Journal Pre-proof

Nanoadsorbents for water and wastewater remediation

Mohamed E.A. El-Sayed

PII: S0048-9697(20)33423-9
DOI: https://doi.org/10.1016/j.scitotenv.2020.139903
Reference: STOTEN 139903

To appear in: Science of the Total Environment

Received date: 8 February 2020

Revised date: 31 May 2020
Accepted date: 31 May 2020

Please cite this article as: M.E.A. El-Sayed, Nanoadsorbents for water and wastewater
remediation, Science of the Total Environment (2020), https://doi.org/10.1016/
j.scitotenv.2020.139903

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Nanoadsorbents for Water and Wastewater Remediation

Mohamed E. A. El-Sayed

Soils, Water, and Environmental Research Institute, Agriculture Research Center, El-Giza,

Egypt

Author for correspondence: Dr. Mohamed El-sayed, Ph.D.; email: eid1592003@yahoo.com

Abstract

Water has a wide-ranging effect on all aspects of human life, such as health and food. However,

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the water has often become polluted by the waste of our industrial, agricultural, and day-to-day

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activities due to the impact of humans. Therefore, there is an urgent need for new technologies to

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remove the contaminants from water/wastewater. Thence, many ways and techniques have been
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developed for water/wastewater remediation. Amongst all the methods of water and wastewater

remediation techniques, the adsorption process has gained tremendous importance as a suitable
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water/wastewater remediation. The application of nanoadsorbent materials is a growing solution

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to solving this environmental problem. The unique physical and chemical properties of

nanoadsorbents enhance their application due to its higher in ranking, status, and quality and
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beneficial in different fields compared to traditional adsorbents.

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Recently, numerous studies reported that the nanosorbent materials have a great and quite

promising effect on water and wastewater treatment such as carbon tube, polymeric, zeolites, and

metal and metal oxides nanosorbents.

Thus, the aim of this review article is to provide new data on the study and improvement in this

specific field and to provide a version of the uses, benefits and restrictions of nanosorbents in

water and wastewater remediation.

Key words: Water, Wastewater, Remediation, Nanoadsorbents, Technique.

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1. Introduction

Water is one of the most plentiful and constituents life on of Earth. It plays a central part in the

world economy where approximately 70% of the fresh water is used in agriculture. Water

pollution is a universal problem that has potential to affect the health of human residents, plants,

trees, and animals (Fereidoun et al., 2007; Yousefi et al., 2018), as well as water scarcity is one

of the main environmental issues facing the world.

Because of the scarcity of fresh water sources, the reuse of wastewater has become a smart

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choice for conserving and increasing available water sources. The reuse of wastewater has

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numerous applications, including irrigation of agricultural soil, aquaculture, manufacturing

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consumptions, recreational and environmental practices, and artificial ground water recharge
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(Asano et al., 2007). Generally, wastewater may be reused for all purposes which fresh water is

applied - if an appropriate treatment is done to return it to water quality suitable for the intended
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application. With limited exceptions, some countries’ water resource are restricted to primarily
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non-potable supplies, or at most to indirect potable uses of treated wastewater. Thus, certain

criteria and parameters such as electrical conductivity (EC), heavy metals content and dissolved
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organic matter concentration after the treatment process should be evaluated before using
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wastewater (Abedi-Koupai et al., 2006).

Nanotechnology allows the development of novel high-tech materials for more efficient water

and wastewater remediation methods, such as membranes, adsorption materials, nanocatalysts,

functionalized surfaces, coatings, and reagents. However, nanosorbent materials are considered

the most suitable water and wastewater remediation methodology because of it's easy to apply

and there is a wide range of adsorbents (Basheer, 2018).

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Recently, nanomaterials have been influencing the water and wastewater treatment process

unprecedented. Nanomaterials show great promise as the best feasible way to treat organic as

well as inorganic contaminants (Jiang et al., 2018) because of their unique properties such as

high surface area and high adsorption capacity. In addition, the interaction between nanosorbent

materials and contaminates may be chemisorption or physisorption depend on the

functionalization of nanomaterials (Rasheed et al., 2019).

Numerous studies have investigated the interaction of inorganic and organic contaminates with

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nanosorbents materials. For examples, Uddin and Baig (2019) used cobalt-oxide nanoparticles to

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remove methyl orange dye, while Dehghani et al (2019) studied the removal of diazinon

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pesticide from water by using carbon nanotubes. In addition, Khan et al, (2016) illustrated the
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effect of using Fe-Cu binary oxides in removing hexavelant chromium from water, whereas

Mandal et al. (2011) showed the role of novel hybrid material in elimination arsenic (III) from
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water. Nevertheless, Kumari et al (2020) explained the removing of fluoride by using calcium
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and zirconium modified acid activated alumina.

Furthermore, some studies have been carried out to investigate the use of nanosorbent materials
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in wastewater remediation applications. As examples of these sorbents, researchers applied

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different nanosorbent materials such as graphene oxide (Nuji´c and Habuda, 2019), metal oxides

(Ming et al., 2012), and carbon (Ihsanullah et al., 2016) for removing heavy metals from

wastewater. Moreover, Gallo-Cordova et al (2019) reported that synthetic superparamagnetic

nanosorbents (iron oxide) after modified by mesoporous silica had a great effect in eliminating

methyl orange and lead from water due to its extremely high surface area.

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Accordingly, the object of this review article is to provide i) new data on the study and

improvement in this specific field, ii) a version of the uses, benefits and restrictions of

nanoadsorbent materials in water and wastewater remediation compared to previous studies.

