Summary of the studies related to eco-toxicity of the CNTs on different organisms [82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98].
\r\n\t
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Wu",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11916.jpg",keywords:"Business Models, E-commerce Marketing Strategy, E-commerce Business Models, Digital Transformation, Business Intelligence, E-business Applications, Research, Information System Management, Marketing Management, Electronic Commerce, Internet Marketing, Information Systems",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"April 26th 2022",dateEndSecondStepPublish:"June 30th 2022",dateEndThirdStepPublish:"August 29th 2022",dateEndFourthStepPublish:"November 17th 2022",dateEndFifthStepPublish:"January 16th 2023",dateConfirmationOfParticipation:null,remainingDaysToSecondStep:"2 months",secondStepPassed:!0,areRegistrationsClosed:!1,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:'Dr. Wu holds a Ph.D. in e-Commerce, lectures at the School of Engineering and Technology in Australia, and is a Distinguished Professor at Shanxi Normal University, China. In 2011, Dr. Wu was recognized as a ‘Top 100 Outstanding Academic Leader for China’s Informatics’ by the China Informatics Society. He was awarded "Outstanding Contribution in Reviewing" by Q1 Journals such as Electronic Commerce Research and Applications (Elsevier).',coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"190913",title:"Dr.",name:"Robert M.X.",middleName:null,surname:"Wu",slug:"robert-m.x.-wu",fullName:"Robert M.X. Wu",profilePictureURL:"https://mts.intechopen.com/storage/users/190913/images/system/190913.jpg",biography:"Robert M.X. Wu has a diploma in Computer Science, a bachelor’s degree in Economics, and master’s and doctorate degrees in e-Commerce. He is currently lecturing e-commerce / Information Systems at Central Queensland University Australia (CQU). 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There are variations in the elucidations of these reports, and they mainly depend on the type of nanomaterials as well as functionalization methods. Properly functionalized carbon nanotubes were shown nontoxic to animals conducted by various groups [1, 2, 3, 4], whereas raw carbon nanotubes were shown to be toxic to mice lungs in an in vivo study [5, 6, 7, 8]. The latest research revealed that non-functionalized, long MWCNTs might be carcinogenic to mice [9]. Pristine nanotubes are indicated to cause oxidative stress and decrease cell viability [10, 11]; however, there is some sign that leftover catalyst particles also contribute to this effect [12]. The cytotoxicity can be decreased to zero via functionalization with a covalently attached polar functional group [13]. Likewise, the toxicity of noncovalently functionalized carbon nanotubes depends on the variety of the functional group. Cells were viable upon internalization of individually encapsulated DNA-wrapped SWCNT complex [14].
Therefore, the toxicity of carbon nanotube depends on the type of functionalization, aggregation behavior, and the presence of metal catalyst particle leftovers during synthesis.
Manufacturing fundamental elements with great strength to weight ratio using carbon nanotube composite is the contemporary focus of the researchers. One of the likely utilizations of polymer nanocomposite is the CNT-augmented ultrafine fiber via electrospinning [15, 16], which has been known since the 1930s. Today, polymer fibers with nanometer diameter can be produced inexpensively using electrospinning technology. With <100 nm diameter, these fibers are being studied for drug delivery methods, energy storage, and improved functional garments [17, 18, 19]. These applications require improved (i) fiber strength, (ii) thermal conductivity, and (iii) electrical conductivity. Incorporating carbon nanotubes (CNTs) within electrospun fibers offers the probability of simultaneously improving all these three properties [20, 21, 22]. Xie et al. (2005) reviewed the dispersion and alignment of CNTs in the polymer matrix [23]. They found that the serious challenge is the development of means and ways to promote and increase the dispersion and alignment of CNTs in the matrix. Enhanced dispersion of CNTs in the polymer matrix will foster and extend the applications and developments of polymer/CNT nanocomposites.
Though the optical apprehension techniques are probably the most conventional in biology and life sciences, electrochemical or electronic detection techniques have also been adopted in biosensors/biochips due to their great sensitivity, high specificity, and low cost. Those techniques comprise of voltammetric techniques (cyclic voltammetry and differential pulse voltammetry), chronocoulometry, electrochemical impedance spectroscopy, and electronic detection based on electric field [24]. The sensors developed from CNTs have shown the ability to detect a range of analytes such as particular DNA sequences [25] as cancer biomarkers [26] and larger entities such as viruses [27]. These sensor devices have also been used to monitor enzymatic activities and study the behavior of potential drug molecules [28].
The apprehension of the analytes befalls with great specificity and sensitivity in a rationally precise time. Both SWCNT and MWCNT can be altered and conjugated to a bioactive unit and biological varieties including carbohydrates, amino acids and peptides, nucleic acid, and proteins, for various biological applications. Those biological applications are plausible only because the carbon nanotubes own some anomalous properties like the one-dimensional arrangement, large aspect ratio, outstanding mechanical characteristics, and chemical inertness [29]. The carbohydrate-functionalized carbon nanotubes have previously been used for the identification of pathogenic microorganisms, namely, [30, 31]. In the advancement of energy production and storage, nanotubes exhibit exceptional potential in supercapacitors [32], Li-ion batteries [33], solar cells [34], and fuel cells [35]. Energy applications could become the broadest application realm in the gross application of carbon nanotubes. For the advancement of Li-ion batteries’ performance, MnO2 and LiFePO4 are being used as a cathode while MWCNTs and graphene as an anode. In the realm of the fuel cell, proton-exchange membrane fuel cells (PEMFCs), CNTs have been widely studied [36].
In a PEMFC, the conversion of chemical energy to electrical energy occurs via a direct electrochemical reaction, and its efficiency is directly dependent on the catalysts used [37]. The catalysts should have high endurance, low cost, and higher activities in oxygen reduction and/or fuel oxidation reaction [38]. Shortly, the most regularly used catalysts in the PEMFCs are metal NPs, mainly Pt and/or Pt-based alloys, because of high oxygen reduction and/or fuel oxidation reaction due to high Surface area : volume ratio and better Fermi levels for redox reactions [39]. Nonetheless, metal NPs are generally unstable and lose their catalytic activity due to their irreversible aggregation during the electrochemical processes.
Consequently, appropriate methods are obliged to fix and restrict these metal NPs from aggregation, e.g., carbon nanotubes (CNTs) are the most extensively adopted provision in modern development. Though the evolution of PEMFCs is under commercialization process, obstructions including how the CNTs influence the catalytic action of the metal/CNTs and high material cost continue. The evolution of numerous profoundly dynamic catalysts with the economical price for fuel cell commercialization would be one of the notable researches in this domain. Because of the enhanced production and intended use of CNTs in consumer commodities, there is a necessity for evaluation of the implied toxicity of these nanoparticles.
In vivo toxicity knowledge impersonated a vital role in risk evaluation. Those techniques can be applied to determine acute toxicity, chronic toxicity, developmental toxicity, genotoxicity, and reproductive toxicity. In vivo study is indispensable in the fields of medicine including cancer therapy. Several animal trials are performed to highlight the possible serious impressions of newly formed medicines and chemical substances on the human. In some trials, researchers attempt to simulate situations concerning humans (e.g., arthritis, cystic fibrosis, and cancer) in animals, to assess the capabilities of new medicines in treatment. To inscribe the potential side effects of CNTs on human health and environment, animal models have been used to investigate the toxicity of CNTs. Non-functionalized CNTs were instilled intratracheally (IT) into animals, exhibited as pulmonary toxicity including inflammation and fibrotic responses due to the collection of raw CNTs in the lung airways [5].
These outcomes suggest that aerosol vulnerability of untreated CNTs in the workplace should be shunned to preserve human health. Notwithstanding, intratracheal instillation of functionalized soluble CNTs has little inference to the toxicology profile. In the latest pilot study, asbestos-like pathogenicity was observed by Poland et al. [9] when the mesothelial lining of the body cavity of mice was exposed to large MWCNTs of 80–160 nm diameter and 10–50 nm length [9]. Yet the assumption of this finding for probable negative effects of CNTs on human health is inadequate. It should be heeded that the MWCNT materials utilized in this research were just sonicated in bovine serum albumin (BSA) without surface functionalization.
Furthermore, no noticeable toxic result was observed for smaller and tinier MWCNTs of 1–20 nm length and 10–14 nm diameter, appreciating that the toxicology characterizations of CNTs may vary between CNTs of varying sizes. It is deserving asserting that functionalized SWCNTs utilized in biomedical research have a length of 50–300 nm and diameter of 1–2 nm, which is completely distinct from the geometry of MWCNTs adopted by Poland et al. [9]. Gambhir and colleague applied covalently and noncovalently PEGylated SWCNTs to investigate the in vivo toxicity [3]. The PEGylated SWCNTs (−3 mg kg−1) were intravenously infused into mice and inspected over 4 months. Systolic blood pressure, total blood counts, and serum chemistry are registered every month. Necropsy and tissue histology analyses were executed at the completion of 4 months. The blood chemistry and histological investigations were normal. Those experiments insinuate that functionalized biocompatible SWCNTs may be secured for in vivo biological reinforcements. An added investigation revealed related outcomes, confirming that PEGylated SWCNTs are gradually eliminated from the body after systemic administration in mouse models, without manifesting apparent toxicity in the system [40]. Yang et al. acknowledged that SWCNTs dangled in Tween-80 manifested lesser toxicities to the experimented mice at a high dose of −40 mg kg−1, following intravenous inoculation for 3 months [41]. Toxicity may be due to the oxidative stress engendered by SWCNTs assembled in the liver and lungs of mice [42]. The toxicity published was dose-dependent and appeared to be less acceptable at lower doses. A current article by the same group unveiled that covalently PEGylated SWCNTs displayed an ultra-long blood dissemination half-life in rodents. Though the long-term toxicity of altered SWCNTs is still to be investigated, no critical toxicity has been recorded too at a higher dose of 24 mg kg−1.
