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Wastewater Treatments Based on Adsorption, Catalysis, Biodegradation, and Beyond

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Applied Chemistry".

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 28245

Special Issue Editors


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Guest Editor
School of Water and Environment, Chang'an University, Xi'an 710054, China
Interests: biochar; lignocellulosic biomass; wastewater treatment; nanomaterials; adsorption; heavy metals; groundwater pollution remediation
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Guest Editor
School of Chemistry, Aristolte University of Thessanoliniki, 54124 Thessaloniki, Greece
Interests: physicochemical properties of nanostructured materials; photo-, sono-, thermo- and electromagnetic catalysis; mechanochemistry; sonophotochemistry; interfacial phenomena in catalysis; detoxification of toxic vapors; biomass valorization; selective oxidation processes; air and water remediation; materials chemistry; MOFs and metal-oxide nanocomposites; activated carbons; graphite/graphite oxide; graphitic carbon nitride polymers; semiconductor nanocatalysts; carbon quantum dots
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The continuous widespread technological progress and industrial expansion over the last several decades has been accompanied with the serious environmental problem of water pollution. The pollution of water is related to the uncontrollable contamination of water bodies such as lakes, rivers, oceans, and groundwater by a plethora of substances/pollutants that can be harmful for humans, as well as for flora and fauna, even at very low concentration. For example, heavy metals/metalloids can accumulate in living organisms, causing permanent cell damage and disorders leading to disease and even death. The unmanageable disposal of pharmaceuticals and personal care products (PPCPs) to water bodies can cause serious ecotoxicological problems and pose extraordinary threats to ecosystems or organisms. Microplastics are a class of emerging pollutants that generate severe environmental issues because of their small size, unique morphology, and enhanced chemical heterogeneity, but above all due to their stability and ability to act as pollutant carriers.

Environmental protection is regarded as key in the design and development of a sustainable future, and hence the attention of researchers and the public is concentrated on novel remediation approaches. Intense emphasis is placed on the removal of heavy metals, PPCPs, MPs, and other pollutants from water and wastewater. The diverse composition of the polluted water bodies, and of industrial wastewater, requires a variety of treatment methods. Heavy metal ions are most often removed by the precipitation of their hardly soluble compounds. Ion exchange and sorption methods are also widely used. Sorption is an effective method for the removal of emerging contaminants and heavy metals from water and wastewater. Sorbents derived from discarded biomass, wastes and other feedstocks are widely studied for the treatment of contaminated water, since this material development strategy is within the framework of sustainable (bio)economy. Additionally, biodegradation and catalytic degradation methods are receiving attention for the removal of PPCPs and MPs. Therefore, the research and development of novel and efficient materials for environmental remediation applications, and especially for the removal of pollutants from water bodies, remains an active field of research.  

This Special Issue aims to contribute both towards the search for new methods beyond sorption, biodegradation and catalytic degradation, and to present new materials for effective (waste)water treatment and purification.

We especially welcome works which address emerging pollutants or compounds which are not broadly studied. We encourage the publication of scientific articles, critical reviews, and case studies relevant to the context above, and which generally fall within the field of modern environmental remediation applications.

Dr. Yongchang Sun
Dr. Dimitrios Giannakoudakis
Guest Editors

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Keywords

  • wastewater
  • adsorption
  • biodegradation
  • catalytic degradation
  • photocatalysis
  • heavy metal
  • emerging contaminant
  • biosorbent
  • mechanism

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Published Papers (16 papers)

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19 pages, 3987 KiB  
Article
A Strategy to Valorize a By-Product of Pine Wood (Pinus pinaster) for Copper Removal from Aqueous Solutions
by Chiara Mongioví, Maélys Jaillet, Dario Lacalamita, Nadia Morin-Crini, Michael Lecourt, Sandra Tapin-Lingua and Grégorio Crini
Molecules 2023, 28(18), 6436; https://doi.org/10.3390/molecules28186436 - 05 Sep 2023
Viewed by 815
Abstract
This study describes the valorization of a pine wood by-product (Pinus pinaster) in the form of individualized fibers to a complex copper or more broadly metals present in an aqueous solution using a batch process. The adsorption results show that pine [...] Read more.