2. Water

Fresh and safe water is necessary for everyday life and the life cycles of all organisms. It is vital

for health, hygiene and meets the basic requirements of life. Water sources can become

contaminated by different ways. Thence, the process of water remediation can be different from

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location to another due to which technique has been used, but the basic principles are essentially

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the same due to the source of contaminates.

3. Wastewater
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Wastewater is produced in numerous ways, e.g. household/domestic, business and industrial

activities. Surface and ground water may also contribute to the wastewater effluent system and
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increase the total volume of wastewater to process. The source of wastewater plays an important
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role on and its properties and treated process such as domestic wastewater (house and business

wastewater) normally holds contaminants like; vegetable materials, grease and scum detergents,
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and sediment. Otherwise, industrial wastewater may contain; toxic chemicals and metals, organic
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wastes, radioactive elements, great quantities of sediment, high temperature waste or acidic/basic

waste. While wastewater that comes from streets and parking lots through a rainstorm (storm

wastewater) may include; oil, fuel, insecticides, herbicides and residual sediments (Feachem et

al., 1983; Abedi-Koupai et al., 2006).

4. Contaminants types in water/wastewater

Contaminants of water and wastewater have been classified into inorganic, biological and

organic pollutants based on their nature and radix. The types of contaminants are summarized in

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Fig. 1 (Gupta and Ali, 2012). Amongst all the contaminants in water and wastewater, heavy

metals are among the most hazardous because they bioaccumulate. Bioaccumulation is a rise in

the concentration of a chemical in an organism that is greater than its concentration in the

environment. Elements accumulate in living systems once these are taken up and stored earlier

than broken down or excreted (Verma and Dwivedi, 2013).

The term “heavy metals” is commonly used to refer to metals that have a specific density of

more than 5 g/cm3, and having atomic weights between 63.5 and 200.6 (Suwei and Xianglin,

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2001). While these metals are fundamental to maintaining different biochemical and

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physiological tasks in living organisms at low concentrations they become toxic once they

exceed threshold concentration levels.

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Widespread applications of chemicals have increased the load of unwanted pollutants in

available wastewater supplies at all over the world. Thence, this causes decreasing in human and
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environmental health, and economic security. Consequently, the quality of water must be
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enhanced through improving the efficiency of remediation tools (Detmar and Andrea, 2008).

Organic matter is also considered a major water contaminant type category. It is quantified as the
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total organic carbon (TOC). The TOC contains dissolved and particulate matter. Consequently
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TOC influenced by oscillations in suspended solids, that could be fairly noticeable in rivers.

Organic carbon in fresh waters comes from living material and is a component of numerous

waste materials and effluents. Thus, the TOC of the water is considered a useful sign of the

degree of contamination (Chapman and Kimstach, 1996). The main sources of organic pollutants

of water, domestic sewage, regular run-off, materials are resulting from the life cycle of aquatic

plants and animals. The various combinations of organic materials in water, result in the

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production of the off-taste and unpleasant odor of water and inhibiting the remediation of water

for manufacturing and domestic usage (Middleton and Rosen, 1956).

5. General techniques for remediation contamination from water/wastewater

Numerous procedures of water and wastewater purification can be used to produce clean and

safe water (Fig. 2). Today, different processes for water and wastewater purification are used in

public treatment as follows:

I- Ion exchange

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II- Chemical precipitation

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III- Reverse osmosis

IV- Electrolysis
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V- Coagulation/Flocculation

VI- Ultrafilteration
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VII- Adsorption
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The choice of which technique to use depends upon the type and the concentration of both

supportive materials available and the sorbent employed, as well as their costs.
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I- Ion exchange
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Ion exchange is a reversible chemical reaction in which an ion in aqueous solution is replaced a

similarly-charged ion that is linked to an “exchange site” on an immobile solid particle. Some of

these particles are naturally occurring, such as zeolites and clay minerals while some of them are

synthetically produced as inorganic and organic resins. Ion exchange procedures have been

effectively applied in the elimination of numerous heavy metal cations in water and wastewater.

Some researchers have found that the removal of some heavy metals such as lead are challenging

because of the competition between the resin’s active ion exchange sites and those sites which

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occur naturally such as aluminosilicate colloids. These studies demonstrated the effectiveness for

the elimination of dissolved lead and cadmium during 18 h in batch containers, with greater

elimination efficiencies (>95%) in the acidic pH range (Martin and Griswold, 2009).

II. Chemical precipitation

This procedure depends on the formation of a solid material inside the water through a chemical

reaction. The solid created is pointed as a precipitate and that can compress by a centrifuge as a

pellet. The liquid residual overhead the solid is called the supernate or supernatant. Chemical

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precipitation techniques are commonly applied to eliminate heavy metal ions from water and

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wastewater due to its low cost and simplicity.

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Heavy metal elimination by chemical precipitation techniques are generally comprised of the
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following steps:

1-The addition of a chemical material (e.g. magnesium hydroxide, soda ash) precipitates the
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heavy metal ions as hydroxides or carbonates.

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2- Eliminate the precipitated heavy metal produced in the first stage by gravity separation

approaches or other separation techniques appropriate to the scale of the water being treated.
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Many techniques such as magnetic separation, dissolved air flotation, vortex separation or any
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other technique which uses field powers fairly than filtration to eradicate particles from the water

and wastewater can be used.

3- The remaining heavy metals in solution can be precipitated after stages (1) and (2) by adding

organic sulfides, inorganic sulfides or other chemicals that can effectively precipitate low

concentrations of heavy metal ions.

4- Precipitated heavy metals in stage (3) can be removed by any separation techniques.

