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Emerging and Nanomaterial Contaminants in Wastewater: Advanced Treatment Technologies

Emerging and Nanomaterial Contaminants in Wastewater: Advanced Treatment Technologies

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Emerging and Nanomaterial Contaminants in Wastewater: Advanced Treatment Technologies

688 pagine
7 ore
Nov 1, 2019


Emerging and Nanomaterial Contaminants in Wastewater: Advanced Treatment Technologies describes the state-of-the-art of remediation technologies, such as those involving nanotechnology, filtration devices (e.g. membranes), strategies involving adsorption and precipitation processes, development of new sorbents, nanosorbents, biosorbents, green technology, bio-electrokinetics, degradation of pollutants, advanced oxidative process, oxidative electrochemical and photocatalytic processes, catalytic degradation, and emerging hybrid technologies, such as photocatalyst membrane photoreactors using TiO2. Scientists and researchers in academia and industry will benefit from this comprehensive resource on the fundamental science behind the mechanisms at which wastewater sources can be purified from emerging contaminants.

  • Provides a fundamental understanding of emerging contaminants to help readers select appropriate remediation technologies
  • Discusses, in detail, new and advanced green technologies that remove emerging contaminants from wastewater
  • Shows how to ensure water quality and save public health by protecting water resources from contaminants
Nov 1, 2019

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Emerging and Nanomaterial Contaminants in Wastewater - Elsevier Science


Part 1

General overview

Chapter 1

An overview of treatment technologies for the removal of emerging and nanomaterials contaminants from municipal and industrial wastewater

Sangeeta Adhikaria; Sandip Mandalb; Do-Heyoung Kima; Ajay Kumar Mishrac    a School of Chemical Engineering, Chonnam National University, Gwangju, Republic of Korea

b Department of Chemistry, National Institute of Technology, Jamshedpur, India

c Nanotechnology and Water Sustainability Research Unit, College of Engineering, Science and Technology, University of South Africa, Johannesburg, South Africa


The increase in the production of engineered nanomaterials and their introduction in the current consumer products have augmented the demand in the removal of nanomaterials from municipal and industrial wastewater systems. With the rapid emergence of nanotechnology, application-based development of products includes nanoparticles substantially that are anticipated to upsurge in the future. The existence of nanomaterials is soon going to be persistent in our atmosphere driving our concern toward its detrimental effect on the ecosystem and human health. However, we are still outlying the efficient and appropriate analytical methods/tools to obtain the standard statistics on the characteristics of chemicals, its concentration, and their transport in the environment that eventually resolve in the aquatic system. There has been no establishment so far for absolute treatment and protection from the very exposure of these nanomaterials. Thus, efficient removal processes are necessary for classifying the various categories of nanomaterials and their analysis in the context of developing future treatment technologies for the eradication of these nanomaterials from industrial and municipal wastewater bodies. A more detailed investigation is needed to demonstrate the complex interface interactions between the water dissolved species and nanomaterials to completely change the environment for clearance. Based on the previous perspective, efforts have been made to put forward the potential risks of nanomaterials, their source in water streams, and solution in terms of treatment technologies.


Emerging nanocontaminants; Engineered nanomaterials; Fate and transport; Contaminant detection; Treatment technologies

1 Introduction

Recently, the advanced nanotechnologies have made utilization of nanomaterials in almost all sectors that have envisioned to the booming industries. The enactment of nanomaterials in advantageous products or as process enhancers in manufacturing is rapidly growing (Moore, 2006). These nanomaterials are significantly influencing the everyday human life, by the introduction of new methodologies for the fabrication of novel materials and clean energy and also for medicinal or pharmaceutical application for serious diseases (Maynard et al., 2006). If we put a thought toward emerging and nanomaterial contaminant, which is a group of chemical compounds or nanomaterials that has been characterized for its potential threat and has a new pathway or source for its introduction to humans, the potential contribution to the environment is in the practices from several treatment processes in industries and pollution control and also from the remediation technologies that use high-surface-area nanomaterials (increased surface-to-volume ratio) for high reactivity (Ahmed et al., 2014). The concerns should be made on the attractive properties of nanostructured materials that could potentially lead to unforeseen environmental and health hazards. Apprehensions in relation to the ecological and human health repercussion rooting from the very exposure of emerging and nanomaterial contaminants (NCs) should be proliferated (Chrzanowska and Załęska-Radziwiłł, 2014; Drlickova et al., 2018). In reality, the basic understanding in terms of health and safety is still in its formative stage. Current nanotech research era focuses on the carbon-based materials (Li et al., 2015; Laux et al., 2018), metals and its substitutes (Diez et al., 2017; Lai et al., 2018), metal oxides (Faizal et al., 2013) and sulfides (Rui et al., 2014), quantum dots (Bhamore et al., 2018; Zhao et al., 2018), and nanosilver (Natarajan et al., 2017; Subhan et al., 2018) for versatile application in electronics, medicines, environmental treatment processes, and biological activities for the betterment of human future and making the survival easier. The possible harm in reality or phantom is intimidating to slow the nanotechnology development unless a standard, independent, and verifiable information is established for the prospective risks followed by approaches to prevent them (Yokel and MacPhail, 2011).

