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435
15
Multifunctional Silver, Copper and Zero Valent Iron Metallic Nanoparticles for
Wastewater Treatment
S.C.G. Kiruba Daniel1, S. Malathi2, S. Balasubramanian2, M. Sivakumar1
and T. Anitha Sironmani*, 3
1Division of Nanoscience and Technology, Anna University, BIT Campus,
Tiruchirappalli, India2Department of Inorganic Chemistry, Maraimalai Campus, University of Madras,
Chennai, India 3Department of Genetic Engineering, School of Biotechnology, Madurai Kamaraj
University, Madurai, India
AbstractWith the advent of diff erent nanomaterials, nanotechnology plays a key role in
water treatment. Metal nanoparticles, especially silver, copper and zero valent
iron nanoparticles, have the properties of microbe inactivation and heavy metal
removal. In this chapter we will be focusing on the role of hybrid metallic copper,
silver and iron nanoparticles in wastewater treatment due to their ability for anti-
microbial activities and removal of various pollutants. In our previous studies we
have treated wastewater, textile and tannery effl uents using such multifunctional
hybrid nanoparticles. We will also be discussing the existing multifunctional
metal nanoparticle products available for wastewater treatment and new varia-
tions being made by researchers around the world.
Keywords: Silver nanoparticles, copper nanoparticles, zero-valent iron nanopar-
436 Application of Nanotechnology in Water Research
15.1 Introduction
Water is called “the elixir of life.” Wastewater may be industrial effl uents, domestic waste from households or sewage which are deleterious to the environment. Industrial effl uents include tannery and textile dye effl uents which are being released into precious water resources without treatment. Pesticides and fertilizers commonly used in agriculture also pose potential pollution threats. Microbes which include viruses, bacteria, fungi, etc., and heavy metals like lead, mercury, chromium, arsenic, etc., from the above-said effl uents are terribly damaging to the environment on a large scale in both developing and developed countries. Most of these pollutants easily integrate with water resources which are one of the most vulnerable natu-ral resources that can be easily and rapidly polluted. Th ey are one of the most important causes of diseases and disorders in the world. Waterborne diseases are leading causes of mortality and morbidity in developing coun-tries [1]. Target 10 of the UN Millennium Development goals is to reduce by half the proportion of people without sustainable access to safe drinking water by 2015 [1].
Waterborne diseases mainly arising from microbial contamination are a global problem that aff ect all parts of the world. Worldwide, 80% of all sickness and disease results directly or indirectly from a poor water supply and 19% of deaths are due to waterborne infections. In devel-oping countries like India 80,000 people die per day because of poor water supply and sanitation. Around 37.7 million Indians are aff ected by waterborne diseases annually; 1.5 million children are estimated to die of diarrhea alone, and 73 million working days are lost due to water-borne disease each year. Th e resulting economic burden is estimated at $600 million a year. Th e need for a clean and safe water supply is not only important for the rural villages but also in metropolitan cities where there is a lack of adequate infrastructure to purify and treat the water. Wastewater treatment and water purifi cation are done conventionally by reverse osmosis [2, 3], ion exchange [4, 5], cyanide treatment [6], electro-chemical precipitation [6], and adsorption [7–14]. Some of these meth-ods have been pursued from time immemorial. For example, the fi rst recorded use of the ion exchange process is present in the New Testament of the Holy Bible [15].
Metal nanoparticles are being explored for many applications, including biosensors, antimicrobial agents, labels for cells and biomolecules, anti-microbial agents and cancer therapeutics [16–21]. Th ey have wide indus-trial applications in electrocatalysis, chemical sensors, catalysis and optical
Nanoparticles for Wastewater Treatment 437
devices [22–24]. Currently metal nanoparticle-based water treatment tech-nologies are being pursued and products have come out on the market.