III. Reverse osmosis

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Reverse osmosis is a technique based on a molecular filter that eliminates more than 99% of all

soluble salts in a water feedstock. The solute concentrations on each side of the membrane are

balanced by the mobility of solvent and this led to generate a pressure called an "osmotic

gradient". Using an external pressure to reverse the natural flow of the perspicuous solvent, this

called reverse osmosis (Ghabris et al., 1989). In this method, the water or wastewater passes

through a membrane, but the dissolved and particulate substances are too large relative to the

membrane pore diameters and remain behind. This method is extremely effective for the

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elimination all ionic types from water and wastewater solution. A significant advantage of the

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technique is the concentrated by-product solution (referred to as the retentate) which makes the

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final recapture of metals more cost effective. In addition, a significant advantage of this process
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is the capacity to decrease the concentration of other ionic pollutants, as well as soluble organic

compounds, more than other traditional water purification technologies. Furthermore, this
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process has been used in heavy metal elimination in small scales as well as large scales.
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However, the membranes are comparatively expensive both to procure and operate. And the high

pressures required to operate a system lead to that this method became costly and sensitive to
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operating conditions.
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IV. Electrolysis

This process depends on the application of a direct electric current through an ionic material that

is dissolved in an appropriate solvent resulting in chemical reactions at the electrodes that lead to

separation of the materials.

Some definition and terms important in the electrolysis process:

- Electrolyte: a material having free ions that are the transporters of electrical current in the

electrolyte. In soil salt case, the ions aren’t moving, the electrolysis cannot occur.

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- Direct current (DC) supply: affords the energy needed to produce or release the ions in the

electrolyte.

- Electrodes: are the conductors affording the physical border among the electrical circuit

providing the energy and the electrolyte.

Many types of electrodes can be widely used such as metallic, graphite and semiconductor

materials. The suitable electrode choice balances the chemical reactivity between the electrode

and the electrolyte as well as the cost of production (Ghabris et al., 1989).

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V. Coagulation / Flocculation

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This process is an important tool for water / wastewater remediation and purification (El-sayed et

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al., 2018). The coagulation process is a chemical reaction that happens after adding a suitable
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chemical material (a coagulant) to the water. The coagulant substance binds the contaminant

substances in the water and wastewater and forming small aggregates called “flocs”. The flocs
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are continuing to interact with the coagulant. The flocculation process is a slow and gentle
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mixing of the water to push the flocs to increase its size that causes precipitation of the

contamination as the floc particles grow. Lately, some researchers used an electrocoagulation
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process for treating aqueous solutions containing heavy metal ions such as copper ions (Mateen
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et al., 2019).

The disadvantage of this method is the cost of added reagents and formation of a large amount of

sludge whose disposal is also considered a major environmental issue.

VI. Ultrafiltration

This process is a separation technique that uses membranes with pore sizes that range from 0.1 to

0.001 micron. Usually, ultrafiltration eliminates high molecular-weight materials, colloidal

substances, and all polymeric molecule types. Like reverse osmosis, it is defined as a pressure-

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driven treatment method where the water and low molecular weight molecules pass through the

membrane while macromolecules and colloid particles remain behind the membrane. The main

separation mechanism is size elimination; however the efficiency of this purification method is

also affected by the surface charge and the surface charteristics of the particles and membranes.

The generation of sludge is considered the main problem associates with this method (Łaskawiec

et al., 2018).

Recently, some nanomaterials have been used as a membrane such as nanocarbon tube.

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Ihsanullah (2019) discussed a broad overview of synthesis of CNT membranes and its potential

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application in water purification.

VII. Adsorption
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Adsorption is a surface phenomenon and widely used mechanism for the elimination of all types
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of pollutants. The adsorption process depends on the interaction between an adsorbable solute
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and a solid adsorbent which has a highly porous surface structure. The attractive forces between
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the solute and the adsorbent cause the solute molecules to be concentrated on the adsorbent

surface. The adsorption process leads to increasing the concentration of the adsorbate on the
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adsorbent surface.
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Amongst all the above methods, adsorption considers a very appropriate technique for water and

wastewater purification, due to its high efficacy, cost-effectiveness, versatility and easy control

(Wang et al., 2005; Yadanaparthi et al., 2009). Furthermore, in many cases the adsorbent is

cheap and does not need a pre-treatment step before its application. Moreover, unlike other

treatment technologies, adsorption does not produce any toxic intermediate(s) or by-product (s)

of particularly complex organic contaminants. Consequently, adsorption process is the best and

final choice that has been commonly applied by the world ecologists for the removal of

dangerous and poisonous inorganic and organic contaminants. Most of the above techniques are

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time consuming and use expensive equipment, simply to create secondary contaminants and

continue chemical replacement. Hence, more studies carried out for finding efficient and low

cost techniques for water/wastewater remediation.

6. Types of adsorption

The type of adsorption method is classified by the nature of the surface attachment which can be

physical, chemical or exchange adsorption (Wong et al., 1997):

1. Physical adsorption (Physisorption) is caused by Vander Waals forces and is the easiest to

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separate because these forces are weak in nature. It does not include sharing or transfer of

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electrons and it is essentially reversible.

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2. Chemical adsorption (Chemisorption) takes place through chemical bonding between
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adsorbate and adsorbent. Chemisorption happens only as a monolayer. In addition, materials

that chemisorbed on solid surface are difficult to remove. It is principally irreversible. Under
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favorable conditions, both procedures could happen simultaneously or alternately.

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3. Exchange adsorption is caused by the charge attraction between adsorbate and the surface.