This study describes the valorization of a pine wood by-product (Pinus pinaster) in the form of individualized fibers to a complex copper or more broadly metals present in an aqueous solution using a batch process. The adsorption results show that pine fibres activated by sodium carbonate are effective in recovering copper ions from monocontaminated or polycontaminated solutions of varying concentrations in a few minutes. One gram of material captures 2.5 mg of copper present in 100 mL of solution at pH 5 in less than 10 min. The results are perfectly reproducible and independent of pH between 3 and 5. The presence of the Na+ cation at concentrations of 0.1 M has no impact on material performance, unlike that of Ca2+ ions, which competes with Cu2+ ions for active sites. The adsorption process can be considered as rapid, as most of the copper is adsorbed within the first 10 min of exposure. Investigation of modeling possibilities shows some limitations. Indeed, the Weber and Morris and Elovich models show poor possibilities to describe all the kinetic data for copper adsorption on fibres. This may prove that the mechanism is far more complex than simple physisorption, chemisorption and/or diffusion. Complexation by wood fibers can be extended to solutions containing several types of metals. The results of this study show that the field of selective metal recovery could be a new way of valorizing by-products from the wood industry. Full article
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16 pages, 3231 KiB  
Article
Treatment of Organic and Sulfate/Sulfide Contaminated Wastewater and Bioelectricity Generation by Sulfate-Reducing Bioreactor Coupling with Sulfide-Oxidizing Fuel Cell
by Thi Quynh Hoa Kieu, Thi Yen Nguyen and Chi Linh Do
Molecules 2023, 28(17), 6197; https://doi.org/10.3390/molecules28176197 - 23 Aug 2023
Viewed by 1177
Abstract
A wastewater treatment system has been established based on sulfate-reducing and sulfide—oxidizing processes for treating organic wastewater containing high sulfate/sulfide. The influence of COD/SO42− ratio and hydraulic retention time (HRT) on removal efficiencies of sulfate, COD, sulfide and electricity generation was [...] Read more.
A wastewater treatment system has been established based on sulfate-reducing and sulfide—oxidizing processes for treating organic wastewater containing high sulfate/sulfide. The influence of COD/SO42− ratio and hydraulic retention time (HRT) on removal efficiencies of sulfate, COD, sulfide and electricity generation was investigated. The continuous operation of the treatment system was carried out for 63 days with the optimum COD/SO42− ratio and HRT. The result showed that the COD and sulfate removal efficiencies were stable, reaching 94.8 ± 0.6 and 93.0 ± 1.3% during the operation. A power density level of 18.0 ± 1.6 mW/m2 was obtained with a sulfide removal efficiency of 93.0 ± 1.2%. However, the sulfide removal efficiency and power density decreased gradually after 45 days. The results from scanning electron microscopy (SEM) with an energy dispersive X-ray (EDX) show that sulfur accumulated on the anode, which could explain the decline in sulfide oxidation and electricity generation. This study provides a promising treatment system to scale up for its actual applications in this type of wastewater. Full article
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18 pages, 7646 KiB  
Article
Hydrothermal Synthesis of a Technical Lignin-Based Nanotube for the Efficient and Selective Removal of Cr(VI) from Aqueous Solution
by Qiongyao Wang, Yongchang Sun, Mingge Hao, Fangxin Yu and Juanni He
Molecules 2023, 28(15), 5789; https://doi.org/10.3390/molecules28155789 - 31 Jul 2023
Viewed by 684
Abstract
Aminated lignin (AL) was obtained by modifying technical lignin (TL) with the Mannich reaction, and aminated lignin-based titanate nanotubes (AL-TiNTs) were successfully prepared based on the AL by a facile hydrothermal synthesis method. The characterization of AL-TiNTs showed that a Ti–O bond was [...] Read more.