A guinea pig was inoculated intratracheally with the soot of CNT. Breathing rate, tidal capacity, pulmonary obstruction, bronchoalveolar fluid, and protein content were estimated. The authors admitted that working with soot-carrying CNT was probably not a health jeopardy, but they did not present their pathological investigation [43]. Research in mice is conducted by Lam et al. [5], and they authenticated that SWCNT could be toxic if they entered the lungs; Warheit et al. [6] conveyed a related investigation in rats, reporting the granuloma development apparently due to the collection of CNT. Muller et al. analyzed carbon black, MWCNT, and asbestos influences, implanted in the trachea of rodents. Scholars demonstrated dose-dependent inflammation, and granuloma production, increased considerably with MWCNT than with carbon black than asbestos. The early granulomatous reaction, abnormal acute inflammatory response, and progressive fibrosis were observed upon exposure of SWCNT in mice. Pharyngeal aspiration was used alternately of the intratracheal instillation used in the earlier investigations and rendered aerosolization of fine SWNCT particles. Another contemporary study insinuates shifts in deposition prototype and pulmonary response when SWCNT is uniformly dispersed in the suspension antecedent to pharyngeal aspiration [44]. Current research insinuates MWCNT immigration to the subpleural and associated pleural mononuclear cells and subpleural fibrosis in mice upon inhalation [45] and further admonition, and decent security models are prescribed when manipulating CNT. Research by [46] confirms the earlier reports; they characterized in vitro and in vivo stimulation of collagen deposition, lung fibroblast propagation, and metalloproteinase intensified expression without inflammation when dispersed SWCNT was applied. Following inhalation, the different variety of nanoparticles may enter the central nervous system (CNS) [47] by a method called transcytosis [48]. The investigation unveiled that sniffed gold nanoparticles aggregate in the olfactory tubercle of rats and enter the cerebral cortex, lung, and the distinct organs such as the tongue, esophagus, kidney, spleen, aorta, septum, heart, and blood [49]. Those remarks vindicate that nanoparticles can infiltrate into the CNS via the olfactory venation if they are being in high doses in the air. Those nanoparticles may impact not only on the respiratory tract and neighboring organs but disseminated to remote organs.
Knowledge of bio-distribution of CNTs following systemic inoculation inside animals is a pretty serious concern. Numerous investigators investigated in vivo bio-distribution and pharmacokinetic investigations in the preceding several years. Scientist adopted various CNT materials, different surface functionalization methods, and various tracking methodologies. Consequently, they got unsteady and seldom ambiguous results. Singh et al. and Lacerda et al. utilized radiolabeled (1n-DTPA) SWCNTs and MWCNTs to describe bio-distribution [50, 51]. Exceptionally, following intravenous inoculation of CNTs into mice, no uptake in the reticuloendothelial system (RES) such as the liver and spleen was witnessed. But, quick urinal removal of CNTs was witnessed. More than ninety five percent of CNTs were removed within 3 hours. Those results are comparable to the in vivo response of minute particles yet distinct from that prognosticated of maximum nanoparticles with sizes exceeding the glomerular filtration threshold. To defend their conclusions, the researchers stated that the short diameters of CNTs were eliminated in urine notwithstanding they were large in length. However, this theory is unsettled. For example, for the protein bio-distribution and elimination function of quantum dots (QDs), published by Choi et al., it is observed that the 6 nm maximum size of spherical QDs including coatings was obliged to fast urinal elimination. Nevertheless, the QDs are much shorter than the diameter of SWCNT bundles (10–40 nm) or MWCNTs (20–80 nm) [51] practiced in those bio-distribution investigations. Therefore, the inscribed fast urinal excretion of CNTs requires validation. Various other labs have also assessed the bio-distribution of radiolabeled CNTs in rodents. Wang et al. noticed delayed urinal elimination and weak RES uptake in their primary research. But, consecutive articles by the same association utilizing 14C-taurine-functionalized CNTs recorded steadfast liver accumulation of CNTs following intravenous inoculation [52]. Research carried out by McDevitt et al., utilizing antibody-conjugated radiolabeled CNTs functionalized by 1,3-dipolar cycloaddition, also confirmed delayed urinal excretion and high CNT uptake in the liver and spleen [53]. The bio-distribution investigations of radiolabeled, PEGylated SWCNTs unveiled uptake of SWCNT in RES organs without active clearance [54]. A substantial quantity of CNTs is persisting, even after 15 days. The radiolabel system is a proper technique to identify the bio-distribution of material but may commence to inaccurate outcomes, if excess-free radioisotopes in the radiolabeled CNT specimens are not separated effectively. The free radioisotopes are tiny particles that could be quickly excreted in urine following intravenous inoculation. Moreover, radiolabels could be undeviatingly released from CNTs in vivo and be regularly eliminated in the free form. Consequently, radiolabeling is not an excellent approach to investigate the elimination and long-term predestination of CNTs. The expert has discovered that photoluminescence is the inherent characteristics of CNTs. Cherukuri et al. used single semiconducting SWCNTs which show NIR photoluminescence, to trace nanotubes in rabbits [55]. Without obtaining complete bio-distribution data, the expert could not testify SWCNT photoluminescence signals in every organ besides the liver. Yang et al. carried out the research to comprehend the bio-distribution of 13C-fortified unfunctionalized SWCNTs over a month utilizing isotope ratio mass spectroscopy [56]. The event conferred unusual nanotube uptake in the liver, lung, and spleen without notable elimination within 28 days. Raman spectroscopy has been applied to analyze the long-term predestination of PEGylated nanotubes in rodents. It was reported that most of the PEGylated SWCNTs were assembled in the liver and spleen following intravenous inoculation but gradually eliminated through the biliary pathway toward the feces within months. A low SWCNT Raman signal was also identified in the mouse kidney and bladder. It is unveiled that little portion of SWCNTs with short lengths was eliminated into the urine.
In vitro, toxicological investigations are a highly significant means for nanotoxicology, corresponding to in vivo investigations because of moderate expense, lessening ethical anxieties, and diminishing the number of laboratory animals needed for trial.
The subject of carbon nanotube toxicity is still unresolved even in cell culture experiments. Inhibition of HEK 293 cell proliferation following exposure to SWCNTs [10], MWCNTs, inducing cell cycle arrest and increasing apoptosis/necrosis of human skin fibroblasts were examined by different research groups [57]. Nevertheless, it is worth stating that functionalized CNTs were not used in those investigations. Bottini et al. observed T-lymphocyte apoptosis evoked by oxidized MWCNTs [58]. Because simple oxidation, used in these studies, is not enough to disperse carbon nanotubes in saline and cell culture media since it is not a kind of biocompatible functionalization. Sayes et al. indicated that toxicity of CNTs was also dependent on the density of functionalization. Inconsiderable toxicity was observed for those functionalized with the high density of phenyl-SO3X groups [13]. These results are understandable because CNTs without proper functionalization carry a highly hydrophobic surface. Consequently, they may aggregate in the cell culture medium. The aggregation of CNT channels to binding of several biological species, including proteins, via hydrophobic interactions, provokes cell toxicity. Khalid et al. reported no toxicity of functionalized MWCNT to Saos cell lines up to the tested concentration of 1000 μg/mL [59]. Other factors like surfactants may also play a role in the noted toxicity of CNT in vitro. Extra surfactants, present in the CNT suspensions, are known to be highly toxic to cells [60]. The metal catalyst, used during the synthesis of CNTs, should also be examined as an important factor when the toxicity of carbon nanotubes is analyzed [61]. Furthermore, proper analytical methods must be hired in toxicity analysis to prevent interference of carbon nanotubes with the test reagents [62]. Davoren et al. reported concentration-dependent cytotoxicity of SWCNT on a lung carcinoma cell line (A549) [63]. Another study, led by Sharma, unveiled that SWCNT induced oxidative stress in rat lung cells [64]. Herzog et al. reported the same oxidative stress linked to alterations in primary bronchial epithelial cells and A549 cells, but the study also revealed that the reaction is strongly dependent on the dispersion medium used [65]. Pulskamp used two cells lines (human A549 and rat macrophages NR8383) and tested with CNTs and revealed, as oxidative stress was provoked to these cell lines. However, when purified SWCNT corresponded with commercial CNT, it is unveiled that all the biological consequences are associated with the metal traces. There is a complicated result between WST (2-(4-iodopheny1)-3-(4-nitropheny1)-5-(2,4-disulfopheny1)-2H-tetrazolium, monosodium salt) and MTT (344, 5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) viability assays. These dyes depend on the mitochondrial dehydrogenase activity [66]. The modifications can only be described based on associations of CNT with non-soluble formazan crystals in MTT. That is why suitable assay methods and well-characterized materials are the most important requirements for in vitro toxicity assays of carbon nanotubes.
