Among biopolymer-based adsorbents, composites in the form of beads have shown promising results in terms of high adsorption capacity and ease of separation from the effluents. This review addresses the potential of biopolymer-based beads to remediate wastewaters polluted with emerging organic contaminants, for instance dyes, active pharmaceutical ingredients, pesticides, phenols, oils, polyaromatic hydrocarbons, and polychlorinated biphenyls. High adsorption capacities up to 2541.76 mg g-1 for dyes, 392 mg g-1 for pesticides and phenols, 1890.3 mg g-1 for pharmaceuticals, and 537 g g-1 for oils and organic solvents have been reported. The review also attempted to convey to its readers the significance of wastewater treatment through adsorption by providing an overview on decontamination technologies of organic water contaminants. Various preparation methods of biopolymer-based gel beads and adsorption mechanisms involved in the process of decontamination have been summarized and analyzed. Therefore, we believe there is an urge to discuss the current state of the application of biopolymer-based gel beads for the adsorption of organic pollutants from wastewater and future perspectives in this regard since it is imperative to treat wastewater before releasing into freshwater bodies.
Effective removal of 4-chloro-2-methylphenoxyacetic acid (MCPA), an emerging agrochemical contaminant in water with carcinogenic and mutagenic health effects has been reported using hydrothermally synthesized MIL-101(Cr) metal-organic framework (MOF). The properties of the MOF were ascertained using powdered X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and surface area and porosimetry (SAP). The BET surface area and pore volume of the MOF were 1439 m2 g-1 and 0.77 cm3 g-1, respectively. Artificial neural network (ANN) model was significantly employed for the accurate prediction of the experimental adsorption capacity (qe ) values with minimal error. A rapid removal of the pollutant (99%) was recorded within short time (approx. 25 min), and the reusability of the MOF (20 mg) was achieved up to six cycles with over 90% removal efficiency. The kinetics, isotherm and thermodynamics of the process were described by the pseudo-second-order, Freundlich and endothermic adsorption, respectively. The adsorption process is spontaneous based on the negative Gibbs free energy values. The significant correlation between the experimental findings and simulation results suggests the great potential of MIL-101(Cr) for the remediation of MCPA from water matrices.
Perfluorooctanoic acid (PFOA) has been identified as the most toxic specie of the family of perfluorinated carboxylic acids (PFCAs). It has been widely distributed and frequently detected in environmental wastewater. The compound's unique features such as inherent stability, rigidity, and resistance to harsh chemical and thermal conditions, due to its multiple and strong C-F bonds have resulted in its resistance to conventional wastewater remediations. Photolysis and bioremediation methods have been proven to be inefficient in their elimination, hence this article presents intensive literature studies and summarized findings reported on the application of advanced oxidation processes (AOPs) and photocatalytic degradation techniques as the best alternatives for the PFOA elimination from wastewater. Techniques of persulfate, photo-Fenton, electrochemical, photoelectrochemical and photocatalytic degradation have been explored and their mechanisms for the degradation and defluorination of the PFOA have been demonstrated. The major advantage of AOPs techniques has been centralized on the generation of active radicals such as sulfate (SO4•-) hydroxyl (•OH). While for the photocatalytic process, photogenerated species (electron (e) and holes (h + vb)) initiated the process. These active radicals and photogenerated species possessed potentiality to attack the PFOA molecule and caused the cleavage of the C-C and C-F bonds, resulting in its efficient degradation. Shorter-chain PFCAs have been identified as the major intermediates detected and the final stage entails its complete mineralization to carbon dioxide (CO2) and fluoride ion (F-). The prospects and challenges associated with the outlined techniques have been highlighted for better understanding of the subject matter for the PFOA elimination from real wastewaters.
Corrosion prevention has been a global phenomenon, particularly in metallic and construction engineering. Most inhibitors are expensive and toxic. Therefore, developing nontoxic and cheap corrosion inhibitors has been a way forward. In this work, L-arginine was successfully grafted on chitosan by the thermal technique using a reflux condenser. This copolymer was characterized by Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The corrosion inhibition performance of the composite polymer was tested on mild steel in 0.5M HCl by electrochemical methods. The potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) results were consistent. The inhibition efficiency at optimum concentration rose to 91.4%. The quantum chemical calculation parameters show good properties of the material as a corrosion inhibitor. The molecular structure of the inhibitor was subjected to density functional theory (DFT) to understand its theoretical properties, and the results confirmed the inhibition efficiency of the grafted polymer for corrosion prevention.