Aminated lignin (AL) was obtained by modifying technical lignin (TL) with the Mannich reaction, and aminated lignin-based titanate nanotubes (AL-TiNTs) were successfully prepared based on the AL by a facile hydrothermal synthesis method. The characterization of AL-TiNTs showed that a Ti–O bond was introduced into the AL, and the layered and nanotubular structure was formed in the fabrication of the nanotubes. Results showed that the specific surface area increased significantly from 5.9 m2/g (TL) to 188.51 m2/g (AL-TiNTs), indicating the successful modification of TL. The AL-TiNTs quickly adsorbed 86.22% of Cr(VI) in 10 min, with 99.80% removal efficiency after equilibration. Under visible light, AL-TiNTs adsorbed and reduced Cr(VI) in one step, the Cr(III) production rate was 29.76%, and the amount of total chromium (Cr) removal by AL-TiNTs was 90.0 mg/g. AL-TiNTs showed excellent adsorption capacities of Zn2+ (63.78 mg/g), Cd2+ (59.20 mg/g), and Cu2+ (66.35 mg/g). After four cycles, the adsorption capacity of AL-TiNTs still exceeded 40 mg/g. AL-TiNTs showed a high Cr(VI) removal efficiency of 95.86% in simulated wastewater, suggesting a promising practical application in heavy metal removal from wastewater. Full article
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18 pages, 11402 KiB  
Article
Effective Removal of Fe (III) from Strongly Acidic Wastewater by Pyridine-Modified Chitosan: Synthesis, Efficiency, and Mechanism
by Lei Zhang, Heng Liu, Jiaqi Zhu, Xueling Liu, Likun Li, Yanjun Huang, Benquan Fu, Guozhi Fan and Yi Wang
Molecules 2023, 28(8), 3445; https://doi.org/10.3390/molecules28083445 - 13 Apr 2023
Cited by 2 | Viewed by 1299
Abstract
A novel pyridine-modified chitosan (PYCS) adsorbent was prepared in a multistep procedure including the successive grafting of 2-(chloromethyl) pyridine hydrochloride and crosslinking with glutaraldehyde. Then, the as-prepared materials were used as adsorbents for the removal of metal ions from acidic wastewater. Batch adsorption [...] Read more.
A novel pyridine-modified chitosan (PYCS) adsorbent was prepared in a multistep procedure including the successive grafting of 2-(chloromethyl) pyridine hydrochloride and crosslinking with glutaraldehyde. Then, the as-prepared materials were used as adsorbents for the removal of metal ions from acidic wastewater. Batch adsorption experiments were carried out to study the impact of various factors such as solution pH value, contact time, temperature, and Fe (III) concentration. The results showed that the absorbent exhibited a high capacity of Fe (III) and the maximum adsorption capacity was up to 66.20 mg/g under optimal experimental conditions (the adsorption time = 12 h, pH = 2.5, and T = 303 K). Adsorption kinetics and isotherm data were accurately described by the pseudo-second-order kinetic model and Sips model, respectively. Thermodynamic studies confirmed that the adsorption was a spontaneous endothermic process. Moreover, the adsorption mechanism was investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results revealed the pyridine group forms a stable chelate with iron (III) ions. Therefore, this acid-resistant adsorbent exhibited excellent adsorption performance for heavy metal ions from acidic wastewater compared to the conventional adsorbents, helping realize direct decontamination and secondary utilization. Full article
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16 pages, 2807 KiB  
Article
An Investigation of a Natural Biosorbent for Removing Methylene Blue Dye from Aqueous Solution
by Basma G. Alhogbi and Ghadeer S. Al Balawi
Molecules 2023, 28(6), 2785; https://doi.org/10.3390/molecules28062785 - 20 Mar 2023
Cited by 2 | Viewed by 1498
Abstract
T he current study reports the use of zeolite prepared from a kaolin composite via physical mixing with different ratios from fiber of palm tree (Zeo-FPT) as a sustainable solid sorbent for the removal of methylene blue (MB) dye from aqueous solutions. The [...] Read more.