2 Classification of emerging NCs

The class of small-scale matters and specifically nanomaterial contaminants are those diverse structures having their structural components smaller than 100 of the nanometer in at least one dimension. They include particles having the dimensions between 1 and 100 nm (Nazarenko et al., 2011; Lubick, 2008). Some of the naturally occurring nanoparticles or aerosol is designated as ultrafine particles. It depends on the origin that has distinguished NCs in three different categories as natural, incidental, and engineered. Naturals are those that have existed in the earth from the very beginning in the form of dust from volcanoes and lunar and mineral composites. Anthropogenic waste materials resulting from manmade industrial processes are termed as incidental NCs. However, looking into the third category of NCs that are engineered to have positive effects on sectors such as consumer products, pharmaceuticals, cosmetics, energy, transportation, and agriculture has large-scale productions (Vance et al., 2015). On contrary, the exponential increment in incorporation may lead to the release of these NCs during their life cycle increasing the mere occurrence in the environment that includes aquatic, terrestrial, and atmospheric media. The fate of NCs in the environment depends on their unique properties allowing their utility in various applications (Nowack and Bucheli, 2007). Table 1 presents the majorly contributing NCs categorically based on their specific physical/chemical properties, their sources/exposure media, surface properties, and adverse effects on the environment. With the growing expansion in applications, it has become very crucial to understand the transformation, transport phenomena, and environmental risks possessed by these NCs for the development of an efficient and strong removal process as the ultimate destination of these NCs is the water/sediment interface irrespective of their pathways (Weinberg et al., 2011). Thus, it is quite significant to know about the recent developments and technologically active treatments for the removal of these NCs from their ultimate disclosure routes (Dwivedi et al., 2015).

Table 1

It can be very well noted that the growing production and utility of NCs in various diverse processes throughout the industries, construction companies, medicals, pharmaceuticals, and consumer products are increasing the illegitimate exposure of NCs. Categorizing the type of wastewater generated by anthropogenic activities is the municipal and industrial wastewater. Municipal water accumulates wastes from sinks, showers, baths, toilets, and laundries and also contains body waste and residual body oils. Apart from these, it also constitutes new and emerging NCs such as antibiotics, antimicrobial/antifungal agents, nonsteroidal antiinflammatory drugs (NSAIDs), anticonvulsants/antidepressants, artificial sweeteners, beta-adrenoceptor blocking agents, lipid-regulating drugs, steroidal hormones, UV filters like TiO2 and ZnO, antiitching drugs, insect repellants, plasticizers, X-ray contrast media, stimulants, and surfactants. Depending on the industries, wastewater can contain residual acids, plating metals, and other toxic chemicals both organic and inorganic.

3 Fate and destination of emerging NCs

The behavior and transport of NCs strongly depend on the material properties like particle size, pH, surface charge, electrolyte valence, and ionic strength. The translocation of NCs from their site of deposition to biological interaction increases with smaller size, large surface area, and increasing solubilization. There is a drastic increase in the circulation time with the high water solubility of NCs. Due to their smaller size and slow rate of gravitational settling, some NCs are readily transported due to their suspension. NCs can undergo several environmental processes in water streams before reaching the final destination of treatment. NCs can dissolute by losing its particle state and can stain the surface by changing its phase. They can sediment moving out of its suspension media and can also form agglomerates by sorption due to the high surface area of the particles. NCs are highly mobile, and they can adjust into the interlayer spaces that can travel a long distance before getting stuck in the soil matrix. Furthermore, NCs can be affected by the surface coating when in contact with the aqueous environment as some NCs can be harmless when in soil but if surface coated can have adverse effects on water. The focus should also be driven to the water quality leaving its sources as it is the representation of water that will be consumed after long-term processing. Thus, it is important to note that the mobility of NCs in the aqueous phase will have an impact over surface recreational waters. The possible upstream and downstream pathways of nanocontaminants accumulating from various sources are schematically shown in Fig. 1. There will be a high-quality difference between surface recreational water and drinking water. The quality of recreational water is different as the contaminant dilution in lakes is less efficient due to less mixing resulting from being stagnant. Regular monitoring should be carried out for these water systems as NCs can well associate themselves with the present environment.