As an option to animal cell lines, bacteria and yeast can be a relevant model for studying how single-celled microorganisms react to the environmental stressors such as CNTs [67]. Copious toxicity mechanisms have been suggested for CNT including interruption/penetration of the cell envelope, oxidation of cell ingredients, the arrest of transmembrane electron transfer, and generation of secondary products such as reactive oxygen species (ROS) or dissolved heavy metal ions [68]. Toxicity of a CNT is depending on its structure along with its geometry and surface functionalization. Various researches have shown that adequately functionalized, serum-stable CNTs are innoxious to animal cells, whereas CNTs without functionalization seemed critically toxic to human or animal cell lines at the moderate dosage [2]. The SWCNT displays a potent antimicrobial response for both suspended and deposited bacteria and interrupts the accumulation of bacterial films. The immediate interaction among the SWCNT and bacteria is apparently the central cause to induce cell death [68]. Well-dispersed individual SWCNT is more toxic than agglomerates due to greater physical puncturing of bacterial membranes and impairs the cell integrity [69]. The CNT bacteria interplay is determined by surface functionalization and length of CNT. It may govern the toxic effect also. A negatively charged or neutral SWCNT functionalized with -OH or -COOH aggregates more efficiently with bacteria and diminishes bacteria viability as contrasted to the positively charged SWCNTs functionalized with -NH2 [70]. Likewise, longer SWCNTs exhibited concentration and time-dependent toxicity to bacteria, whereas short SWCNTs were limited toxically as they aggregate themselves [71]. The purity of SWCNTs may also influence bacterial toxicity. Pure SWCNTs were observed to be less toxic than SWCNTs with higher metal content due to glutathione oxidation following contact [72]. Additionally, greater ionic strength suspensions, such as phosphate buffered saline (PBS) or brain heart infusion broth, also lessen SWCNT toxicity due to decreased intensity of interactions between SWCNT and cells, compared to low ionic strength suspensions (deionized water or saline). Likewise, a film with natural organic matter (NOM) limits SWCNT toxicity, notwithstanding diminished aggregation [73]. Other studies unveiled that SWCNT reduces enzyme activity and microbial biomass at concentration 300 mg kg−1 and above [74]. As it is clear that SWCNT provokes bacterial death, a surface coating with SWCNT would decrease biofilm expansion in both real and industrial settings [75]. The MWCNT appears to be runty toxic to bacteria as contrasted to SWCNT [76]. The decreased toxicity may be due to minor interactions among bacteria and MWCNT. The limited interaction might be due to the greater rigidity and presumably inferior van der Waal’s forces at the MWCNT surface. Thin MWCNT with less diameter exhibits greater toxicity to bacteria corresponding to larger ones [77]. When the consequence of the length of MWCNT was estimated, shorter MWCNTs were extra toxic to
As the production and widespread application of CNTs in industrial and customer products are progressing, the release of this nanomaterial into the environment too will scale up. Many scientific reviews have evaluated the sources, behavior, fate, and the mechanisms of toxicity of carbon nanomaterial. Maximum of these assessments apprehended that additional research is obligatory in the field of nano-ecotoxicology (Table 1).
Summary of the studies related to eco-toxicity of the CNTs on different organisms [82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98].
Abbreviations: LOEC: Least observable effect concentration, EC 50: Effective concentration 50, NOEC: No observed effect concentration, NOM: Natural organic matter.
Toxicity of carbon nanomaterials is an essential concern in the modern world for the scientific community, environmentalists, and governments. The chances of exposure to the environment are more like the application of carbon nanomaterial which is increasing every day. Some research shows the different toxicity patterns for the materials when it is exposed to living cells in vitro or in vivo, whereas other studies say that the adequately functionalized bearing carboxylic or hydroxyl group and serum-stable CNTs are safe for living cells. I want to conclude my discussion by highlighting the factors involved in toxicity and the toxicity mechanism. The toxicity of the nanomaterials depends on many factors including functionalization, catalyst, size, shape, dimensions, dispersion, and methods used for detecting toxicity. The pristine carbon nanotubes are more damaging to the cells than the functionalized one. The covalently functionalized CNTs are more compatible for the cells than non-covalent functionalization. The catalyst used during the production of the nanotubes like platinum or iron also contributes to the toxicity of the cells. Hence it is imperative to differentiate the toxicity of carbon nanotubes and catalyst. Dispersion in the high ionic strength solvent like PBS makes the CNTs more compatible with living cells compared to the less ionic strength solvent like deionized water. Hence it is always recommended to prepare the solution in PBS or other high ionic strength solvents for better compatibility and less toxicity. The short and broken CNTs with a small diameter are observed to be damaging to bacterial cells because of physical puncturing. In vivo studies help us to understand the acute toxicity, chronic toxicity, developmental toxicity, genotoxicity, and reproductive toxicity of CNTs in laboratory animals. No critical acute toxicity, chronic toxicity, developmental toxicity, genotoxicity, and reproductive toxicity are observed following intravenous or intratracheal instillation of CNTs. Adequately functionalized CNTs are biocompatible and promptly eliminated through urine or biliary pathway following intravenous inoculation. Pharmacokinetic studies of CNTs show very less or no uptake of CNTs to the reticuloendothelial systems including the liver, lung, and spleen. Various mechanisms are also listed to study the toxicity of the CNTs to the living cells which includes oxidation of cell components, arrest of electron transport chain, reactive oxygen species, and physical puncturing of the cell. Further studies need to be conducted in the field of eco-toxicity of CNTs and validation of the toxicological data for the safety of aquatic and aerial animals. These studies shall help the public regulatory organization to frame a rule for ensuring the safety of this modern engineered nanoparticle.
Nanotechnology is one of the most prominent promising technologies that offer solutions to different problems in various aspects of our life. In fact, nowadays, nanotechnology used in the synthesis of nanoparticles has attracted great interest in different applications (environment, emerging, industries…etc.) [1, 2, 3]. A healthy environment is a major challenge faced by the world today. In connection with the rapid industrialization, scientists reported the presence of more than 700 carcinogenic and highly toxic inorganic and organic micro pollutants. Toxic inorganic metals included instance chromium, mercury, cadmium, lead...etc. and inorganic oxyanions included fluoride, nitrate, phosphate etc. while organic contaminants included, phenols, dye, hydrocarbons, and pesticides. They are considered persistent environmental pollutants non-biotransformable or non-biodegradable [3]. Mining operations, metal plating facilities, textile industries, fertilizer industries and pharmaceutical industries are the most common sources of these hazardous substances [4, 5, 6, 7, 8]. Consequently, developing efficient techniques for the treatment of effluent fertilizers and industrial before being discharged into the environment is a considerable issue in terms of public health and environmental protection.
The need for sustainable technologies to conserve the environment leads to the development of a lot of technologies in the field of water treatment [9]. In this scenario, research efforts have been conducted to remove these contaminants from wastewater using several methods such as adsorption, electrolysis electrodialysis, ion exchange, reverse osmosis, coagulation and flocculation, and chemical precipitation have demonstrated different degrees of remediation efficiency [9, 10, 11] .
Many of these methods, such as coagulation and flocculation, ion-exchange, and reverse osmosis, are expensive and cannot be applied in developing countries. Conventional coagulation methods and chemical precipitation cause secondary contaminants requiring an additional treatment and increasing the treatment cost [3, 11].
Interestingly, adsorption is the most attractive process in developing countries due to its lower cost, easy-to-use and its high efficiency to remove different types of contaminants [3, 12, 13]; thus, the adsorption method produces low quantities of sludge, which is largely produced by other methods (chemical precipitation) [3], but it requires a good choice of adsorbent. Generally, the selection of the useful adsorbent for water treatments is controlled by many factors such as the adsorption capacity of the material toward the target contaminant, cost/efficiency ratio, and the type and concentration of the contaminants present in water [3]. Ideal adsorbents must therefore meet a number of criteria, such as: (1) should be environmentally benign; (2) should demonstrate a high sorption capacity and high selectivity especially to the pollutants occurring in water at low concentration; (3) the adsorbed pollutants can be easily removed from its surface, and (4) should be recyclable [14]. A sorbent with the above characteristics would be considered an excellent adsorbent in wastewater treatment. Efficient adsorbents of biological, organic or mineral origin have been used for wastewater treatment [15, 16]. The most important used adsorbents are agricultural wastes [17], clay minerals [18, 19], modified clays [20, 21], zeolites [22], and activated carbon [23]…etc.
Nanotechnology has great potential for improving the efficiency in preventing water pollution and improving the treatment methods [9]. In fact, the application of nanotechnology in water treatment extends to various fields like nanoscale filtration techniques, adsorption of pollutants on nanoparticles and breakdown of contaminants by nanoparticle catalysis [3, 15].
Among various nanoparticles ‘clay minerals’ generally speaking, clay minerals which are constituted of layered mineral silicates in the nano dimension, are cheap and non- hazardous, and are characterized by high surface reactivity and stability due to their large surface area [24]. Compared with other adsorbent materials, clay minerals with physical adsorption ability and surface chemical activity, are readily available, making them increasing focus as of late [25, 26]. Nevertheless, the adsorption ability of clay is mainly dependent on fundamental traits, for instance, the charge characteristics of the adsorbent, pH, competing ions and pollutant type [18]. Moreover, clays that exhibit the crystal structure and negative charge have restricted their application [27]. In order to overcome these limitations, many studies in recent years have addressed the improvement of the mechanical properties of clay through the use of various types of modifications [21].
Recently, there has been an increasing interest in using organoclay for the removal of contaminants from soil and aquatic environments due to here the large specific surface and a hydrophobic behavior. Indeed, the intercalation of cationic surfactants changes the surface properties from hydrophilic to hydrophobic, greatly increases the specific surface and increases the basal spacing resulting in exposure of more adsorption sites [28, 29], thus, adsorption capacity especially when surfactant loading exceeds the CEC of clay [30]. Organoclay are a group of surfactant modified clays with hydrophobic properties, which have been extensively used in remediation of heavy metals, herbicides and pesticides, organic compounds and anionic contaminants [31].
The overall aim of this chapter was the investigation of the preparation and characterization of organoclay and their capacities to remove various pollutants as well as empirical findings on the equilibrium isotherms and kinetics. The literature for the chapter included published studies on hazardous substances.
This section of the chapter describes the preparation of organoclay on the laboratory run, with various experimental conditions, clays from different regions, and various kinds of surfactants. Organoclay material is defined as hybrid materials resulting from clay mineral association with surfactant [28].