Among all of the above methods, adsorption is considered a very appropriate technique for water
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and wastewater purification due to its high efficacy, cost-effectiveness, versatility, and easy
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control (Wang et al., 2005; Yadanaparthi et al., 2009). In many cases the adsorbent is cheap and

does not need a pre-treatment step before its application. Consequently, the adsorption process

has been the often the best choice for water treatment that and commonly applied by the world

ecologists for the removal of dangerous and poisonous inorganic and organic contaminants.

However, like other treatment technologies, adsorption does produce a material that can pose

challenges in responsibly disposing of.

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All of these techniques discussed here are time consuming and use expensive equipment. While

they purify the water they create materials that must be disposed of and require continual

chemical inputs. These realizations have resulted in many more studies to find efficient and low

cost techniques for wastewater remediation that minimize these negative consequences.

7. Nanoadsorbents for Water/ Wastewater Remediation

The nature of an adsorbent is a very important factor in adsorption process where the adsorbent

determines the efficiency, versatility and economics of the adsorption method. Although

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traditional sorbents, such as activated carbons (Kobya et al., 2005), clay minerals

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(Oubagaranadin and Murthy, 2009), chelating materials (Sun et al., 2006), and chitosan/natural

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zeolites (Wang et al., 2009) can eliminate heavy metal cations from water / wastewater, however
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some properties, like the low sorption capacities, can decrease the efficiency in an application. In

the last ten years nanomaterials, substances with a particle size range between 1 nm to 100 nm,
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have been used to avoid the deficiencies of traditional sorbents (Stone et al., 2010).
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7.1 Nanosorbent material properties

Nanomaterials are effective adsorbents because they possess a very large surface area, multiple
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sorption sites, low temperature modification, short intraparticle diffusion distance, tunable pore
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size and surface chemistry (Khin et al., 2012). The shape and the morphology of nanosorbent

materials also plays very important role in its properties and efficiency. The diverse

morphologies are designed as a result of the delicate balance between the energy from the polar

charges, surface area, and elastic deformation. Gatoo et al. 2014 reported that the morphology

beside to surface area and composition effected on the behavior of nanosrorbent materials

towards toxic materials. These chemical and physical characteristics led to their increasing

application as a sorbents compared to traditional sorbents (El-sayed et al., 2019).

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Furthermore, physical, material, and chemical properties were highly affected by Innate Surface

Properties, intrinsic compositions, apparent sizes, and external Functionalization of nanosorbent

materials as reported by Khajeh et al (2013). Wheresoever, the nature and distribution of active

sites on the surface and types and number of function groups of nanosorbents materials lead to

explain the behavior and properties of nanosorbents materials such as location of the most atoms

in the surface, high surface area, high chemical activity, high adsorptive capacity, and high

surface binding energy.

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7.2 Synthesis of nanosorbent materials

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Synthesis of nanosorbent materials depend on two main methods; bottom-up processes and top-

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down processes. The top-down process uses a traditional approach for synthesis of nonabsorbent
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materials and then reduces the particle size through erosion and different approaches such as

mechanical alloying, reactive milling, and high-energy ball milling. The bottom-up process is the
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most modern process. It depends on the building of a substance from the bottom: atom by atom,
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or molecule by molecule like molecular self-assembly, sol–gel, and chemical/physical vapor

deposition. Each method has its advantages and disadvantages. The main problem associated
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with the top-down process is damage of crystallographic and surface structure during particle
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size reduction. In any case of the deficiencies created by top-down process, this process will still

play an important role in the synthesis of nano particle. In bottom-up processes, the two main

problems are that chemical purification is required and large scale production is difficult. Despite

this, the bottom-up process is considered the preferred technology at the present because it can

produce materials that have specific properties tailored to the remediation need depending on the

route chosen to fabricate them (Tulinski and Jurczyk, 2017). Examples of each process are

illustrated in Table 1 with some examples of nanomaterial synthesis strategies.

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Moreover, chemical and physical ways for synthesis nanosorbent materials often synthesis

nanosorbent materials with a definite shape and size, though, these methods verified to be unsafe

to the environment due to the application of poisonous chemical agents and the high

temperatures employed during the synthesis processes (El-Gendy and Omran, 2019). Biological

synthetic methods of nanosrorbent materials with a definite shape and size need more

examination, as the biological synthesis of nanosorbent materials is performed via biological

entities such as bacteria (Ahmed et al., 2017), fungi (Ballottin et al., 2017), algae (Pugazhendhia

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et al., 2018), and plant extracts (Appapalam and Panchamoorthy, 2017). The microbial synthesis

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of nanomaterials can be performed via extracellular and intracellular mechanisms as illustrated in

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the biological entities are proving to be high secretors of proteins and enzymes that are mainly
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responsible for the reduction of metal ions and controlling of nanosorbent materials. Biogenic

synthesis of nanomaterials is a green method and environmental friendly, due to that no harmful
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chemicals are needed during this process. Furthermore, the synthesis method usually carried out
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at normal condition such as pressure and temperature. For this reason, numerous researchers are

focusing their attention towards the biological synthesis of nanomaterials rather than using the
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chemical or physical methods (El-Gendy and Omran, 2019).

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8. Nanosorbent materials classification and applications

Several forms of nanomaterials like nanowires, nanotubes, particles, and quantum dots have been

produced and applied in different applications (Lubick and Betts, 2008). The purification of

water and wastewater carried out using modern synthetic nanosorbent materials that have unique

properties and high efficiency for removing pollutants from water and wastewater was studied by

Gupta et al. (2015).

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Nanomaterials have been applied to eliminating contaminants from water and wastewater

(Sadegh et al., 2017). Numerous studies have investigated the influence of using nanosorbent

materials for water and wastewater remediation, and Wang et al. (2012) applied nanosorbent

materials for removing heavy metal cations and dyes from water and wastewater.