Covalent organic frameworks (COFs) are class of porous coordination polymers made up of organic building blocks joined together by covalent bonding through thermodynamic and controlled reversible polymerization reactions. This review discussed versatile applications of COFs for remediation of wastewater containing dyes, emphasizing the advantages of both pristine and modified materials in adsorption, membrane separation, and advanced oxidations processes. The excellent performance of COFs towards adsorption and membrane filtration has been centered to their higher crystallinity and porosity, exhibiting exceptionally high surface area, pore size and pore volumes. Thus, they provide more active sites for trapping the dye molecules. On one hand, the photocatalytic performance of the COFs was attributed to their semiconducting properties, and when coupled with other functional semiconducting materials, they achieve good mechanical and thermal stabilities, positive light response, and narrow band gap, a typical characteristic of excellent photocatalysts. As such, COFs and their composites have demonstrated excellent potentialities for the elimination of the dyes.
Perfluoroalkyl carboxylic acids (PFCAs) are sub-class of perfluoroalkyl substances commonly detected in water matrices. They are persistent in the environment, hence highly toxic to living organisms. Their occurrence at trace amount, complex nature and prone to matrix interference make their extraction and detection a challenge. This study consolidates current advancements in solid-phase extraction (SPE) techniques for the trace-level analysis of PFCAs from water matrices. The advantages of the methods in terms of ease of applications, low-cost, robustness, low solvents consumption, high pre-concentration factors, better extraction efficiency, good selectivity and recovery of the analytes have been emphasized. The article also demonstrated effectiveness of some porous materials for the adsorptive removal of the PFCAs from the water matrices. Mechanisms of the SPE/adsorption techniques have been discussed. The success and limitations of the processes have been elucidated.
The widespread consumption of pharmaceutical drugs and their incomplete breakdown in organisms has led to their extensive presence in aquatic environments. The indiscriminate use of antibiotics, such as sulfonamides, has contributed to the development of drug-resistant bacteria and the persistent pollution of water bodies, posing a threat to human health and the safety of the environment. Thus, it is paramount to explore remediation technologies aimed at decomposing and complete elimination of the toxic contaminants from pharmaceutical wastewater. The review aims to explore the utilization of metal-oxide nanoparticles (MONPs) and graphitic carbon nitrides (g-C3N4) in photocatalytic degradation of sulfonamides from wastewater. Recent advances in oxidation techniques such as photocatalytic degradation are being exploited in the elimination of the sulfonamides from wastewater. MONP and g-C3N4 are commonly evolved nano substances with intrinsic properties. They possessed nano-scale structure, considerable porosity semi-conducting properties, responsible for decomposing wide range of water pollutants. They are widely applied for photocatalytic degradation of organic and inorganic substances which continue to evolve due to the low-cost, efficiency, less toxicity, and more environmentally friendliness of the materials. The review focuses on the current advances in the application of these materials, their efficiencies, degradation mechanisms, and recyclability in the context of sulfonamides photocatalytic degradation.
Water-borne emerging pollutants are among the greatest concern of our modern society. Many of these pollutants are categorized as endocrine disruptors due to their environmental toxicities. They are harmful to humans, aquatic animals, and plants, to the larger extent, destroying the ecosystem. Thus, effective environmental remediations of these pollutants became necessary. Among the various remediation techniques, adsorption and photocatalytic degradation have been single out as the most promising. This review is devoted to the compilations and analysis of the role of metal-organic frameworks (MOFs) and their composites as potential materials for such applications. Emerging organic pollutants, like dyes, herbicides, pesticides, pharmaceutical products, phenols, polycyclic aromatic hydrocarbons, and perfluorinated alkyl substances, have been extensively studied. Important parameters that affect these processes, such as surface area, bandgap, percentage removal, equilibrium time, adsorption capacity, and recyclability, are documented. Finally, we paint the current scenario and challenges that need to be addressed for MOFs and their composites to be exploited for commercial applications.