15.2 Metal Nanoparticles and Microbial Inactivation
15.2.1 Silver Nanoparticles
Wastewater contains a number of microorganisms leading to the rapid spread of diseases in humans and animals. Silver nanoparticles are known to possess antimicrobial properties against more than 700 microorganisms and are one of the most broad spectrum antimicrobial agents [25]. Silver nanoparticles target the microorganisms in more than three mechanisms; hence the microbes are unable to create mutations to exhibit resistance [25]. Size-dependent activity has been studied and these nanoparticles work effi ciently even at low concentrations [26, 27]. Silver ion binding to bacterial DNA can inhibit a number of transport mechanisms, like suc-cinate and phosphate uptake, and may interfere with the cellular oxidation process and respiratory mechanisms [28]. Silver nanoparticle-embedded alginate [29], polyvinyl alcohol [30], cellulose acetate [31], PLGA, PTBAM and PMMA [32] membranes have been fabricated for membrane-based separation processes. Biocidal polymers are being introduced with silver to have durable antimicrobial activity [32]. Silver nanoparticles are also being used as larvicidal and vermicidal agents. Th ey are being evaluated to form antifouling membranes to be used in ultrafi ltration processes. Th e silver nanoparticles inherent ability to kill microorganisms has been put to use against multidrug-resistant microbes and biofi lm-forming bacterial cells. Biofi lm-forming microbes are not like normal microorganisms since they form a hardened cyst which is diffi cult to act upon. Silver nanoparticle-based polymeric membranes prevent such biofi lm formation. Such anti-fouling membranes are essential in wastewater treatment. Table 15.1 lists the antimicrobial activity exhibited by diff erent nanoparticles and their composites against various infectious pathogens.
15.2.2 Copper Nanoparticles
Copper and its derivatives have been used for centuries as antibacterial and antiviral agents [63]. Copper nanoparticles exhibit antimicrobial activity against both gram-positive and gram-negative bacteria, viz E.coli.
438 Application of Nanotechnology in Water Research
Table 15.1 List of silver, copper and zero-valent iron nanoparticles, its
27 Zero-valent Iron Escherichia coli, Staphylococcus
aureus
[56]
28 Iron oxide Staphylococcus aureus [57]
440 Application of Nanotechnology in Water Research
S.No Nanoparticle/
Nanocomposite
Pathogen Reference
29 Iron oxide Staphylococcus aureus (MTCC
1144), Shigella fl exneri (Lab
isolate), Bacillus lichenifor-
mis (MTCC 7425), Bacillus
brevis (MTCC7404), Vibrio
cholerae (MTCC 3904),
Pseudomonas aeruginosa
(MTCC 1034), Streptococcus
aureus (Labisolate),
Staphylococcus epidermidis
(MTCC 3615), Bacillus
subtilis (MTCC 7164) and
E. coli (MTCC 1089)
[58]
30 Zinc/iron oxide composite Staphylococcus aureus and
Escherichia coli
[59]
31 Cu2O E.coli [60]
32 Soda-lime glass containing
Copper
E. coli [61]
33 Copper Micrococcus luteus,
Staphylococcus aureus,
Escherichia coli, Klebsiella
pneumoniae, and
Pseudomonas aeruginosa,
fungus like Aspergillus
flavus, Aspergillus niger and
Candida albicans.
[62]
Yoon et al. [64] reported the antibacterial eff ects of silver and copper nanoparticles using single representative strains of Escherichia coli and Bacillus subtilis, where copper nanoparticles demonstrated superior anti-bacterial activity compared to the silver nanoparticles. Ruparelia et al. [65] have compared the antibacterial eff ects of silver and copper nanopar-ticles against E.coli, B.subtilis and S.aureus in which copper nanoparticles showed better antimicrobial activity against B.subtilis than silver nanopar-ticles because the copper nanoparticles have greater affi nity towards the surface active groups of B.subtilis, which leads to its better bactericidal eff ect. We have reported that the biosynthesized copper nanoparticles using Dodonea viscosa leaf extract exhibited more effi cient antibacterial activity [66] then earlier studies. Copper nanoparticle polymer composite having antifungal and bacteriostatic properties has been investigated by
Table 15.1 (cont.)
Nanoparticles for Wastewater Treatment 441
Cioffi et al. [67]. Sepiolite–copper nanoparticle composite has been evalu-ated for antibacterial activity by Esteban-Cubillo et al. [68]. Individual and synergistic activities of copper and silver ions on the inactivation of Legionella pnuemophila has been evaluated by Lin et al. [69]. Similarly, Lin et al. [70] have investigated the antimicrobial activity of silver ions against Mycobacterium avium.
15.2.3 Zero-Valent Iron Nanoparticles
Commercial iron granules have been studied for the inactivation and removal of viruses [71]. Th e zero-valent iron nanoparticles in aqueous solution rapidly inactivated gram-negative E.coli, which was not observed in other types of iron compounds [72]. Th e nanoscale zero-valent iron (nZVI) particles have been reported to completely inactivate Pseudomonas fl uoroscens and B.subtilis [73].