Recently, several novel nanosorbent materials have been modified for improving the adequacy

and adsorption capacities for eradicating pollutants from water and wastewater such as silica-

shell coating onto Fe3O4 particles (Gallo-Cordova et al. 2019). Furthermore, Naushad et al.

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(2017) used Nickel ferrite bearing nitrogen-doped mesoporous carbon for removing highly toxic

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heavy metals from wastewater, while Dehghani et al. (2019) used novel adsorbents (multi-

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walled carbon nanotubes and γ-alumina) to remove cobalt (II) from aqueous solution as example
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for heavy metal cations. On the other hand, Adhikari et al. (2017) investigated the mechanism of

dye adsorption on nanocrystalline WO3 as metal oxide. Moreover, some review articles
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summarized using nanotechnology in water and wastewater treatment (Khan et al. 2019) and
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Engineered nanomaterials for removing heavy metals (Jawed et al. 2020). At the same time,

Bolade et al. (2019) investigated the role of green synthesis of iron-based nanomaterials in
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environmental remediation.
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Moreover, numerous studies carried out on the effect of nanoadsorbent materials on removing

pharmaceutical compounds from water and wastewater. Yoon et al. (2017) reported that iron

oxide nanoparticles can be used in removing carbamazepine and diatrizoate from aqueous

solution, as well as D’Cruz et al. (2020) investigated the rapid removing of promazine from

wastewater by using magnetic AC-Fe3O4 nanocomposite.

The criteria for ideal nanosorbent materials for water and wastewater remediation purposes were

described by Gupta et al. (2016):

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1. The nanosorbent materials should be non-toxic.

2. The nanosorbent materials have high sorption capacities and high accuracy for

removing the low concentration of contaminants.

3. The surface of the nanosorbent materials should be easily reactivated.

Various improvements and development have been addressed to eliminate contaminants from

water and wastewater. Thence, the present studies generally focus on one or more of these

categories of nanosorbents:

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 Carbon-based nanosorbents such as carbon nanotubes (CNTs)

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 Polymeric nanoadsorbents

 Zeolites.
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 Metal-based nanoadsorbents

 Other nanosorbents
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8.1 Carbon nanotubes

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Carbon nanotubes (CNTs) are carbon nano-structures that have a cylindrical form. According to

the synthesis process, CNTs are classified to single-walled or multi-walled nanotubes. CNTs
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have a high surface area, high adsorption sites, and tunable surface chemistry. The hydrophobic
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surface properties of CNTs cause stabilization by particle aggregation in aqueous solution to

obviate the decreases in surface activity. The CNTs can be applied for pollutant remediation as

well as determine the pre-concentrate and reveal pollutants. The interaction between CNTs and

metal cations carried out by electrostatic attraction and chemical bonding (Rao et al., 2008).

Anjum et al. (2019) explained the mechanism of oil contaminates from wastewater by using

carbon nanotubes (Fig. 3)

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The antimicrobial properties of CNTs have also been observed by removal of bacterial cell walls

as a result of oxidative stress. While chemical oxidation happens, no-toxic by-products are

formed, which represented an additional advantage over classic disinfection procedures like

chlorination (Liu et al., 2013). The CNTs can be simply renewed through suitable modifications

of the operating settings, such as pH conditions.

Hashim et al. (2012) created a synthetic sponge from pure CNTs that could be used for oil

remediation. By the addition of boron the sponge displayed a significant capacity to absorb oil

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from water. The sponge retained the oil for later recovery and could be reused.

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The conventional techniques of desalination are energy-consuming and technically challenging.

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Techniques that are based on the adsorption are simple and easy to apply for water and
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wastewater remediation; however the ability to separate salts is still limited. Plasma-modified

ultra-long CNTs were developed to have highly specific adsorption capacity for salt removal as
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compared to traditional carbon-based adsorbents that used in remediation systems. The ultra-long
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CNTs also had a significant capacity for removing the organic and inorganic pollutants (Yan et

al., 2013; Gehrke et al., 2015; Ihsanullah, 2019).

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The CNTs have significant advantages over activated carbon; however, using it on an industrial
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scale to treat a large amount of wastewater treatment is not cost effective at this time due to high

manufacturing costs while, on the short term the CNTs application will be more competitive

(Cong et al., 2013; Qu et al., 2013).

8.2 Polymeric nanoadsorbents

Polymeric adsorbents have been considered as a replacement for conventional adsorbents as a

result of their high surface area, adaptable surface chemistry, ideal mechanical rigidity, pore size

distribution, and practicable development under some conditions (Zare et al., 2018). Polymeric

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nanoadsorbents are composite materials that are classified into four major types based on their

composition: graphene/polymer nanocomposites, carbon nanotube/polymer nanocomposites,

metal and metal oxide/polymer nanocomposites, and dendrimer-based nanocomposite (Rani and

Bushra, 2018).

Dendrimers, which has repetitively branched molecules, consider a perfect example for

polymeric nanoadsorbents and their impact on removing organic and inorganic contaminates.

Heavy metals can be adsorbed through the external branches, while organic materials can be

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adsorbed through the internal hydrophobic fractions. Diallo et al. (2005) combined dendrimers

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with ultrafiltration technique to eliminate copper from the water, which led to removing all

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copper cations. The shift of pH plays an important role in reactivity of the nanoadsorbent
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materials. Because of the complex multistage synthesis of dendrimers, only few recent

companies produce commercial dendrimers.