Surfactant compounds are amphiphilic molecules, meaning they have two parts of different polarity, one hydrophobic is apolar and the other hydrophilic is polar (Figure 1).
General structure of a clay mineral [
Clay minerals are fundamentally hydrous alumino-silicates with highly fine particle sizes. Most clay minerals are made by a stack of sheets; these sheets are made by a stack of tetrahedral and octahedral layers that shape the frame of all clay mineral assemblage; the arrangement of these tetrahedral and octahedral layers makes it possible to discern three main types of clay (1:1 or TO type, 2:1 or TOT type, 2:1:1 or TOTO type) [24]. Clay minerals have different types of physical properties like- the CEC, plasticity, hardness, porosity and adsorption ability (Figure 1).
Clay organophilization depends on the characterizations (structure, propriety, type, chemical nature…etc.) of the used clay and surfactant. Among the clay minerals, smectites (2:1 or TOT type), have been widely employed to prepare Organoclay since of their excellent properties. For example, several pieces of research [24, 28, 34] are noted among the expandable clay minerals, montmorillonites were the most popular material for the preparation of organoclays because of their singular properties: charge density, cation exchange capacity (CEC) and swelling ability, its abundance in the ground, and thus its low cost. Thus, Jlassi et al. [24] noted a high CEC of clay and a uniform surface charge density promote clay organophilization; therefore montmorillonites are the most favorable swelling clay for the intercalation of organic species in its interlayer space. The compensating cation size (to be replaced) has an impact on clay organophilization. Indeed, the smaller, more mobile, and more easily hydratable the compensating cation are, the easier the exchange is [24]. For this, the purification of the raw clay in order to obtain sodium clay is an essential step in the preparation of organophilic clays. In Fact, Na+ cations are very exchangeable compared to K+ and Ca2+ cations. The net amount of surfactant adsorbed to the clay minerals can exceed the CEC of the clay minerals. Therefore the entire researcher prepares organoclay with a surfactant concentration exceeding the CEC of the clay used [34].
There are some types of organoclay based on the used surfactant; the best-known surfactants are cationic (quaternary alkylammonium, exotic (zwitterionic) and nonionic ones [28]. For cationic and zwitterionic surfactants, organoclays are obtained by the substitution of the inorganic cations located within the interlayer space through cation exchange, whereas these exchange hydrated cations are kept in the case of nonionic compounds, leading to hybrid materials with a dual hydrophilic hydrophobic behavior [28]. Cationic surfactants were principally used for the preparation of organoclay. The quaternary alkylammonium salts are the cationic surfactants the most preferred for the modification of clay minerals where her arrangements depend on both the length of the alkyl chains and the concentration of the amphiphilic molecules [28]. Therefore, currently, there is a significant several of research on the modification of clay minerals with several kinds of quaternary alkylammonium salts on a laboratory scale.
In literature, various methods are used for the preparation of organoclay such as cation exchange, organosilane, iodonium, and diazonium salt grafting. Of the methods of organophilic preparation, cation exchange is the most commonly employed [24, 34]; cation exchange has been used for five decades. This technique aims to exchange interlayer cations of the clay mineral with surfactant [24, 34].
Experimentally, organoclay can be prepared through three routes in humid states by liquid–solid or liquid–liquid interaction with the use of solvents, or by solid-state reaction with solid–solid interaction without the use of any solvents [24, 34]. The first, a solid–solid process, consists of grinding a mixture of clay powders and surfactant that is subsequently heated to ensure the diffusion of surfactant molecules in the interlayer space [24]. The solid-state reactions of clay minerals and ammonium cations were reported in 1990 [34]. The dry process leads to heterogeneous exchanged organoclays. Even if the intercalation of the compounds (cationic or polar molecules), is confirmed by the expansion of the interlayer space identified by following the 00 l reflection through X-ray diffraction (XRD) [35]. But, the absence of solvents preceding the preparation is environmentally good and makes the process more suitable for industrialization [28]. The second is carried out by a liquid–solid process by putting clay, originally powdered, in contact with an organic cation solution at a known concentration. The third method is a liquid–liquid process and consists of mixing dispersed clay slurry with a solution of organic salt. The easiest way for organoclay preparation, which was reported in many studies, is surely in an aqueous solution. Indeed, in solution the presence of water surrounding the exchangeable cations amplifies then repulsive forces at long-range order leading to exfoliation of the phyllosilicates sheets offering total access to the entire specific surface area, making easier the adsorption and interaction with surfactants of which chemical nature control the properties of the organoclays [28].
In a general view of the literature, we note that the synthesis is done in two steps, first The preparation starts with a purification step, which is a long and time-consuming process, leading most of the time to sodium clays [24]; which then facilitates the exchange with the molecule of surfactant in the second step (Figure 2):
Preparation of organoclay.
Pre-treatment of clay minerals: The clay fraction (<2 μm) was separated by sedimentation of the clay suspension (based on Stokes Law calculations), and would remove the larger sized particles (>2 μm). Free carbonate remove by attacks with a solution of hydrochloric acid HCl followed by washing several times with water to remove excess HCL; Organic matter was removed by suspension in H2O2 followed by washing several times with water to remove excess H2O2; finally, treatment with a NaCl solution. This step is essential because firstly it eliminates the impurities (calcite, quartz, etc.) and secondly, it replaces the cations between the sheets with Na + (homoiconic clays). Homoionic clays are made to facilitate exchange; thus avoiding the different degree of exchange and/or competition between the pollutant to be adsorbed and the ions initially present [36].
Preparation of organo-clays: In literature, the most frequently used method is as follows: A given mass in (g) of sodium clay mixes with a given volume in (mL) of a surfactant solution with a concentration multiple of the cation exchange capacity of the sodium clay. This mixture is then stirred for 2 to 24 hours and then centrifuged. The surfactant-modified clay is washed several times with distilled water. The organoclay obtained is dried at 60° C, then ground and sieved (Figure 2).
In the literature, most organic clay used in the treatment of water prepares under these conditions: the type of clay used is smectite, the quaternary ammonium ions as surfactant and by an ion-exchange mechanism (Cation exchange); with Surfactant concentration equals 0.5 to 4 times CEC of the clay used.
He et al. [37] used hexadecyltrimethylammonium bromide (HDTMAB) to prepare HDTMA-montmorillonite organoclays to elucidate the relation between the morphology of organoclay and the surfactant packing density within the montmorillonites galleries. The concentrations of HDTMA were 0.5 CEC, 1.5 CEC and 5.0 CEC of montmorillonite, respectively.
Hamdi and Srasra [38] prepared an organo-smectite by cation exchange with hexadecyltrimethylammonium bromide (HDTMAB) at different concentrations (1.0 to 3.0 CEC of clay CEC—cationic exchange capacity). The clay used for preparation was collected from Gabes (southeast of Tunisia).
Msadok et al. [39] modified Tunisian clay with hexadécylpyridinium (HDPy) in a concentration equivalent to 0.5 to 4.0 of cation exchange capacity of purified clay (CEC). This organoclay was also used for application as viscosifier in oil drilling fluid.
Gammoudi et al. [40] studied the influence of exchangeable cation of smectite on surfactant adsorption, Organoclays were prepared Tunisian smectite saturated with Na+, Ca2+ and Zn2+ ions and the cationic surfactant hexadecyltrimethylammonium bromide.
Yunfei et al. [41] modified sodium montmorillonite by an ion-exchange mechanism using three cationic surfactants: octadecyltrimethylammonium bromide, dimethyldioctadecylammonium bromide, and methyltrioctadecylammonium bromide. These organoclaye were prepared to investigate changes in the surfaces and structures were characterized using X-ray diffraction (XRD), thermal analysis (TG) and infrared (IR) spectroscopy.
Shirzad-Siboni et al. [42] treated montmorillonites with cetyltrimethylammonium bromide (CTAB) by the intercalation method and used it as an adsorbent to uptake herbicide from aqueous solutions.
Guégana and Le Forestierc [43] with the objective of performance evaluation of organoclays for the amoxicillin retention in a dynamic context were modified Na-montmorillonite (Na-Mt) using a set of short and moderate chain surfactant (TMA, BTA, BTMA and TOM), and a long chain organoclay (HDTMA).
De Oliveira and Guégan also prepared organophilic montmorillonite exchanged by various amounts of benzyldimethyltetradecyl ammonium chloride cationic surfactant (BDTAC) up to four times the cation exchange capacity (CEC), to be used for the adsorption of diclofenac [44].
Pandey and De [43] employed a cationic surfactant cetyl tri methyl ammonium bromide (CTAB), wich was prepared in order to explore the adsorption potential of natural bentonite for organic pollutant and anionic molecules.
The solid-state reaction is an alternative route of preparation of organoclays, but it has been less employed than cation exchange. Therefore, Table 1 summarized 22 important papers in the recent literature, indicating a strong tendency for the use of smectite, quaternary alkylammonium salts and the cation exchange technique to prepare organoclay.
Clay | Surfactant | Concentration | Reference |
---|---|---|---|
Smectite | HDPy and HDTMA | 0.5 to 3.0CEC | [45] |
Bentonite | HDTMA and MTMAB | 2CEC | [46] |
Montmorillonite | CTAB | 1CEC | [42] |
Montmorillonites | TMA and HDTMA | 40–100% CEC | [47] |
Smectite | BDTAC | 4.0CEC | [44] |
Bentonite | CTAB | — | [43] |
bentonite, | HDTMA | 2 and 4 CEC | [30] |
Bentonite | CTMAB | 0.04 to 0.28 CEC | [48] |
Bentonite. | CPC | — | [49] |
Smectite | HDPy | 3.0CEC | [50] |
Smectite | HDTMA and (HDPy) | 120 and 170% CEC | [51] |
Smectite | HDPy | 1 to 3 CEC | [52] |
Montmorillonites | HDTMA | 0.5 to 2CEC | [53] |
Montmorillonites | DDAB | — | [54] |
Bentonite. | HDPy | — | [55] |
Montmorillonites | HDPy | 20–400%. | [56] |
Montmorillonite | DDTMA and DDDMA) | 0.5–2.0 CEC | [57] |
Montmorillonite | DTAB and CTAB | 1 CEC | [58] |
Montmorillonite | BTMA | — | [59] |
montmorillonite | HDTMA | 20% | [60] |
montmorillonite | HDPy | 4 CEC | [29] |
Bentonite | HDTMA—BTEA | — | [36] |
Kinds of clay and surfactant, routes of preparations to prepare organoclay.