15.3 Metal Nanoparticles for Heavy Metal and Dye Removal
Among the metal nanoparticles, zero-valent iron (ZVI) nanoparticles are the most commonly used nanoparticles for heavy metal sequestration due to their high reactivity. Since they can be synthesized easily and are inexpen-sive, ZVI nanoparticles are the most preferable. Zero-valent iron has been used for dechlorination of chlorinated solvents in contaminated groundwa-ter [74, 75], reduction of nitrate to atmospheric N
2 [76–78], immobilization
of numerous inorganic cations and anions [79–81, 75, 82–85], reduction of metallic elements [86], and the reduction of aromatic azo dye compounds [87, 88] and other organics such as pentachlorophenol [89] and haloacetic acids [90]. Similarly, ZVI nanoparticles are being used extensively for per-meable reactive barriers (PRB) for in situ groundwater decontamination. Th e ZVI nanoparticles are reported in the treatment of acid mine water, which is from uranium leaching [91]. Green synthesized ZVI nanoparticles are used as Fenton-like catalyst for the degradation of cationic and anionic dyes [92].
Selvakumar et al. [93] reported the development of silver nanoparticles with yeast cells as adsorbent for arsenate removal. Similarly, Tuan et al. [94] reported the use of silver nanoparticles for the removal of E. coli and arsenate. Th ere is a partial list of heavy metals and dyes treated by Ag, Cu and ZVI nanoparticles in Table 15.2. Silver nanoparticles are also being evaluated for the removal of dyes like methyl orange [95 ,96], methylene
442 Application of Nanotechnology in Water Research
Table 15.2 List of heavy metals and dyes treated by Ag, Cu and ZVI
blue [97], sunset yellow [98], and bromophenol red [99]. Amidoxime fi bers surface coated with silver nanoparticles were evaluated for the pho-todegradation of methyl orange [95]. Silver nanoparticles capped by mer-captosuccinic acid supported on activated alumina have been used for the removal of mercury from water [100]. Silver nanoparticle-based reduction of aromatic–nitro compounds have been investigated by Pradhan et al. [101]. Heavy metal ions removal by naked and monolayer protected silver nanoparticles has been investigated by Bootharaja and Pradeep [102] by X-ray photoelectron spectroscopic studies. Semiconductor AgBr/Ag
5P
3O
10
heterojunctions have been developed by Song et al. [103] for enhanced photocatalytic activity. Copper nanoparticles are generally used to alloy with other metallic elements for removal of heavy metals and degradation of dyes. Pouretedal et al. [104] reported the use of zinc sulfi de doped with copper and other elements for the photodegradation of methylene blue and safranin dye. Copper oxide incorporated alumina has been used to remove As(III) and As(V) from wastewater [105]. Copper oxide nanopar-ticles have been reported for the removal of As(III) and As(V) in a wide pH range [106].
15.4 Multifunctional Hybrid Nanoparticles – Ag, Cu and ZVI
Metal nanoparticles are currently being explored for their multifunctional action to create smart materials with two or more diff erent actions. Earlier nanomaterials were being developed to serve a problem of bacterial inactivation or sensing or heavy metal removal or superhydrophobicity. Recently research has been going on that focuses on making/developing
444 Application of Nanotechnology in Water Research
products utilizing nanotechnology to impart diff erent functions, viz mul-titasking at the same time. For example, Li et al. [120] have developed silver nanoparticle–PVDF membrane which has the dual eff ects of anti-fouling and superhydrophilicity. Earlier, Chauchan et al. [121] from NPL India have reported the use of amine-functionalized gold nanoparticles for single-step sensing and removal of cadmium, cobalt and mercury ions from wastewater. In our study we have reported the use of biosynthesized nanoparticle–membrane composites [31, 30] for better biocompatibility and antimicrobial activity.