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Some researchers enhanced the efficiency of dendrimers by synthesizing a combined compound

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like chitosan-dendrimer nanostructure to increasing its capacity in the eliminating of some

anionic compounds from wastewater such as dyes (Sadeghi-Kiakhani et al., 2013). They are
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biodegradable, biocompatible, and non-toxic materials that have a great dye removal efficiencies,
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approximately 99%.

8.3 Zeolites

Zeolites are aluminosilicate minerals with a surface structure containing a large number of

electrostatic holes that are occupied by cations and water molecules. The cations and water

molecules have a significant choice of movement, allowing the ion exchange and reversible

dehydration (Fig. 4). The normal size of zeolite is a micro scale; however nano zeolite can be

produced within the range 10 – 500 nm. The zeolite in nano scale has greater adsorption

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capacity, higher density of adsorption sites, and higher surface area (400 -1000 m2/g) than

traditional zeolite (Machado and Bergmann, 2011). Thus, nano-zeolite has great affinity and

efficiently towards pollutants.

Zeolite used in conjunction with silver has been known since 1980. The zeolite structure has a

porous form where silver ions could be integrated. Egger et al. (2009) studied and compared the

behavior of different materials containing nanosilver, including zeolites, against microbes. They

reported that the silver attacks microbes and inhibits their growth. A minor quantity of silver

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cations is lost from the metal surface once the material interacts with solutions (Nagy et al.

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2011). Moreover, due to the Water Research Commission Report, zeolites considered a source of

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silver ions, consequently zeolites can act as a disinfectant due to their adsorbent to silver
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nanoparticles (Azizi-Lalabadi et al., 2019). Some companies produced a compound made from

zeolites having silver ions that display antibacterial properties. Tiwari et al. (2008) prepared
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nano-zeolites by laser-induced fragmentation from zeolite in microparticles scale and applied

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nanozeolites in sequencing batch reactors for water and wastewater remediation.

Both CNTs and nanometals as nanoadsorbents are extremely effective on the removal of
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inorganic contaminates like cadmium, lead, and arsenic. The main advantage of nanometals and
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zeolites is their low cost and compatibility with the current water remediation protocols since

nanometals and zeolites may be applied in the form of pellets and beads as fixed adsorbents.

While manufacture of CNTs is quite expensive and extra procedural devices, such as, membrane

filtration plants must be used in conjunction with them to be certain that no nanoparticles settle

out in the aqueous medium. A main CNT benefit with regard to micro-contaminate removal is its

potent adsorption capacity for polar organic substances. CNTs are highly cost-competitive

compared to broad-spectrum adsorbents such as activated carbon. Future applications wil

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concentrate on how CNTs can be applied in small quantities for highly specific adsorption

processes.

Although nanometals and CNTs are manufactured accessible for various implementations, while

polymeric nanoadsorbents are still continuing access to market. According to the method

efficacy, polymeric nanoadsorbents are highly progressive substances letting to eliminate

inorganic and organic pollutants in the same step. The major restriction to these novel

nanosorbent materials is the high manufacturing cost and the technical method that can be used

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to enhance the polymeric dendrimers.

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In regard to ecotoxicity of nanosorbent materials such as zeolites, nanometals, and CNTs,

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nanosorbent materials are categorized as nontoxic materials due to their origin and
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characterizations. However, the size and shape of the nanoadsorbents effect on their potential

toxicity, likewise chemical stabilizers and surface adaptations. The ecotoxicity of each novel
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modification of a known nanomaterials have to re-evaluate, however, the assessments of

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nanoadsorbents are not common in regard to their toxic potential.

8.4 Nanometals and nanometal oxides

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Nano-metal oxides are an effective replacement for activated carbon and consider as more active
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adsorbents for removing of heavy metals and radioactive elements. Furthermore, due to their

high surface area, nanometal oxides have a small intraparticle diffusion distance and can be

compressed without decreasing their surface area. Several nanometal oxides are super

paramagnetic, for example nanomagnetite, which allows them to be easily separated and

recovered through a low-gradient magnetic field. Nanoscale metal oxides may be applied to

adsorptive media filters and slurry reactors (Qu et al., 2013). As another example for nanometal

oxides, nano iron hydroxide [α-FeO (OH)] which is a strong abrasion-resistant adsorbent with a

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large surface area that effectively removes arsenic from water or wastewater (Aredes et al.,

2012). Nanometal oxides and nanometals can also be compressed into porous pellets or applied

in powder form to be easy use in existing treatment practices (Gehrke et al., 2015).

Some nanometals and nanometal oxides such as nanosilver and nano-titanium dioxide, magnetic

nanoparticles, and nano-zero valent iron will be discussed briefly to explain their roles in water

and wastewater remediation.

 Nanosilver and nano-titanium dioxide

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Since 1800s, nanosilver was applied during the photo development procedure. While, the United

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States Environmental Protection Agency used it as a swimming pool algaecide in 1954 and in

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drinking water in 1970. Although, nanosilver has broad-spectrum antimicrobial activity it also
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has a harmful effect on humans. Moreover, it has been previously used as a disinfectant and anti-

biofouling agent on surfaces in water or wastewater (Nowack et al., 2011). Kim et al., (2012)
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showed that the advantages of nano-titanium dioxide (TiO2) are: has a high chemical stability,
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has a strong effect as a disinfectant substance, has strong efficacy in removing pollutants,

causing low human toxicity, and consider less expensive comparing to other materials. Their
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supplementary data illustrated that nano-titanium dioxide has highly effective as a photocatalyst.
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Nano-TiO2 has more benefits than nanosilver in stable, persistent material coverings, because

TiO2 as a catalytic agent is still stable through the organic and micro-organisms loosestrife.

Nanosilver antimicrobial properties result refers from the uninterrupted discharge of silver ions.