The following sections are organized to study the characterization of these organoclays and their application.
Understanding the structure of organoclays is essential for their practical applications. Consequently, after the synthesis of organoclay, the verification of the intercalation of surfactant in the inter-layer space of the clay by comparison before and after intercalation is essential. In literature, various characterization methods were used on the original clays and the organo-modified clays to get information on structure, expansion capacity, layer charge, pore size, crystallite size, charge distribution and pore distribution. The indispensable methods for characterization are X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FTIR), Scanning electron micrographs (SEM) and transmission electron microscopy (TEM) and determination of physic-chemical properties (CEC, area-specific, pHpzc … etc.).
Intercalation of organic surfactant between layers of clays greatly changes (increases) the basal spacing of the layers; X-ray diffraction was used to study this Changement. Otherwise, X-ray diffraction (XRD) can give the basal spacing (d001) information of the organo-clays which is very important for explaining the intercalation and configuration of surfactant between clay layers. The arrangement of cationic surfactant in the interlayer space of clay minerals was initially deduced in 1969 [34]. Generally speaking, on the basis of XRD results for raw clay the into-foliar cations only form monolayers; but in the case of organoclay, the organic cations (surfactant) may form monolayers, bilayers and paraffin-type layers. The arrangement of organic cations (surfactant) in organoclay depends on the layer charge (=interlayer cation density = packing density of the alkylammonium ions) of the clay mineral and the chain length of the organic ion. On the other hand, with an increasing concentration of added surfactants, the arrangement of surfactant change from monolayer to paraffin-type layers (Figure 3) [24, 28, 34].
Arrangement of surfactants in the interlayer space of a clay.
For example, Msodok et al. [39] notated that according to the literature, the thickness of the montmorillonite is 9.7 Å and the molecular size of HDPy is approximately 23.1 Å in length and 4.6 Å in height. At a small concentration of the cationic surfactant, the interlayer spacing (d001) of 0.5 CEC was 14.4 Å which is attributed to monolayer arrangement. For the 1.0 CEC sample, the basal spacing was 21.96 Å which is assigned to the pseudo-trimolecular arrangement. From 2.0CEC, 3.0CEC and 4.0 CEC data, the basal spacing increased in respect of 0.5 CEC-A with the maximum (d001) was 44.51 Å for 4.0 CEC. These data indicate that the surfactant molecules are located as paraffinic bilayer arrangement in the interlayer space of the montmorillonites (Figure 4) [39]. This result is in accordance with another study [45, 61].
(A) XRD patterns; and (B) FTIR spectra of clay and organoclays [
Also, He et al. [37] and Hamdi and Srasra [38] prepared an organoclay by cation exchange with hexadecyltrimethylammonium bromide at different concentrations. The X-ray diffraction analysis of various organoclays prepared indicates the basal spacings are expanded as expected depending on the surfactant concentrations. After treatment with a surfactant (0.5, 1 and 2 CEC of clay) the peak d001 of smectite at 12.69 Å passed to 17.59, 19.25 and 21.62 Å, respectively. The increase in the basal spacing of sodium clay with HDTMA cations can be attributed to the replacement of the inorganic interlayer cations and their hydration water with HDTMA cations [38].
Xi et al. prepared Organoclays based on halloysite, kaolinite and bentonite and used DRX and IR for characterization. XRD pattern has shown that the exchange of cations by surfactant causes the expansion of different clay layers. The expansion is proportional to the concentrations of HDTMA used and varied between the types of clay. For bentonite modified with 2CEC one dominant reflection at 20.2 Å was noted corresponding to basal spacing with surfactant molecules laying flat between clay mineral layers. But For bentonite modified with 4 CEC two d001 spacings were observed at18.5 Å corresponding to the bentonite expanded with HDTMA molecule laying flat between two layers and 35.7 Å attributed to the surfactant molecules at right angles to the clay mineral surface. On the other hand, the HDTMA modified kaolinite and halloysite did not show much change in XRD patterns compared to those of untreated ones [30].
Infrared spectroscopy is a powerful tool for the study of the bonding mechanisms on a molecular scale. In FTIR the cationic surfactant is characterized by the presence of C–N (vibrations in tertiary amines) and C\\H stretching bands and aliphatic C\\H stretching bands of CH2. In fact, Fourier transforms infrared spectroscopy (FTIR) will further confirm the presence of organics in the clay materials and offers the additional advantage of confirming the configuration of the organic molecule.
Generally, if examining the spectra of raw clay compared to the organoclay; noting the presence of similar bands between both clay such as (H–O–H stretching, H–O–H bending, stretching mode of Si–O...etc.). Thus, additional bands in organoclay: C–N vibrations of tertiary amines and of C–H stretching bands and aliphatic C–H of CH2. The intensity and width of the similar and additionally bands of absorbance for raw clay and organoclay exhibit distinct differences. Generally, the decrease of band intensity of the OH stretching and bending vibrations are explained by the replacement of the hydrated cations with cationic surfactants [62], which indicates the change of surface clay to the organophilic character. Thus, the increase of surfactant concentration added in clay engenders a slight shift for the symmetric bands of CH2. Generally, this shift of CH2 antisymmetric frequency was used to identify the environment surfactant in the interlayer space of organoclay [45]. The higher frequencies indicate a liquid-like environment while the lower frequencies indicate a solid-like environment.
Using infrared spectroscopy, Gammoudi et al. [45] compared the spectrum of raw clay and organic clay showing the presence of similar bands and new bands in organic clay-like as the peaks at 1463 and 1473 cm−1 indicate the presence of C–N vibrations in tertiary amines and the N–H stretching peak at 3016 cm−1 appeared only after the addition of HDTMA at concentrations greater than 3 CEC and the peak of C\\H stretching bands of CH2 and aliphatic C\\H stretching bands. The frequency and the intensity of asymmetric and symmetric stretching bands of CH2 change with the amount of intercalated surfactant. This indicates that, as the loading surfactant on sodium clay increased, the confined amine chains changed to gauche conformation for trans conformation (to lateral arrangement for paraffin arrangement). This finding is in concordance with previous studies [39] (Figure 4).
Thus in the work of Shirzad-Siboni et al. [42], the comparison of FTIR spectra of organoclay with raw clay exhibits significant changes in some of the peaks. In particular, the shift in the siloxane peak after loading of surfactant, the additional peaks appointed to –CH–stretching vibration, could be observed only in organoclay. Additionally are noted that the band at 3460 cm−1 disappeared after the modification of MMT nonmaterial with CTAB, which indicates the removal of water molecules and the change in the hydrophobicity of MMT nonmaterial. Also, is noted that with the loading of surfactant asymmetric (CH2) shifts from 2927 to 2922 cm−1 and symmetric (CH2) shifts slightly from 2856 to 2852 cm−1 for organoclay. This indicates that, in the existence of added surfactant, the confined surfactant chains adopt a fundamentally all-trans conformation. This result clearly reveals that the surface modification of MMT is achieved by surfactants.
SEM and TEM are used to collect detailed information on the morphology.
Msodek et al. [39] used SEM to determine the change in surface morphology of raw clay upon the intercalation of HDPy surfactant. Results showed that the photomicrography of raw clay exhibits massive and aggregate morphology (Figure 5). While, at low surfactant concentration (1.0 CEC ≤), the particles exhibit a compact form that can be explained by the interactions between the R groups of alkyl chains of surfactant. For the concentrations in exceeded the CEC of clay, the particles were changed to flat layers.
Photomicrographs of clay and organoclays [
Using SEM and TEM, Pandey and De observed that the raw clay (bentonite) showed rough surface morphology however organo-bentonite showed a smooth surface with large size particles.
Thus Shirzad-Siboni et al. [42] employed SEM analysis to evaluate the surface morphology of the raw clay (montmorillonites,MMT) and organoclay (montmorillonite). Results reveal that the surface morphologies of both raw clay and organoclay have an uneven structure with non-uniform size distribution. The MMT shows massive, aggregated morphology, while, after modification, the clay surface was changed to a non-aggregated morphology with severely crumpled structures. Furthermore, the surface of Organoclay was expanded.
The intercalation of surfactants in clay changes their Physicochemical properties (CEC, pore volume, Pore size, pHPZC…etc.).
Hamdi et al. noted that specific surface area decreases significantly as a function of the increase of exchanged surfactant in the specimen. The same results were obtained for the CEC and The pore volume (Vp). However, the value of PZC increased with the increase of exchanged surfactant in the raw clay. The SSA decrease indicates a compact packing of larger surfactant molecules between the silicate layers of mineral clay and blocking the passage of nitrogen molecules [63]. The same outcomes were reported by Pandey and De noted that The Pore size, surface area, as well as micro and mesopore volume, was drastically reduced after cationic surfactant treatment (Table 2).