Fig. 1 Schematic for possible pathways by which NCs can enter the water community. (* represents where treatment and detection could be carried out).

A proper protocol to address the fate and behavior of NCs in the complex environmental medium is missing. It is quite likely that several analytical methods have to be combined for adequate investigation of the broad spectrum of NCs. Another concern with the development of analytical method is the limited reference standards for accurate quantification. In this context, it has become necessary to approach for an advanced extraction method with subsequent high-end analytical methods. With diverse categories of pollutants, the necessity for accurate quantification of each species should be the prime objective. In concern to the exposure of NCs, assignment of toxicity index and determination of the existing protection or treatment technology should be questioned to meet the objective.

4 Characteristic detection of emerging NCs

The emerging NCs should be detected and quantified prior to any effective risk assessment as they variate in size, dispersion, structure, and distribution. Thus, the analysis of NCs for the wastewater samples should include multiple technologies in tandem where it can include separation based on size in combination with the particle counting methods followed by investigation of morphology and chemicals present in the wastewater. Since NCs are highly unstable in the aqueous media which can undergo several environmental processes when in contact with other aqueous components. Thus, the collection of samples and its preparation for further analysis can be an uncertain source that can even bias the quantification and characterization of the NCs. For example, in the case of metal-containing NCs, the organic ligands associated with metals can prevent the metal atomization in an inductively coupled plasma (ICP) (Fabricius et al., 2014). Conventionally, concentrated acids are used to dissolute metal-containing solutions; thus, it is always suggested to prepare metal NC solutions in chromic or nitric acid. Gold NCs have strong affinity toward wall of plastic and Teflon containers than glass vessels (Adams et al., 2006). It is essential to note that the sample collection vessel, its type, and the chemical preservatives to be used for sample stability until extraction are of equal importance along with detection and analysis. The NCs in the wastewater are expected to have lower concentration that challenges the available technologies for determination of its preconcentration and detection. In consequence, it has driven the attention of researchers and industrialists to come up with new separation approaches.

4.1 Separation and size fractionation

Based on the sizes of NCs, the most conventional practices for studying size distribution include centrifugation/ultracentrifugation, cross flow ultrafiltration, size exclusion chromatography (SEC), hydrodynamic chromatography (HDC), field-flow fractionation (FFF), and capillary electrophoresis. Size fractionation using centrifugation has been used widely after sedimentation. The separation stage during centrifugation includes fractionation from 9000–750 to 180–12 nm, kept in separate centrifuge tubes for detailed particle size characterization using transmission electron microscopy or atomic force microscopy. However, in the case of ultracentrifugation that produces accelerations of up to 10⁶ g, it can separate fibrous polysaccharide having 50 nm height and spherical black dots (5–10 nm in diameter) that can be identified in AFM analysis. Cross flow ultrafiltration considers the membrane pore size and separates the particles into fractions. Even though the fractionation is through multiple steps with variant membrane pore sizes, the resolution of size distribution is limited.

SEC is a chromatographic technique that isolates the NCs and is used in combination with detecting methods like inductively coupled plasma mass spectrometry (ICP-MS), multiangle laser light scattering (MALLS), dynamic light scattering (DLS), and voltammetry. This particular technique has been found useful in characterizing Au nanoparticles, single-walled carbon nanotubes and quantum dots. One major lacuna in SEC is that the column packing material can adsorb NCs irreversibly. A strong interaction between nanoparticles and the stationary phase can alter the characteristics of samples that can mislead the size distribution interpretation. SEC has allowed high resolution analysis of alkanethiolate-stabilized Au nanoparticles having size below 3 nm with a porous hydrophobic microgel column operation (Al-Somali et al., 2004). Citrate-stabilized Au nanoparticles are highly water soluble; thus, an anionic surfactant is to be added to prevent analyte adsorption and coagulation (Liu, 2009). HDC is an improvement made to SEC that uses nanoporous bead columns for separation through flow velocity and the gradient velocity across them (Small et al., 1976). HDC interfaced with ICP-MS has been reported to demonstrate the effectiveness of the technique, which produces size distributions in Ag nanoparticles jagged into a supernatant sample from sewage sludge. It is also helpful in the separation of mixed particles using an online column technique that provides efficient matrix removal with analyte preconcentration (Tiede et al., 2009a). Poor peak resolution is a challenge in this technique. The common sorbents used in SEC are Sephadex, Bio-beads and Lipidex and show successful results. Applicability of SEC for tracing the organic contaminants from food matrices and drug residues such as urea pesticides, organochloride residues, polycyclic aromatic hydrocarbons, anticoccidial drugs, and polyether antibiotics is well reported.