T he current study reports the use of zeolite prepared from a kaolin composite via physical mixing with different ratios from fiber of palm tree (Zeo-FPT) as a sustainable solid sorbent for the removal of methylene blue (MB) dye from aqueous solutions. The prepared biosorbent was fully characterized using XRD, TGA, SEM, and FTIR. The impacts of various analytical parameters, for example, contact time, dosage, MB dye concentration, and the pH of the solution, on the dye adsorption process were determined. After a contact time of 40 min, the capacity to remove MB dye was 0.438 mg g−1 at a Zeo-FPT composition ratio of 1F:1Z. At pH 8, Zeo-FPT (1F:1Z) had a removal efficiency of 87% at a sorbent dosage of 0.5 g for a concentration of MB dye in an aqueous phase of 10 mg L−1. The experimental data were also analyzed using the kinetic and adsorption isotherm models. The retention process fitted well with the pseudo-second-order model (R2 0.998), where the Qe,calc of 0.353 mg g−1 was in acceptable agreement with the Qe,exp of 0.438 mg g−1. The data also fitted well with the Freundlich isotherm model, as indicated by the correlation coefficient value (R2 0.969). The Zeo-FPT attained a high percentage (99%) in the removal of MB dye from environmental water samples (tap water, bottled water, and well water). Thus, it can be concluded that the proposed zeolite composite with fiber of palm tree (Zeo-FPT) is a suitable, environmentally friendly, and low-cost adsorbent for removing dyes from wastewater. Full article
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14 pages, 3180 KiB  
Article
Adsorption Performance of Methylene Blue by KOH/FeCl3 Modified Biochar/Alginate Composite Beads Derived from Agricultural Waste
by Heng Liu, Jiaqi Zhu, Qimei Li, Likun Li, Yanjun Huang, Yi Wang, Guozhi Fan and Lei Zhang
Molecules 2023, 28(6), 2507; https://doi.org/10.3390/molecules28062507 - 09 Mar 2023
Cited by 6 | Viewed by 2004
Abstract
In this study, high-performance modified biochar/alginate composite bead (MCB/ALG) adsorbents were prepared from recycled agricultural waste corncobs by a high-temperature pyrolysis and KOH/FeCl3 activation process. The prepared MCB/ALG beads were tested for the adsorption of methylene blue (MB) dye from wastewater. A [...] Read more.
In this study, high-performance modified biochar/alginate composite bead (MCB/ALG) adsorbents were prepared from recycled agricultural waste corncobs by a high-temperature pyrolysis and KOH/FeCl3 activation process. The prepared MCB/ALG beads were tested for the adsorption of methylene blue (MB) dye from wastewater. A variety of analytical methods, such as SEM, BET, FTIR and XRD, were used to investigate the structure and properties of the as-prepared adsorbents. The effects of solution pH, time, initial MB concentration and adsorption temperature on the adsorption performance of MCB/ALG beads were discussed in detail. The results showed that the adsorption equilibrium of MB dye was consistent with the Langmuir isothermal model and the pseudo-second-order kinetic model. The maximum adsorption capacity of MCB/ALG−1 could reach 1373.49 mg/g at 303 K. The thermodynamic studies implied endothermic and spontaneous properties of the adsorption system. This high adsorption performance of MCB/ALG was mainly attributed to pore filling, hydrogen bonding and electrostatic interactions. The regeneration experiments showed that the removal rate of MB could still reach 85% even after five cycles of experiments, indicating that MCB/ALG had good reusability and stability. These results suggested that a win-win strategy of applying agricultural waste to water remediation was feasible. Full article
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21 pages, 1808 KiB  
Article
Study of the Influence of the Wastewater Matrix in the Adsorption of Three Pharmaceuticals by Powdered Activated Carbon
by Marina Gutiérrez, Paola Verlicchi and Dragana Mutavdžić Pavlović
Molecules 2023, 28(5), 2098; https://doi.org/10.3390/molecules28052098 - 23 Feb 2023
Cited by 5 | Viewed by 1566
Abstract
The use of powdered activated carbon (PAC) as an absorbent has become a promising option to upgrade wastewater treatment plants (WWTPs) that were not designed to remove pharmaceuticals. However, PAC adsorption mechanisms are not yet fully understood, especially with regard to the nature [...] Read more.
The use of powdered activated carbon (PAC) as an absorbent has become a promising option to upgrade wastewater treatment plants (WWTPs) that were not designed to remove pharmaceuticals. However, PAC adsorption mechanisms are not yet fully understood, especially with regard to the nature of the wastewater. In this study, we tested the adsorption of three pharmaceuticals, namely diclofenac, sulfamethoxazole and trimethoprim, onto PAC under four different water matrices: ultra-pure water, humic acid solution, effluent and mixed liquor from a real WWTP. The adsorption affinity was defined primarily by the pharmaceutical physicochemical properties (charge and hydrophobicity), with better results obtained for trimethoprim, followed by diclofenac and sulfamethoxazole. In ultra-pure water, the results show that all pharmaceuticals followed pseudo-second order kinetics, and they were limited by a boundary layer effect on the surface of the adsorbent. Depending on the water matrix and compound, the PAC capacity and the adsorption process varied accordingly. The higher adsorption capacity was observed for diclofenac and sulfamethoxazole in humic acid solution (Langmuir isotherm, R2 > 0.98), whereas better results were obtained for trimethoprim in the WWTP effluent. Adsorption in mixed liquor (Freundlich isotherm, R2 > 0.94) was limited, presumably due to its complex nature and the presence of suspended solids. Full article
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22 pages, 8967 KiB  
Article
Modification of Multiwalled Carbon Nanotubes and Their Mechanism of Demanganization
by Yuan Zhou, Yingying He, Ruixue Wang, Yongwei Mao, Jun Bai and Yan Dou
Molecules 2023, 28(4), 1870; https://doi.org/10.3390/molecules28041870 - 16 Feb 2023
Cited by 2 | Viewed by 1398
Abstract
Multiwalled carbon nanotubes (MWCNTs) were modified by oxidation and acidification with concentrated HNO3 and H2SO4, and the modified multiwalled carbon nanotubes (M-MWCNTs) and raw MWCNTs were characterized by several analytical techniques. Then the demanganization effects of MWCNTs and [...] Read more.