Adsorbent | SBET | Vp | CEC | pHPZC | Pore size | Reference |
---|---|---|---|---|---|---|
Organosmectites | ||||||
0.5CEC | 14.83 | 0.0861 | 56 | 7 | — | [38] |
1CEC | 3.42 | 0.0157 | 33 | 7.7 | — | |
2CEC | 1.96 | 0.0006 | 28 | 8 | — | |
Bentonite | 33.02 | 0.10 | 97.6 | — | 11.52 | [43] |
CTAB–bentonite | 10.40 | 0.04 | — | — | 16.11 | |
Na- montmorillonites | 29.089 | 0.035 | — | — | [64] | |
DTAB- montmorillonites | 13.345 | 0.028 | — | 6.5 | — | |
CTAB- montmorillonites | 6.036 | 0.022 | — | 11.2 | — | |
Na-Bentonite | 36.5 | 0.52 | 4.5 | [65] | ||
Organoclay | 27.9 | 0.72 | 7.8 |
Physicochemical properties of the raw clay and organoclay.
Organoclays have been used in various applications. These applications include adsorbents, rheological control agents, paints, grease, cosmetics, personal care products, and oil well drilling fluids. Currently, an important application of the organoclays is in pollutant adsorption. In fact, a view of the literature shows that various studies have shown that replacing the inorganic exchange cations of clay minerals with organic cations can result in greatly enhanced abilities to remove various contaminants from water:
Phosphate, fluoride and nitrate are essential nutrients in the aquatic environment, but excessive phosphate (above 0.02 mg/L), nitrate (above 0.02 mg/L) and Fluoride (above 1.5 mg/L) input may lead to eutrophication (causing degradation of water quality) respectively. Nowadays, the presence of fluoride, phosphate and nitrate in the environment has been identified as one of the acute problems worldwide. Organoclay has been successfully utilized for the removal of nitrate, phosphate and fluoride:
Gammoudi et al. prepared organoclay with smectite using two cationic surfactants (HDPy and HDTMA) for fluoride removal from wastewaters. The optimal condition suitable for defluoridation consists of low fluoride concentration, contact time equal to 6 h and acidic pH. These organoclays showed high removal capacities for fluoride ions [45].
Xi et al. prepared various Organoclays with on halloysite, kaolinite and bentonite for removal of nitrate. The results showed that all these raw clays showed poor adsorption amounts for nitrate. However, when these clays were modified with surfactant HDTMA in 2 or 4 CEC, the removal amounts of these clays were greatly improved. Thus, among all these organoclays, HDTMA modified bentonite showed the best result [30].
Ma and Zhu [48] used inorganic–organo-bentonite which is prepared by replacing the exchangeable inorganic cations with cetyltrimethylammonium bromide (CTMAB) to phosphures from water. The results of this study reveal that inorganic–organo-bentonite can act as a successful adsorbent for removing the phosphures from contaminated water. More than 95% phosphate and 99% phenanthrene were removed from the water within 30 min. The amount of sorbed phosphate increased as pH decreased and the sorption amount increased slightly with an increase in temperature [48].
Dyes and pigments are widely used by several industries like plastics, textile, cosmetics…etc. Textile dyeing process is an important source of contamination responsible for the continuous pollution of the environment. In recent years Organo-clays have been attractive for use as selective sorbents for dyes:
Tabak et al. [49] studied the adsorption of the Reactive Red 120 by cetylpyridinium modified Resadiye bentonite (CP-bentonite) prepared by ion exchange at different temperature, force ionique and pH levels. Their results showed that the structural arrangement of cetylpyridinium ions in the CP-bentonite sample, as well as the pH, temperature and ionic strength of the bulk solution, influenced the adsorption of RR 120 dye from aqueous solutions by CP-bentonite [49].
Ma et al. [46] showed that bentonite modified with hexadecyltrimethylammonium bromide could be used as a highly efficient adsorbent for the removal of acid dyes from an aqueous solution. The study reveals that the adsorption capacity of organobentonites is affected by the surfactant alkyl chain length [46].
Gammoudi and Srassra [50] studied the removal of three dyes (methyl orange (MO), indigo carmine (IC) and phenol red (PR) on the surface of Tunisian HDPy-modified; the maximum adsorption capacity from the Langmuir equation was calculated at 227.27, 326.40, and 344.82 mg/g, respectively. The results revealed that the kinetics uptake was fast and equilibrium was attained within 30 min for IC, PR and 60 min for MO.
Shirzad-Siboni et al. [42] were prepare surfactant-modified pillared montmorillonites using cetyltrimethylammonium bromide and used them as adsorbents to remove bentazon from aqueous solutions. Results showed that the maximum adsorption capacity was estimated to be 500 mg/g at pH 3 and room temperature. The removal efficiency at optimum pH 3 was found to increase with the increase in contact time and adsorption dosage, but to decrease with an increase in initial bentazon concentration [42].
Carrizosa et al. [41] examined the adsorption of the herbicide dicamba by organoclays at various concentrations and pH levels. Their results showed that the adsorption capacity of organoclays is favored for high-layer charge and saturation with bulky organic cations close to the CEC.
Some heavy metals are notorious water pollutants with high toxicity and carcinogenicity. Heavy metals have been removed from water by adsorption technology using nanoparticles. Organoclay is effective for the removal of various heavy metals. The elimination efficacies of these contaminants are discussed below.
HDTMA modified natural kaolin has been confirmed effective sorbent for Cr (VI) with a maximum adsorption capacity of 27.8 mg/g, while the unmodified natural kaolin was only 0.7 mg/g [60]. Results indicate that most of the adsorption of chromate occurred through the anion exchange of the Br-anion of the HDTMA ion pair [66].
Similarly, the adsorption scheme of oxygen anions of Cr and Mowas studied with bentonite modified by cetylpyridine bromide (CPBr). The equilibrium adsorption capacity of Mo (VI) of 1.4 mmol/g quantity to double the capacity of Cr(VI) (0.7 mmol/g), indicating that Mo (VI) was removed on organic bentonite in the form of polynuclear anions [67].
Various researches have reported the successful elimination of pharmaceutical pollutants using organoclay:
Saitoh and Shibayama synthesized organo-clays: Didodecyldimethylammonium bromide (DDAB)-montmorillonite which was used for the removal of 1β-lactam antibiotics from water. The study showed that the removal of antibiotics increased with increasing the amount of organoclay added and the amount of DDAB sorbed on MT. Thus, the authors postulated that the Didodecyldimethylammonium bromide (DDAB)-montmorillonite (MT) organoclay was a useful sorbent not only for the removal of β-lactam antibiotics from water but for their eco-friendly degradation [54].
Polubesova et al. [68] examined tetracycline and sulfonamide antibiotics sorption by the BDMHDA modified montmorillonite. Their results indicated that BDMHDA modified montmorillonite is very efficient for water purification from tetracycline and sulfonamide antibiotics [68].
Guégan and Le Forestier [47] used modified montmorillonite with tetramethyl ammonium (TMA) and hexadecyl trimethyl ammonium (HDTMA) cationic surfactants as adsorbents for the retention of amoxicillin (AMX) [47].
Masooleh et al. [53] studied the performance of a organically modified nanoclay for petroleum hydrocarbon adsorption. The obtained results that the adsorption capacity of the organoclay was clearly higher than that of the unmodified clay and the hydrocarbons the adsorption capacity was in the range of 4 to 10 g of adsorbent. Also, adsorption equilibrium was attained within 1 h.
Park et al. [57] prepared two types of organoclays from different surfactants (DDTMA and DDDMA) for the adsorption of phenolic compounds. This study revealed the potential utility of the organoclays as adsorbents for the uptake of industrial pollutants in environmental applications.
Zhang et al. [64] were prepared organoclays using withdodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB); were used as adsorbents for 4-chlorophenol and 2,4-dichlorophenol. This study demonstrates that the adsorption process is affected by the initial solution pH and temperature.
Bentonite clay is suggested as a buffer material in various concepts for repositories for high-level radioactive waste. Two different mechanisms have been established to study the importance of the ionic balance between the interlayer space of montmorillonites and an external solution: the Donnan equilibrium and the ion exchange equilibrium [69].
Yang et al. [55] synthesized Hexadecylpyridinium Chloride Monohydrate modified bentonite (HDPy-bent) and used it as an adsorbent to remove-99 (99Tc). Results are demonstrated that the HDPy-bent is a low-cost sorbent which can efficiently eliminate Technetium-99 from wastewaters.
Li et al. [58] examined the efficacy of organoclay as sorbents to bind iodide (I−) and iodate (IO3−) from groundwater. Results showed that these sorbents were highly effective at removing I− and IO3 from groundwater under oxic conditions, with the adsorption capacity up to 30 mg I/g sorbent.
Some studies, evaluate the efficiency and capability of organoclay to simultaneously remove various pollutants from wastewater:
Yahya et al. [61] used smectitic clay modified using cationic surfactant (hexadecylpyridinium for the removal of fluoride and phosphate single and industrial aqueous solutions. The results show low adsorption ability for fluoride and phosphate ions comparing the case of single solutions. Thus, the selectivity of fluoride is better than phosphate and with coexisting chloride, sulfate ions and other cations.
Xiaoying et al. [36] are studying the possibility of organoclays used to simultaneously remove amoxicillin (AMX) and Cu (II) from wastewater. Results showed that the adsorption of AMX onto organ-bentonite was 6 times higher than that using bentonite (control), while adsorption of Cu (II) on organ-bentonite showed comparable results as that using bentonite. The simultaneous adsorption of AMX and Cu (II) onto organ-bentonite occurred through partition for AMX and ion-exchange for Cu (II). More than 34.8% AMX and 43.6% Cu (II) were removed from industrial wastewater, indicating its great potential removal of mixed organic and metal contaminants.