FFF is a single-phase chromatography technique with asymmetric field-flow fractionation (AFFF) as subtechnique that is mostly frequented. The separation of size by this technique is attained due to different diffusion coefficients of the particles. There is no stationary-phase and sample interaction that makes the separation process gentle, fast, and noncalamitous. There is a thin flat channel that allows the sample elution, which creates a parabolic flow profile due to laminar flow of the liquid. A cross flow perpendicular to the channel flow is applied, which forces the sample particles toward the lower wall of the channel where it gets accumulated. A counteracting motion is produced as particles also undergo Brownian motion along with diffusion. The smaller particles having high rate of diffusion tend to reach higher in the channel, which is an equilibrium position due to faster longitudinal flow. The particle separation is attributed to the velocity gradient along the channel where the smaller particles get eluted first. The channel is impermeable at the upper wall, and the accumulation wall cuts off the larger particles due to ultrafiltration membrane, but the solvent is allowed through the passage. This fractionation is governed by simple physical properties, and the hydrodynamic diameter of the particles can be calculated from the time of retention and dimension of the channel. AFFF separation spans the size from 1 nm to 100 μm. It has high resolving power that enables baseline separation of BSA monomer and dimer. This method is widely used in the analysis of metals, metal oxides, SiO2, and carbon black from suspended soils and from colloids of marine and fresh water (Baalousha and Lead, 2007). An important note in fractionation technique is that the characteristics of NCs should not be compromised while processing. Thus, the choice of carrier liquid type should be able to prohibit the particle interactions and not change the characteristics of the particles. For instance, Au nanoparticles with negative surface charge would require an anionic surfactant, but the concentration should be taken care such that it would not affect the detection (Sermsri et al., 2010). The flow rate and the liquid carrier are compatible with the ICP-MS interface, which makes the technique a potential online approach for characterization and quantification. Flow-FFF (Fl-FFF) has been used in the investigation of effect of salinity on the size distribution of humic acid aggregates in the estuarine water. Fl-FFF along with ICP-MS examined the salinity effect on size distribution of metals like Cd, Ce, Cu, Mn, and Pb binding with the humic acid aggregates. The results depicted that humic acid aggregates with large size fraction shows more affinity toward Pb, Cd, Ce, and Mn than Cu, but the small size fraction aggregates finds it more comfortable to bind with Cu (Suwanpetch et al., 2017).

Capillary electrophoresis is another well-suited methodology for size separation in a mixture of water-soluble and charged components. The electrophoretic mobility is well related to the electrical double layer deformation around the particles, which is the function of zeta potential of the particles. As the nanoparticle surface charge affects the zeta potential, thus, the use of adapting agents in the buffer mobile phase can tune the migration rate toward the electrode (Liu, 2009). The major restriction in the commercial CE systems is their low sample volume and the lack of sensitivity in online detectors such as spectrophotometric absorption. On the other hand, sensitive detection of gold and gold/silver core/shell nanoparticles was carried out using reversed electrode and polarity tracking as an online preconcentration technique (Lin et al., 2007). This method is quite consistent in correlating and particle diameter and electrophoresis mobility when accounting the interactions between particles and capillary surface. Capillary surface modification and pH suppression of the buffer are tactics that are used to prohibit the capillary surface retention (Surugau and Urban, 2009). CE with diode array detection and MS in combination with solid-phase extraction were employed for identifying reactive vinylsulfone and chlorotriazine dyes with their hydrolyzed products in spent dyebaths and raw and treated wastewater. This methodology has been applied and found fruitful for the detection of hydrolysis products (which ranged from 23 to 42 μg/L) of reactive dyes in both influent and effluent of municipal wastewater treatment plant (Poiger et al., 2000). Coupling of CE with spectroscopic techniques like UV-vis absorption and fluorescence is quite common. Recently, CE method is coupled with laser-induced fluorescence (LIF) for the detection of endotoxins and lipopolysaccharides (LPS) from different bacterial stains. Initially, derivatives of LPS with amino-reactive fluorescent dye and fluorescein isothiocyanate (FITC) are separated under optimal conditions by capillary zone electrophoresis (CZE) with 50-mM sodium tetraborate buffer followed by LIF detection. A solid-phase extraction preconcentration technique improved the sensitivity of CZE-LIF for trace amount determination of endotoxins and also for possible elimination of interference between materials in environmental samples. It successfully determined the LPS levels in wastewater and tap water with high sensitivity, reproducibility, and reliability (Fung et al., 2017). The fluorescence detection with CE is a versatile and compatible method with enhanced selectivity in comparison with UV-vis absorption detection. It also reveals about the structural information of single-walled CNTs. CE in combination with interfaced light scattering can separate polystyrene spheres in which nanoparticles greater than 110 nm were detected individually (Surugau and Urban, 2009). Interfacing CE with MS is an interesting development hinted from the results of CE collected gold nanoclusters using fractions followed by offline matrix-assisted laser desorption/ionization MS (Lo et al., 2008). It seems realistic for CE separation with online detector as most particles in wastewater systems are nanorange.