It destroys bacteria without extra energy-consuming device requirement. Thus, nanosilver is a

promising disinfectant can be used for water remediation process (Quang et al., 2013; Jo et al.,

2018; Pooyamanesh et al., 2019).

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Nano-titanium dioxide has many advantages as a photocatalys such as its broad-spectrum impact

on the chemical degradation of the bulk of organic pollutants and micro-organisms as well as its

low price, availability, and inertness. Thus, TiO2 will be an ideal, robust, durable and influential

nanomaterial for water and wastewater remediation methods in both small and large scales

handling design without the formation of chemical by-product. Though, the effectiveness of

specific ultraviolet-visible photocatalytic of TiO2 was comparatively low related to the similar

oxidation methods such as ozonation. Moreover, the effectiveness of nano-TiO2 can be enhanced

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by the visible light successfully, photocatalysis will convert to be the major talented water and

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wastewater and wastewater remediation technologies refer to its flexible and various applications

and simply expendable.

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Additional nanosilver advantages are its low toxicity, high availability, and well established

antibacterial impact.
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 Magnetic nanoparticles
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Magnetite (Fe3O4) has been used to remove groundwater contaminants such as arsenic (Gupta et

al., 2010). The traditionally utilized “pump-and-treat” process for the handling of ground water
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where after pumping up the groundwater to the surface, the remediation has been done via using
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activated carbon. Thus, the operating hours and the costs of environmental cleanup may be

reduced significantly through the applying of this process.

An additional advantage to using magnetic nanoparticles that interact directly with the

contaminants is that a magnetic field can be used to remove loaded particles. Likewise, through

ground water purification, the magnetic recaptures produced a perfect nanoparticles substance to

raise the osmotic pressure of the sol that utilized in the forward osmosis where the water draws

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from the less osmotic pressure to another solution has a greater osmotic pressure by the osmotic

gradient (Kim et al., 2011).

Namdeo (2017) reported the effect of using nano magnetite in water purification and illustrated

the synthesis, surface fictionalization, application and regeneration of magnetite nanoparticles in

the extraction of toxic metals (Fig. 5). Whilst, Azadi et al. (2018) explicated the green synthesis

of magnetite to be more environmentally friendly and explored the its application in wastewater

desalination.

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 Nano-zero valent iron

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Nano-zero valent iron (N-ZVI) was applied for the treatment of groundwater from pollutants like

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chlorinated hydrocarbon solutions and per-chlorates. The N-ZVI suspension could be directly
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added to the groundwater, permitting in situ remediation of the system. Because of its high

specific surface, area N-ZVI is more interactive than classical granular iron; and due to its high
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reactivity, the N-ZVI lifetime is quite low. Consequently, surface adaptations are necessary to
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achieve the stability of these nanomaterials (Homhoul et al. 2011; Matlochova et al., 2014).

Magnetic nanoparticles generally have more efficiency than N-ZVI for ground water purification
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and the potential toxicity of nanometal oxides is quite low.

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The main significant properties, applications, and pioneering attitudes comprising some

nanomaterials are summarized in Table 12.2. The nanometals and nanometal oxides can be

intensely applied in the water or wastewater remediation due to the stability and efficiency of

nanometals and nanometal oxides (Gehrke et al., 2015).

8.5 Other nanosorbents

Some nanosorbents materials may belong to different categorise such as zeolites and nanometal

oxides, which have great efficiency toward the inorganic and organic contaminants such as nano-

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hydroxyapatite, and nano-clay minerals. These other nanosorbent materials also can be applied in

water/wastewater remediation. The main advances of nano-hydroxyapatite and nano-clay

mineral materials represent in the low price and the high surface area of these materials (El-

sayed, 2019).

Nano-hydroxyapatite is a natural mineral with a chemical formula of Ca10 (PO4)6 (OH)2. The

applications of nano-hydroxyapatite are due to its characteristics, like inner charge and

hydrophilic behavior (Tanaka et al., 2005). Many studies have focused on the increasing nano-

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hydroxyapatite capacity to react with heavy metals (Mobasherpour et al., 2011) and organic

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pollutants (Lyczko et al., 2014). Elsayed et al. (2018) found that nano-hydroxyapatite can be

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applied to treat wastewater and it may be modified by another substance like humic acid to

enhance its efficiency in these applications. A nano-hydroxyapatite – humic acid complex has a
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greater affinity than nano-hydroxyapatite in removing all contaminates from wastewater.
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Yang et al. (2019) reported the use of several nanosorbent materials, some fabricated
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nanomaterials and novel nanosorbent materials such as metal-oxide and carbon-based

nanomaterials, zero-valent metal, and nanocomposites in eliminating wastewater heavy metals.

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Each nonabsorbent material was highly different in its efficiency, long term application, and
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advantages over another nanomaterial. They concluded that how nanosorbentds materials can be

applied in future to obtain a highly potential effect in wastewater treatment should be further

studied.

Prathna et al. (2018) showed that nanosorbent materials exhibit higher efficiency and faster rates

in the removal of pollutants from contaminated water when compared with traditional

adsorbents. For example, most of the low cost adsorbents are microparticles and require

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considerable time to achieve maximum removal of pollutants in view of their small surface

contact area.

Furthermore, Gao et al. (2019) explained the ability of use nano magnetic Fe3O4 water and

wastewater treatment. The efficiency of nano magnetic Fe3O4 enhanced after the modification

process for nano magnetic Fe3O4 by some materials such as inorganic and organic small

molecules, or organic polymers in water and wastewater treatment. This refers to formation

more active functional groups on surfaces. These functional groups result in nano magnetic

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Fe3O4 possessing weak coagulation and high stability, and exhibiting excellent performance in

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wastewater treatment.