Oyanedel-Craver et al. [36] were studying the feasibility of using hexadecyltrimethylammonium bentonite clay (HDTMA-clay) and benzyl triethylammonium bentonite clay (BTEA-clay) for simultaneous sorption of benzene and one of four heavy metals (Pb, Cd, Zn and Hg). Results showed that both organoclays tested had dual sorptive properties for both heavy metals and an organic contaminant. But, sorption of Pb, Cd, and Zn on both BTEA- and HDTMA-clay decreases in the presence of benzene relative to the sorption obtained without benzene present.
Generally, the predominant mechanism of the adsorption of dye, inorganic oxyanions (fluoride, phosphate nitrate) is an ion exchange [46, 51, 61] (Figure 6). The mechanisms mainly include electrostatic adsorption of heavy metal, redox, ion exchange, precipitation, coordination (chelation), as well as surface complexation. For heavy metals, the mechanisms mainly include surface complexation, redox, ion exchange, precipitation, coordination (chelation) and electrostatic adsorption (Figure 7) [26].
Mechanism of pollutant (P) uptake in organoclay.
Adsorption mechanisms of functional organoclays for heavy metal ions [
Table 3 represents various applications of organoclay for the removal of wastewaters pollutants by adsorption.
Pollutants | Removing capacities | Isotherm study | Kinetics study | Mechanism | Reference |
---|---|---|---|---|---|
Dye | 144.08–249.62 | — | — | ion-exchange | [46] |
Dye | 227.27–344.82 | Langmuir | pseudo-second order | ion-exchange | [50] |
Dye | 81.97 | Langmuir | pseudo-second order | ion-exchange | [49] |
Dye | 324.36–399.74 | Freundlich | pseudo-second order | — | [65] |
Heavy metal | 11.970 | Langmuir | pseudo-second order | Complexation | [70] |
Heavy metal | — | Freundlich | pseudo-second order | ion-exchange | [71] |
Herbicide | 500 mg/g | Langmuir | pseudo-second order | — | [42] |
Nitrate | (0.287 meq/g | Langmuir | pseudo-second order | — | [72] |
Chromate-molybdate | 0.7–1.4 mmol/g | — | pseudo-second order | ion-exchange | [73] |
chlorophenols | 458.2–585.80 | Langmuir | pseudo-second order | Complexation | [64] |
Phenol | — | Freundlich | pseudo-second order | various mechanisms | [57] |
Iodide and iodate | 21.1–27. | Langmuir | — | — | [58] |
Antibiotics | 96–99.9% | Langmuir | — | — | [68] |
Fluoride | 14.02 | Langmuir | pseudo-second order | ion-exchange | [45] |
Nitrate | 2.63–15.38 | Langmuir | pseudo-second order | ion-exchange | [74] |
Dey | 49.53 mg g−1 | — | — | — | [43] |
Nitrate-perchlorate | 0.6–1.1 mmolg−1 | Langmuir | pseudo-second order | — | [29] |
Phosphate-fluoride | 11.36–27.77 | Langmuir | pseudo-second order | ion-exchange | [61] |
Amoxicillin-Cu(II) | 34.8–43.6% | Langmuir Freundlich | pseudo-second order pseudo-first order | partition ion-exchange | [60] |
Applications of organoclay for the elimination of water pollutants by adsorption.
The study of organoclays is a vast field and shows immense potential to be explored. This chapter describes the various ways of preparation of organoclays with the use of cationic surfactants (quaternary alkyl ammonium). Generally, organoclay is obtained by the replacement of the inorganic cations through cation exchange with surfactant. Organoclay can be made using a variety of clay minerals; however, smectite is the most commonly used due to its specific properties. Thus, quaternary ammonium cations are most commonly used as surfactants.
A detailed understanding of the structure of organoclay is of importance in its design and applications. In this chapter, FTIR, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction (XRD) has been employed to provide insights into the interlayer structure and morphology of organoclay. The details are as follows:
XRD patterns show that the interlayer spacing increased with the increase of the added surfactant concentration.
FTIR spectra confirm these results were by the changes in frequencies and intensities of symmetric and antisymmetric stretching bands of -CH2.
The intercalation of surfactants in clay decreases the specific surface area, CEC and pore volume. However, increases the value of pH ZPC.
Using SEM and TEM indicate that the raw clay showed rough surface morphology however organoclay showed a smooth surface with large size particles.
Organoclays can be used in various applications including adsorbent systems in the environmental field. These adsorbents display interesting adsorption properties for several organic compounds, especially hydrophobic chemicals.
Despite the potential interest in environmental applications, the use of organoclays appears to be limited to batch experiments but has not yet been explored under dynamic conditions that reduce the efficiency of adsorption.
Finley, overall, in this chapter researchers suggest that the Organoclay could be considered a cheap and efficient adsorbent for the removal of most of the chemical pollutants from wastewater that could be of socioeconomic and environmental relevance.
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Currently, he is a professor of Orthodontics. He holds a Certificate of Advanced Study type A in Technology of Biomaterials used in Dentistry (1995); Certificate of Advanced Study type B in Dento-Facial Orthopaedics (1997) from the Faculty of Dental Surgery, University Denis Diderot-Paris VII, France; Diploma of Advanced Study (DESA) in Biocompatibility of Biomaterials from the Faculty of Medicine and Pharmacy of Casablanca (2002); Certificate of Clinical Occlusodontics from the Faculty of Dentistry of Casablanca (2004); University Diploma of Biostatistics and Perceptual Health Measurement from the Faculty of Medicine and Pharmacy of Casablanca (2011); and a University Diploma of Pedagogy of Odontological Sciences from the Faculty of Dentistry of Casablanca (2013). 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He also obtained an MSc in Molecular and Genetic Medicine, and a Ph.D. in Clinical Immunology and Human Genetics from the University of Sheffield, UK. He also completed a short-term fellowship in Pediatric Clinical Immunology and Bone Marrow Transplantation at Newcastle General Hospital, England. Dr. Rezaei is a Full Professor of Immunology and Vice Dean of International Affairs and Research, at the School of Medicine, Tehran University of Medical Sciences, and the co-founder and head of the Research Center for Immunodeficiencies. He is also the founding president of the Universal Scientific Education and Research Network (USERN). Dr. Rezaei has directed more than 100 research projects and has designed and participated in several international collaborative projects. He is an editor, editorial assistant, or editorial board member of more than forty international journals. He has edited more than 50 international books, presented more than 500 lectures/posters in congresses/meetings, and published more than 1,100 scientific papers in international journals.",institutionString:"Tehran University of Medical Sciences",institution:{name:"Tehran University of Medical Sciences",country:{name:"Iran"}}},{id:"180733",title:"Dr.",name:"Jean",middleName:null,surname:"Engohang-Ndong",slug:"jean-engohang-ndong",fullName:"Jean Engohang-Ndong",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/180733/images/system/180733.png",biography:"Dr. Jean Engohang-Ndong was born and raised in Gabon. After obtaining his Associate Degree of Science at the University of Science and Technology of Masuku, Gabon, he continued his education in France where he obtained his BS, MS, and Ph.D. in Medical Microbiology. He worked as a post-doctoral fellow at the Public Health Research Institute (PHRI), Newark, NJ for four years before accepting a three-year faculty position at Brigham Young University-Hawaii. Dr. Engohang-Ndong is a tenured faculty member with the academic rank of Full Professor at Kent State University, Ohio, where he teaches a wide range of biological science courses and pursues his research in medical and environmental microbiology. Recently, he expanded his research interest to epidemiology and biostatistics of chronic diseases in Gabon.",institutionString:"Kent State University",institution:{name:"Kent State University",country:{name:"United States of America"}}},{id:"188773",title:"Prof.",name:"Emmanuel",middleName:null,surname:"Drouet",slug:"emmanuel-drouet",fullName:"Emmanuel Drouet",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/188773/images/system/188773.png",biography:"Emmanuel Drouet, PharmD, is a Professor of Virology at the Faculty of Pharmacy, the University Grenoble-Alpes, France. As a head scientist at the Institute of Structural Biology in Grenoble, Dr. Drouet’s research investigates persisting viruses in humans (RNA and DNA viruses) and the balance with our host immune system. He focuses on these viruses’ effects on humans (both their impact on pathology and their symbiotic relationships in humans). He has an excellent track record in the herpesvirus field, and his group is engaged in clinical research in the field of Epstein-Barr virus diseases. He is the editor of the online Encyclopedia of Environment and he coordinates the Universal Health Coverage education program for the BioHealth Computing Schools of the European Institute of Science.",institutionString:null,institution:{name:"Grenoble Alpes University",country:{name:"France"}}},{id:"131400",title:"Prof.",name:"Alfonso J.",middleName:null,surname:"Rodriguez-Morales",slug:"alfonso-j.