4.2 Scattering and spectroscopic detection

Scattering and spectroscopic technique is a phenomenon that results from the interaction between the nanoparticles and electromagnetic radiation using light. It helps in the characterization of nanoparticles using the properties such as electromagnetic waves, electron beams, and photons. In accordance to the size, shape, and structure of nanoparticles, the wave vectors are modified without any frequency change and measured in different scattering techniques such as X-ray, electron, or neutron diffraction. With respect to absorption, changes can be made to the frequency of the energy sources. Dynamic light scattering (DLS) is an impressive technique that determines particles and its size distribution in liquid samples (Bootz et al., 2004). It is a nondisturbing in situ measurement technique. The major challenges in this technique are when it has to deal with polydispersity or particles in complex media (Thang et al., 2000). Such light-based techniques can be used in combination with FFF and Fl-FFF for complex size fractionation. Coupling the spectroscopic scattering with separation techniques can help to attenuate the issue and enhance applicability. Further, the structural properties of nanoparticles in solid and fluid media and also in mono-/polydispersed systems are investigated using the small-angle X-ray diffraction (Tiede et al., 2008).

Laser-induced breakdown spectroscopic (LIBS) detection is another sensitive and novel method for noninvasive determination of both counted mean diameter and concentration of nanoparticles in liquids. LIBS is a spectroscopic technique based on atomic emission employing laser pulse as the source of excitation forming plasma for atomization and excitation of samples. This detection technology was used for the detection of aquatic colloids that includes nanocolloids (Bundschuh et al., 2001a). The probability of breakdown is related to the concentration and size of the particles that is approximately proportional to the diameter of particle (mostly spheres). It is highly sensitive toward particles smaller than 70 nm. When the particle size exceeds 70 nm, sensitivity via light scattering is found as a better alternative. This methodology is used to produce size spectra of isolated nanoparticles using ultracentrifugation in treated drinking water (Kaegi et al., 2008). Before the final disinfection, the conventional treated water consisted of nanoparticles in the size range 15–20 nm with 108/mL number density. When compared with the permeate collected after ultrafiltration process, the particle size obtained was less with comparable number density, which governs that other methods impart a higher magnitude of level of detection and also they exhibit detection of nanoparticles in 10-nm range (Latkoczy et al., 2010). LIBS has recently been applied to the waters from different steps in drinking water treatment plant that uses energy curves for the calculation of particle size and 10⁷/mL number density. The employment of ozonation in between coagulation and filtration process as shown in Fig. 1 has resulted in decrement of nanoparticle number density by ~ 3 factor without affecting the diameter (~ 20 nm). On the other hand, filtration via activated carbon is capable to elute the nanoparticles of increased diameter probably due to washing out of carbon. The reduction in nanoparticle diameter to 10 nm is achieved after final ultrafiltration, but the concentration of nanoparticles in final water is still measurable to 4 × 10⁷/mL (Latkoczy et al., 2010). It is not possible to detect the type of nanoparticles in this system; thus, emphasis should be made to develop methods that can ascertain both the number and type of nanoparticles in the treatment systems. An approach toward the development of mobile LIBS both onsite and online has been carried out for the measurement of aqueous colloid and nanoparticle suspensions. Recently, LIBS analysis was performed by deposition of nanoparticles on the surface of sample. Different topologies of nanoparticle-enhanced LIBS experiments were carried out in metal, glass, and liquid solutions, and efficiencies were compared with conventional LIBS. The enhancement in efficiency is related to better ablation efficiency due to coupling of laser magnetic field with induced nanoparticle plasmonic field. A very crucial role is played by the injected atoms and ions provided their breakdown with small amount of samples by LIBS (De Giacomo et al.,

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