Multiwalled carbon nanotubes (MWCNTs) were modified by oxidation and acidification with concentrated HNO3 and H2SO4, and the modified multiwalled carbon nanotubes (M-MWCNTs) and raw MWCNTs were characterized by several analytical techniques. Then the demanganization effects of MWCNTs and M-MWCNTs were well investigated and elucidated. The experimental data demonstrated that the adsorption efficiency of Mn(II) could be greatly promoted by M-MWCNTs from about 20% to 75%, and the optimal adsorption time was 6 h and the optimal pH was 6. The results of the kinetic model studies showed that Mn(II) removal by M-MWCNTs followed the pseudo-second-order model. Isothermal studies were conducted and the results demonstrated that the experimental data fitted well with the three models. The reliability of the experimental results was well verified by PSO–BP simulation, and the present conclusion could be used as a condition for further simulation. The research results provide a potential technology for promoting the removal of manganese from wastewater; at the same time, the application of various mathematical models also provides more scientific ideas for the research of the mechanism of adsorption of heavy metals by nanomaterials. Full article
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17 pages, 4889 KiB  
Article
Synthesis and Characterization of MIPs for Selective Removal of Textile Dye Acid Black-234 from Wastewater Sample
by Maria Sadia, Izaz Ahmad, Zain Ul-Saleheen, Muhammad Zubair, Muhammad Zahoor, Riaz Ullah, Ahmed Bari and Ivar Zekker
Molecules 2023, 28(4), 1555; https://doi.org/10.3390/molecules28041555 - 06 Feb 2023
Cited by 8 | Viewed by 1638
Abstract
Herein, a molecularly imprinted polymer (MIP) was prepared using bulk polymerization and applied to wastewater to aid the adsorption of targeted template molecules using ethylene glycol dimethacrylate (EGDMA), methacrylic acid (MAA), acid black-234 (AB-234), 2,2′-azobisisobutyronitrile (AIBN), and methanol as a cross linker, functional [...] Read more.
Herein, a molecularly imprinted polymer (MIP) was prepared using bulk polymerization and applied to wastewater to aid the adsorption of targeted template molecules using ethylene glycol dimethacrylate (EGDMA), methacrylic acid (MAA), acid black-234 (AB-234), 2,2′-azobisisobutyronitrile (AIBN), and methanol as a cross linker, functional monomer, template, initiator, and porogenic solvent, respectively. For a non-molecularly imprinted polymer (NIP), the same procedure was followed but without adding a template. Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and a surface area analyzer were used to determine the surface functional groups, morphology and specific surface area of the MIP and NIP. At pH 5, the AB-234 adsorption capability of the MIP was higher (94%) than the NIP (31%). The adsorption isotherm data of the MIP correlated very well with the Langmuir adsorption model with Qm 82, 83 and 100 mg/g at 283 K, 298 K, and 313 K, respectively. The adsorption process followed pseudo–second-order kinetics. The imprinted factor (IF) and Kd value of the MIP were 5.13 and 0.53, respectively. Thermodynamic studies show that AB-234 dye adsorption on the MIP and NIP was spontaneous and endothermic. The MIP proved to be the best selective adsorbent for AB-234, even in the presence of dyes with similar and different structures than the NIP. Full article
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17 pages, 2576 KiB  
Article
Synthesis and Characterization of Novel Thiosalicylate-based Solid-Supported Ionic Liquid for Removal of Pb(II) Ions from Aqueous Solution
by Nur Anis Liyana Kamaruddin, Mohd Faisal Taha and Cecilia Devi Wilfred
Molecules 2023, 28(2), 830; https://doi.org/10.3390/molecules28020830 - 13 Jan 2023
Cited by 3 | Viewed by 1365
Abstract
The main objectives of this study are to synthesize a new solid-supported ionic liquid (SSIL) that has a covalent bond between the solid support, i.e., activated silica gel, with thiosalicylate-based ionic liquid and to evaluate the performance of this new SSIL as an [...] Read more.