-rodriguez-morales",fullName:"Alfonso J. Rodriguez-Morales",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/131400/images/system/131400.png",biography:"Dr. Rodriguez-Morales is an expert in tropical and emerging diseases, particularly zoonotic and vector-borne diseases (especially arboviral diseases). He is the president of the Travel Medicine Committee of the Pan-American Infectious Diseases Association (API), as well as the president of the Colombian Association of Infectious Diseases (ACIN). He is a member of the Committee on Tropical Medicine, Zoonoses, and Travel Medicine of ACIN. He is a vice-president of the Latin American Society for Travel Medicine (SLAMVI) and a Member of the Council of the International Society for Infectious Diseases (ISID). Since 2014, he has been recognized as a Senior Researcher, at the Ministry of Science of Colombia. He is a professor at the Faculty of Medicine of the Fundacion Universitaria Autonoma de las Americas, in Pereira, Risaralda, Colombia. He is an External Professor, Master in Research on Tropical Medicine and International Health, Universitat de Barcelona, Spain. He is also a professor at the Master in Clinical Epidemiology and Biostatistics, Universidad Científica del Sur, Lima, Peru. In 2021 he has been awarded the “Raul Isturiz Award” Medal of the API. Also, in 2021, he was awarded with the “Jose Felix Patiño” Asclepius Staff Medal of the Colombian Medical College, due to his scientific contributions to COVID-19 during the pandemic. He is currently the Editor in Chief of the journal Travel Medicine and Infectious Diseases. His Scopus H index is 47 (Google Scholar H index, 68).",institutionString:"Institución Universitaria Visión de las Américas, Colombia",institution:null},{id:"332819",title:"Dr.",name:"Chukwudi Michael",middleName:"Michael",surname:"Egbuche",slug:"chukwudi-michael-egbuche",fullName:"Chukwudi Michael Egbuche",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/332819/images/14624_n.jpg",biography:"I an Dr. Chukwudi Michael Egbuche. I am a Senior Lecturer in the Department of Parasitology and Entomology, Nnamdi Azikiwe University, Awka.",institutionString:null,institution:{name:"Nnamdi Azikiwe University",country:{name:"Nigeria"}}},{id:"284232",title:"Mr.",name:"Nikunj",middleName:"U",surname:"Tandel",slug:"nikunj-tandel",fullName:"Nikunj Tandel",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/284232/images/8275_n.jpg",biography:'Mr. Nikunj Tandel has completed his Master\'s degree in Biotechnology from VIT University, India in the year of 2012. He is having 8 years of research experience especially in the field of malaria epidemiology, immunology, and nanoparticle-based drug delivery system against the infectious diseases, autoimmune disorders and cancer. He has worked for the NIH funded-International Center of Excellence in Malaria Research project "Center for the study of complex malaria in India (CSCMi)" in collaboration with New York University. The preliminary objectives of the study are to understand and develop the evidence-based tools and interventions for the control and prevention of malaria in different sites of the INDIA. Alongside, with the help of next-generation genomics study, the team has studied the antimalarial drug resistance in India. Further, he has extended his research in the development of Humanized mice for the study of liver-stage malaria and identification of molecular marker(s) for the Artemisinin resistance. At present, his research focuses on understanding the role of B cells in the activation of CD8+ T cells in malaria. Received the CSIR-SRF (Senior Research Fellow) award-2018, FIMSA (Federation of Immunological Societies of Asia-Oceania) Travel Bursary award to attend the IUIS-IIS-FIMSA Immunology course-2019',institutionString:"Nirma University",institution:{name:"Nirma University",country:{name:"India"}}},{id:"334383",title:"Ph.D.",name:"Simone",middleName:"Ulrich",surname:"Ulrich Picoli",slug:"simone-ulrich-picoli",fullName:"Simone Ulrich Picoli",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/334383/images/15919_n.jpg",biography:"Graduated in Pharmacy from Universidade Luterana do Brasil (1999), Master in Agricultural and Environmental Microbiology from Federal University of Rio Grande do Sul (2002), Specialization in Clinical Microbiology from Universidade de São Paulo, USP (2007) and PhD in Sciences in Gastroenterology and Hepatology (2012). She is currently an Adjunct Professor at Feevale University in Medicine and Biomedicine courses and a permanent professor of the Academic Master\\'s Degree in Virology. She has experience in the field of Microbiology, with an emphasis on Bacteriology, working mainly on the following topics: bacteriophages, bacterial resistance, clinical microbiology and food microbiology.",institutionString:null,institution:{name:"Universidade Feevale",country:{name:"Brazil"}}},{id:"229220",title:"Dr.",name:"Amjad",middleName:"Islam",surname:"Aqib",slug:"amjad-aqib",fullName:"Amjad Aqib",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/229220/images/system/229220.png",biography:"Dr. Amjad Islam Aqib obtained a DVM and MSc (Hons) from University of Agriculture Faisalabad (UAF), Pakistan, and a PhD from the University of Veterinary and Animal Sciences Lahore, Pakistan. Dr. Aqib joined the Department of Clinical Medicine and Surgery at UAF for one year as an assistant professor where he developed a research laboratory designated for pathogenic bacteria. Since 2018, he has been Assistant Professor/Officer in-charge, Department of Medicine, Manager Research Operations and Development-ORIC, and President One Health Club at Cholistan University of Veterinary and Animal Sciences, Bahawalpur, Pakistan. He has nearly 100 publications to his credit. His research interests include epidemiological patterns and molecular analysis of antimicrobial resistance and modulation and vaccine development against animal pathogens of public health concern.",institutionString:"Cholistan University of Veterinary and Animal Sciences",institution:{name:"University of Agriculture Faisalabad",country:{name:"Pakistan"}}},{id:"333753",title:"Dr.",name:"Rais",middleName:null,surname:"Ahmed",slug:"rais-ahmed",fullName:"Rais Ahmed",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/333753/images/20168_n.jpg",biography:null,institutionString:null,institution:{name:"University of Agriculture Faisalabad",country:{name:"Pakistan"}}},{id:"62900",title:"Prof.",name:"Fethi",middleName:null,surname:"Derbel",slug:"fethi-derbel",fullName:"Fethi Derbel",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/62900/images/system/62900.jpeg",biography:"Professor Fethi Derbel was born in 1960 in Tunisia. He received his medical degree from the Sousse Faculty of Medicine at Sousse, University of Sousse, Tunisia. He completed his surgical residency in General Surgery at the University Hospital Farhat Hached of Sousse and was a member of the Unit of Liver Transplantation in the University of Rennes, France. He then worked in the Department of Surgery at the Sahloul University Hospital in Sousse. Professor Derbel is presently working at the Clinique les Oliviers, Sousse, Tunisia. His hospital activities are mostly concerned with laparoscopic, colorectal, pancreatic, hepatobiliary, and gastric surgery. He is also very interested in hernia surgery and performs ventral hernia repairs and inguinal hernia repairs. He has been a member of the GREPA and Tunisian Hernia Society (THS). During his residency, he managed patients suffering from diabetic foot, and he was very interested in this pathology. For this reason, he decided to coordinate a book project dealing with the diabetic foot. Professor Derbel has published many articles in journals and collaborates intensively with IntechOpen Access Publisher as an editor.",institutionString:"Clinique les Oliviers",institution:null},{id:"300144",title:"Dr.",name:"Meriem",middleName:null,surname:"Braiki",slug:"meriem-braiki",fullName:"Meriem Braiki",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/300144/images/system/300144.jpg",biography:"Dr. Meriem Braiki is a specialist in pediatric surgeon from Tunisia. She was born in 1985. She received her medical degree from the University of Medicine at Sousse, Tunisia. She achieved her surgical residency training periods in Pediatric Surgery departments at University Hospitals in Monastir, Tunis and France.\r\nShe is currently working at the Pediatric surgery department, Sidi Bouzid Hospital, Tunisia. Her hospital activities are mostly concerned with laparoscopic, parietal, urological and digestive surgery. She has published several articles in diffrent journals.",institutionString:"Sidi Bouzid Regional Hospital",institution:null},{id:"229481",title:"Dr.",name:"Erika M.",middleName:"Martins",surname:"de Carvalho",slug:"erika-m.-de-carvalho",fullName:"Erika M. de Carvalho",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/229481/images/6397_n.jpg",biography:null,institutionString:null,institution:{name:"Oswaldo Cruz Foundation",country:{name:"Brazil"}}},{id:"186537",title:"Prof.",name:"Tonay",middleName:null,surname:"Inceboz",slug:"tonay-inceboz",fullName:"Tonay Inceboz",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/186537/images/system/186537.jfif",biography:"I was graduated from Ege University of Medical Faculty (Turkey) in 1988 and completed his Med. PhD degree in Medical Parasitology at the same university. I became an Associate Professor in 2008 and Professor in 2014. I am currently working as a Professor at the Department of Medical Parasitology at Dokuz Eylul University, Izmir, Turkey.\n\nI have given many lectures, presentations in different academic meetings. I have more than 60 articles in peer-reviewed journals, 18 book chapters, 1 book editorship.\n\nMy research interests are Echinococcus granulosus, Echinococcus multilocularis (diagnosis, life cycle, in vitro and in vivo cultivation), and Trichomonas vaginalis (diagnosis, PCR, and in vitro cultivation).",institutionString:"Dokuz Eylül University",institution:{name:"Dokuz Eylül University",country:{name:"Turkey"}}},{id:"71812",title:"Prof.",name:"Hanem Fathy",middleName:"Fathy",surname:"Khater",slug:"hanem-fathy-khater",fullName:"Hanem Fathy Khater",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/71812/images/1167_n.jpg",biography:"Prof. Khater is a Professor of Parasitology at Benha University, Egypt. She studied for her doctoral degree, at the Department of Entomology, College of Agriculture, Food and Natural Resources, University of Missouri, Columbia, USA. She has completed her Ph.D. degrees in Parasitology in Egypt, from where she got the award for “the best scientific Ph.D. dissertation”. She worked at the School of Biological Sciences, Bristol, England, the UK in controlling insects of medical and veterinary importance as a grant from Newton Mosharafa, the British Council. 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She was a recipient of a Commonwealth fellowship supported by British Council tenable at the Centre for Entomology and Parasitology (CAEP), Keele University, United Kingdom between 2004 and 2005. She was awarded an Honorary Visiting Research Fellow at the same university from 2005 to 2007. \nShe has been an external examiner to the Department of Veterinary Microbiology and Parasitology, University of Ibadan, MSc programme between 2010 and 2012. She is a member of the Nigerian Society of Experimental Biology (NISEB), Parasitology and Public Health Society of Nigeria (PPSN), Science Association of Nigeria (SAN), Zoological Society of Nigeria (ZSN), and is Vice Chairperson of the Organisation of Women in Science (OWSG), LASU chapter. She served as Head of Department of Zoology and Environmental Biology, Lagos State University from 2007 to 2010 and 2014 to 2016. 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