the possibility of regeneration and
reuse of iron nanoparticles even after several cycles of dye pollutant
decolorization. It is adding advantage to the nZVI technique, to have
351
control on the fate of the nanoparticles in the environment. However, more bench-scale and pilot-scale studies are needed to support the investigations. Also, detailed investigations are required to
assess nZVI particles corrosion behavior (Guan et al., 2015;
Noubactep, 2015) in textile dyeing wastewater.
Acknowledgments
The authors would like to thank the faculty and technicians in
the department of Nano Science and Technology, Tamil Nadu
Agricultural University, Coimbatore for SEM and TEM instrumentation facility, utilized to observe the morphology of aged iron
nanoparticles, synthesized for this review.
352
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