9. The disadvantage of nanosorbent materials

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Nanosorbent materials have an important role in explaining ecological issues like the purification

of wastewater received a great interest due to having remarkable physiochemical properties.

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However, some of disadvantage can be noted through using nanosorbent materials in water and
na

wastewater (Yaqoob et al., 2020). The two main disadvantages are: 1) the possible toxicity of

the remaining nanomaterial in the water (Zhu et al., 2019), 2) using huge materials of
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nanomaterials in the treatment process to achieve a reasonable treatment time which causes that
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some potential activity is not used. Some studies have tried to separate powder materials from

the water treatment using e.g. membranes, but this adds more cost to the process. Thence, future

studies will be focusing on the advances knowledge and improving the usage of nanoadsorbents

materials.

Conclusion and future perspectives

There are several water/wastewater remediation techniques, but adsorption is the most important,

efficient and widely-used technique. Adsorption can eliminate or reduce all pollutant classes

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(organic and inorganic) without producing by-product (s) or poisonous intermediates. Thus, it

has a wider applicability in removing pollutants from a water source. Recently, nanoadsobent

materials have been used due to their unique properties in the adsorption process. Where, the

nanoadsorbent’s properties enhance its application and became greater and more beneficial in

several fields than older adsorbents. Thus, nanoadsorbent materials consider a next-generation

adsorbents and have several practices and perform very well in environmental purification and

control of pollutants from water and wastewater. Numerous naoadsorbent classes can be used,

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like nanometals and nanometal oxides, zeolites, and polymeric nanoadsorbents, as a result of

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their unique properties like high surface area, stability and microbial effect. Future and novel

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studies can be done with these materials such as chemical stabilization and surface adaptations to
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improve their application in water and wastewater remediation as well as more investigate the

disadvantages of nanoadsorbent materials.

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Conflict of Interest:
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The authors declare that they have no conflict of interest.

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Water and
wastewater
o f
pollutants

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Inorganic Organic

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pollutants pollutants pollutants

Acids and
P r
Metals Anions
alkalis
Pesticides

a l Dyes Phenols Viruses Bacteria Protozon

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Fig. 1. Water and wastewater contaminant types classified by their chemical nature (Gupta and Ali, 2013).

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wastewater
treatment
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Fig. 2. Water / wastewater treatment techniques (Usmani et al., 2017).

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Fig. 3. Proposed schematic diagram of van der Waal interactions between oxidized CNT and the
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benzene ring (Anjum et al., 2019).

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Fig. 4. Nanosbents structures for adsorption processes: (A) dendrimer, (B) zeolite and (C) carbon
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nanotube.
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Fig. 5. Schematic diagram shows the synthesis, surface fictionalization, application and regeneration of

magnetite nanoparticles in the extraction of toxic metals (Namdeo, 2017).

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Table 1. Methods of nanomaterial synthesis and preparation

Physical methods Biological methods Chemical methods

High Energy Ball Milling Microorganisms Assisted Sol-Gel synthesis

Such as: carbon nanoparticles, Biogenesis Such as: Metal oxide, Ceramic,

Metals and metals Oxide Such as: Metal, Metal oxide, and Metal Aluminates

nanoparticles Magnetic and Quantum Dots nanoparticles

Inert Gas Condensation nanoparticles. Microemulsion Technique

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Such as: Metal nanoparticle, and Such as: Semiconduction metal

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intrametallic nanoparticles sulphate, Metal salt, and organic

nanoparticles

Pluse Vapor Deposition -p

Bio-Templetes Assisted Hydrothermal Synthesis
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Such as: Metals and Metallic Biogenesis Such as: Metal, Metal oxide and
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alloys nanopartiles Such as: Au, and Ag Metal sulphuide nanoparticles

Laser Pyrolysis nanoparticles Polyol Synthesis

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Such as: Metals and Non-Metals Such as: Magnetic, and Metal

nanoparticles hybrid nanoparticles

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Flash Spray Pyrolysis Chemical Vapor Synthesis

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Such as: Ceramic nanoparticles Such as: Si/SiO2 and Al drop

ZnO nanoparticles

Electrospraying Plant Extracts Assisted Plasma Enhanced Chemical

Such as: Metals and Ceramic Biogenesis Vapor Deposition

Oxide nanoparticles Such as: Pt and Pd nanoparticles Such as: Carbon and Silicon

Melt Mixing nanoparticles

Such as: Nanocomposition

nanoparticles

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Table 2. Characters, uses, and pioneering methods for nanosorbent materials.

Nanometals and Properties Uses Unique methods

nanometal Advantage Disadvantage

oxides

Nanosilver and Bactericidal, low Nanosilver, Water disinfection, TiO2 adaptation by

nano-TiO2 toxicity limited durability antibiofouling surfaces, visible light

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Nano-TiO2: more Nano-TiO2, cleansing of organic

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chemical stability, requires compounds

very long lifetime ultraviolet

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activation
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Magnetic Easy reactivates by Need action to Groundwater treatment Advancing osmosis
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nanoparticles magnetic field stability

Nano zero- Highly reactive Need action to Groundwater treatment Entrapment in

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valent iron stability polymeric matrices

with regard to
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stability
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Graphical abstract

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Highlights

1- Wastewater reuse became a smart choice for conserving and increasing water availability.

2- Nanosorbent materials are considered the most suitable water and wastewater

remediation

3- Nanosorbents have unique properties such as high surface area and high adsorption

capacity.

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Figure 1
Figure 2
Figure 3
Figure 4
Figure 5