The main objectives of this study are to synthesize a new solid-supported ionic liquid (SSIL) that has a covalent bond between the solid support, i.e., activated silica gel, with thiosalicylate-based ionic liquid and to evaluate the performance of this new SSIL as an extractant, labelled as Si-TS-SSIL, and to remove Pb(II) ions from an aqueous solution. In this study, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium thiosalicylate ([MTMSPI][TS]) ionic liquid was synthesized and the formation of [MTMSPI][TS] was confirmed through structural analysis using NMR, FTIR, IC, TGA, and Karl Fischer Titration. The [MTMSPI][TS] ionic liquid was then chemically immobilized on activated silica gel to produce a new thiosalicylate-based solid-supported ionic liquid (Si-TS-SSIL). The formation of these covalent bonds on Si-TS-SSIL was confirmed by solid-state NMR analysis. Meanwhile, BET analysis was performed to study the surface area of the activated silica gel and the prepared Si-TS-SSIL (before and after washing with solvent) with the purpose to show that all physically immobilized [MTMSPI][TS] has been washed off from Si-TS-SSIL, leaving only chemically immobilized [MTMSPI][TS] on Si-TS-SSIL before proceeding with removal study. The removal study of Pb(II) ions from an aqueous solution was carried out using Si-TS-SSIL as an extractant, whereby the amount of Pb(II) ions removed was determined by AAS. In this removal study, the experiments were carried out at a fixed agitation speed (400 rpm) and fixed amount of Si-TS-SSIL (0.25 g), with different contact times ranging from 2 to 250 min at room temperature. The maximum removal capacity was found to be 8.37 mg/g. The kinetics study was well fitted with the pseudo-second order model. Meanwhile, for the isotherm study, the removal process of Pb(II) ions was well described by the Freundlich isotherm model, as this model exhibited a higher correlation coefficient (R2), i.e., 0.99, as compared to the Langmuir isotherm model. Full article
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15 pages, 4095 KiB  
Article
Adsorption of Toxic Tetracycline, Thiamphenicol and Sulfamethoxazole by a Granular Activated Carbon (GAC) under Different Conditions
by Risheng Li, Wen Sun, Longfei Xia, Zia U, Xubo Sun, Zhao Wang, Yujie Wang and Xu Deng
Molecules 2022, 27(22), 7980; https://doi.org/10.3390/molecules27227980 - 17 Nov 2022
Cited by 5 | Viewed by 1238
Abstract
Activated carbon can be applied to the treatment of wastewater loading with different types of pollutants. In this paper, a kind of activated carbon in granular form (GAC) was utilized to eliminate antibiotics from an aqueous solution, in which Tetracycline (TC), Thiamphenicol (THI), [...] Read more.
Activated carbon can be applied to the treatment of wastewater loading with different types of pollutants. In this paper, a kind of activated carbon in granular form (GAC) was utilized to eliminate antibiotics from an aqueous solution, in which Tetracycline (TC), Thiamphenicol (THI), and Sulfamethoxazole (SMZ) were selected as the testing pollutants. The specific surface area, total pore volume, and micropore volume of GAC were 1059.011 m2/g, 0.625 cm3/g, and 0.488 cm3/g, respectively. The sorption capacity of GAC towards TC, THI, and SMZ was evaluated based on the adsorption kinetics and isotherm. It was found that the pseudo-second-order kinetic model described the sorption of TC, THI, and SMZ on GAC better than the pseudo-first-order kinetic model. According to the Langmuir isotherm model, the maximum adsorption capacity of GAC towards TC, THI, and SMZ was calculated to be 17.02, 30.40, and 26.77 mg/g, respectively. Thermodynamic parameters of ΔG0, ΔS0, and ΔH0 were obtained, indicating that all the sorptions were spontaneous and exothermic in nature. These results provided a knowledge base on using activated carbon to remove TC, THI, and SMZ from water. Full article
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41 pages, 12955 KiB  
Article
New Process for the Sulfonation of Algal/PEI Biosorbent for Enhancing Sr(II) Removal from Aqueous Solutions—Application to Seawater
by Mohammed F. Hamza, Eric Guibal, Khalid Althumayri, Thierry Vincent, Xiangbiao Yin, Yuezhou Wei and Wenlong Li
Molecules 2022, 27(20), 7128; https://doi.org/10.3390/molecules27207128 - 21 Oct 2022
Cited by 10 | Viewed by 1549
Abstract
Sulfonic resins are highly efficient cation exchangers widely used for metal removal from aqueous solutions. Herein, a new sulfonation process is designed for the sulfonation of algal/PEI composite (A*PEI, by reaction with 2-propylene-1-sulfonic acid and hydroxylamine-O-sulfonic acid). The new sulfonated functionalized sorbent (SA*PEI) [...] Read more.