Frequent detection of sulfonamides (SAs) pharmaceuticals in wastewater has necessitated the discovery of suitable technology for their sustainable remediation. Adsorption has been widely investigated due to its effectiveness, simplicity, and availability of various adsorbent materials from natural and artificial sources. This review highlighted the potentials of carbon-based adsorbents derived from agricultural wastes such as lignocellulose, biochar, activated carbon, carbon nanotubes graphene materials as well as organic polymers such as chitosan, molecularly imprinted polymers, metal, and covalent frameworks for SAs removal from wastewater. The promising features of these materials including higher porosity, rich carbon-content, robustness, good stability as well as ease of modification have been emphasized. Thus, the materials have demonstrated excellent performance towards the SAs removal, attributed to their porous nature that provided sufficient active sites for the adsorption of SAs molecules. The modification of physico-chemical features of the materials have been discussed as efficient means for enhancing their adsorption and reusable performance. The article also proposed various interactive mechanisms for the SAs adsorption. Lastly, the prospects and challenges have been highlighted to expand the knowledge gap on the application of the materials for the sustainable removal of the SAs.
Environmental pollution has been increasing since last decade due to increasing industrialisation and urbanisation. Various kinds ofenvironmental pollutants including carbon dioxide (CO2), dyes, pharmaceuticals, phenols, heavy metals along with many organic and inorganic species have been discovered in the various environmental compartments which possess harmful impacts tox human health, wildlife, and ecosystems. Thus, various efforts have been made through regulations, technological advancements, and public awareness campaigns to reduce the impact of the pollution. However, finding suitable alternatives to mitigate their impacts remained a challenge. Metal-organic frameworks (MOFs) are one of the advanced materials with unique features such as high porosity and stability which exhibit versatile applications in environmental remediation. Their composites with titanium oxide nanoparticles (TiO2) have been discovered to offer potential feature such as light harvesting capacity and catalytic activity. The composite integration and properties have been confirmed through characterization using surface area analysis, scanning electron/transmission electron microscopy, atomic force microscopy, fourier transformed infrared spectroscopy, X-ray diffraction analysis, X-ray photoelectron spectroscopy, thermogravimetric analysis, and others. Thus, this work rigorously discussed potential applications of the MOF@TiO2 nanomaterials for the CO2 capture and effective utilization in methanol, ethanol, acetone, acetaldehyde, and other useful products that served as fuel to various industrial processes. Additionally, the work highlights the effective performance of the materials towards photocatalytic degradation of both organic and inorganic pollutants with indepth mechanistic insights. The article will offer significant contribution for the development of sustainable and efficient technologies for the environmental monitoring and pollution mitigation.
In the pursuit of alternatives for conventional diesel, sourced from non-renewable fossil fuel, biodiesel has gained attentions for its intrinsic benefits. However, the commercial production process for biodiesel is still not sufficiently competitive. This review analyses microalgal lipid, one of the important sources of biodiesel, and its cultivation techniques with recent developments in the technical aspects. In fact, the microalgal lipids are the third generation feedstock, used for biodiesel production after its benefits outweigh that of edible vegetable oils (first generation) and non-edible oils (second generation). The critical factors influencing microalgal growth and its lipid production and accumulation are also discussed. Following that is the internal enhancement for cellular lipid production through genetic engineering. Moreover, the microalgae cultivation data modelling was also rationalized, with a specific focus on growth kinetic models that allow for the prediction and optimization of lipid production. Finally, the machine learning and environmental impact analysis are as well presented as important aspects to consider in fulfilling the prime objective of commercial sustainability to produce microalgal biodiesel.
Changing the growth environment for microalgae can overall lead to the fundamental alteration in cellular biochemicals whilst attaching onto palm kernel expeller (PKE) waste to form adhesion complex in easing harvesting at stationary growth phase. This study had initially optimized the PKE dosage, light intensity and photoperiod in maximizing the attached microalgal productivity being attained at 0.72 g/g day. Lipid content increased progressively from pH 3 to pH 11, with the highest value observed at pH 11. Meanwhile, in terms of protein and carbohydrate contents, the highest values were obtained by cultivation medium of pH 5 with 9.92 g and 17.72 g, respectively followed by pH 7 with 9.16 g and 16.36 g, respectively. Moreover, the findings also suggested that the low pH mediums utilized polar interactions in the formation of complexes between PKE and microalgae, whereas at higher pH levels, the non-polar interactions became more significant. The work of attachment was thermodynamically favourable towards the attachment formation with values greater than zero which was also aligned with the microscopic surface topography, i.e., revealing a clustering pattern of microalgae colonizing the PKE surface. These findings contribute to comprehensive understanding of optimizing growth condition and harvesting strategy of attached microalgae in attaining the cellular biochemical components, facilitating the development of efficient and sustainable bioresource utilization.