Hybrid silver, copper and ZVI nanoparticle clusters were developed and patented [122] to treat diff erent industrial effl uents (tannery, textile, pharmaceutical) and sewage. Th ese hybrid clusters contain less silver and more copper and ZVI to reduce the cost of treatment. Th e hybrid clusters were found to disinfect microorganisms and remove excess salts, chlo-rides, fl uorides, heavy metals and dyes from the effl uent. A large num-ber of textile industries were located in Tirupur, a town in the state of Tamil Nadu, India. Textile effl uents were being released periodically on a daily basis directly into the groundwater table and nearby Noyyal River, thereby polluting them. Drinking water and water for agriculture were severely aff ected, leading to the ban of all dying industries in Tamil Nadu by the Supreme Court of India. A lot of people were rendered jobless due to the closure of textile dying units, and subsequently, textile indus-tries in 2012. Th ese actions have led those of us from Madurai Kamaraj University and Anna University to form teams for developing cost-eff ec-tive effl uent treatment strategies. Our work resulted in the development of hybrid nanoparticle clusters, and the treatment of effl uents was dem-onstrated before the State Pollution Control Board (PCB) and the High Court Bench in Madurai; the nanotreatment method was approved by the PCB and was evaluated by the agriculture department of Tamil Nadu. Th e treatment cost is 150 rupees / 3 US dollars for 1500 liters of effl uent. Currently the ban has been revoked provided there is zero discharge from the industries.
In our study we used the biosynthetic approach for the synthesis of hybrid nanoparticles using readily available plants to make the nanotreat-ment cost-eff ective and biocompatible. Figure 15.1 shows the atomic force microscopy image (3D) of the hybrid nanoparticles. Th e HRTEM images at diff erent scales and SAED pattern of the hybrid nanoparticles are depicted in Figure 15.2. Diff erent dye effl uents were treated and evalu-ated (Figure 15.3). Press reports of the work done in Tirupur and Madurai using nanotreatment are depicted in Figure 15.4.
Nanoparticles for Wastewater Treatment 445
y: 4.0 m
y: 7.0 m
x: 4.0 m
x: 7.0 m
3.9 nm
0.0 nm
65 nm
0 nm
Figure 15.1 Atomic force microscopy images of hybrid Ag, Cu and ZVI nanoparticles
evaluated for wastewater treatment [122].
15.5 Mechanism of Action
Antimicrobial activities of metallic nanoparticles are due to their high aspect ratio (size-to-surface ratio). Th e nanoparticles interfere with cel-lular processes once entering the microbes. Also, the nanoparticles surface adhesion with the microbial cell surface leads to its immobilization [28]. Th e zero-valent iron nanoparticles-based reduction process of pollutants is a redox process in which the metal acts as an electron donor for the reduction of oxidized species. In normal conditions, due to their high reac-tivity, ZVI nanoparticles are exemplary in nanoremediation but are eas-ily oxidized when exposed to air, leading to the formation of iron oxides which are less reactive [35]. Th is can be stopped by adding a small sec-ondary catalyst like silver or copper, which leads to accelerated reduction.
446 Application of Nanotechnology in Water Research
Figure 15.2 High-resolution transmission electron microscopy (HRTEM) images and
selected area electron diff raction (SAED) pattern of Ag, Cu and ZVI nanoparticles as
clusters used for wastewater treatment [122].
Figure 15.3 Photographic images of diff erent dye effl uent being treated by hybrid
nanoparticles: (a) untreated effl uent and (b) treated effl uent.
Nanoparticles for Wastewater Treatment 447
Figure 15.4 Nanotreatment work done in Tirupur and Madurai depicted in diff erent
English and vernacular newspapers in Southern India.
448 Application of Nanotechnology in Water Research
Photo-Fenton-like processes are also being pursued for wastewater treat-ment by ZVI nanoparticles using solar irradiation [118].
Th e sequestration of mercury by silver nanoparticles is by amalgama-tion on the surface of nanoparticles [100]. Th e zero-valent form of heavy metals is easily adsorbed by noble metal nanoparticles, especially silver, gold and copper.
15.6 Concluding Remarks and Future Trends
In this chapter, we have discussed the role of silver, copper and zero-valent iron nanoparticles individually and as hybrids for wastewater treatment. Metallic nanoparticles when used in low concentrations would be very useful in nanoremediation. We have also discussed a case study where nanoparticles were directly put to use as treatment strategy for realtime applications. Th e multifunctionality of such nanoparticles in microbial inactivation and heavy metal removal has been evaluated. We are also developing more such products by carrying out application-oriented research which is the need of the hour. In the future, hybrid nanoparti-cles with many more functionalities will be made available, enhancing the potential of nanotechnology in changing this world.
Acknowledgement
S. Malathi would like to thank ICMR, India, for the Senior Research Fellowship. S.C.G. Kiruba Daniel would like to thank TNSCST for RFRS Fellowship from Tamilnadu Government.
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