Sulfonic resins are highly efficient cation exchangers widely used for metal removal from aqueous solutions. Herein, a new sulfonation process is designed for the sulfonation of algal/PEI composite (A*PEI, by reaction with 2-propylene-1-sulfonic acid and hydroxylamine-O-sulfonic acid). The new sulfonated functionalized sorbent (SA*PEI) is successfully tested in batch systems for strontium recovery first in synthetic solutions before investigating with multi-component solutions and final validation with seawater samples. The chemical modification of A*PEI triples the sorption capacity for Sr(II) at pH 4 with a removal rate of up to 7% and 58% for A*PEI and SA*PEI, respectively (with SD: 0.67 g L−1). FTIR shows the strong contribution of sulfonate groups for the functionalized sorbent (in addition to amine and carboxylic groups from the support). The sorption is endothermic (increase in sorption with temperature). The sulfonation improves thermal stability and slightly enhances textural properties. This may explain the fast kinetics (which are controlled by the pseudo-first-order rate equation). The sulfonated sorbent shows a remarkable preference for Sr(II) over competitor mono-, di-, and tri-valent metal cations. Sorption properties are weakly influenced by the excess of NaCl; this can explain the outstanding sorption properties in the treatment of seawater samples. In addition, the sulfonated sorbent shows excellent stability at recycling (for at least 5 cycles), with a loss in capacity of around 2.2%. These preliminary results show the remarkable efficiency of the sorbent for Sr(II) removal from complex solutions (this could open perspectives for the treatment of contaminated seawater samples). Full article
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9 pages, 2923 KiB  
Article
Uranium Isotope (U-232) Removal from Waters by Biochar Fibers: An Adsorption Study in the Sub-Picomolar Concentration Range
by Maria Philippou, Ioannis Pashalidis and Charis R. Theocharis
Molecules 2022, 27(19), 6765; https://doi.org/10.3390/molecules27196765 - 10 Oct 2022
Cited by 4 | Viewed by 1154
Abstract
The adsorption of the U-232 radionuclide by biochar fibers in the sub-picomolar concentration range has been investigated in laboratory aqueous solutions and seawater samples. The adsorption efficiency (Kd values and % relative removal) of untreated and oxidized biochar samples towards U-232 [...] Read more.
The adsorption of the U-232 radionuclide by biochar fibers in the sub-picomolar concentration range has been investigated in laboratory aqueous solutions and seawater samples. The adsorption efficiency (Kd values and % relative removal) of untreated and oxidized biochar samples towards U-232 has been investigated as a function of pH, adsorbent mass, ionic strength and temperature by means of batch-type experiments. According to the experimental data, the solution pH determines to a large degree the adsorption efficiency, and adsorbent mass and surface oxidation lead to significantly higher Kd values. The ionic strength and temperature effect indicate that the adsorption is based on the formation of inner-sphere complexes, and is an endothermic and entropy-driven process (ΔH° and ΔS° > 0), respectively. Regarding the sorption kinetics, the diffusion of U-232 from the solution to the biochar surface seems to be the rate-determining step. The application of biochar-based adsorbents to treat radioactively (U-232) contaminated waters reveals that these materials are very effective adsorbents, even in the sub-picomolar concentration range. Full article
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17 pages, 3234 KiB  
Article
3D Porous Structure-Inspired Lignocellulosic Biosorbent of Medulla tetrapanacis for Efficient Adsorption of Cationic Dyes
by Jie Zhang, Hao Ji, Zepeng Liu, Liping Zhang, Zihao Wang, Ying Guan and Hui Gao
Molecules 2022, 27(19), 6228; https://doi.org/10.3390/molecules27196228 - 22 Sep 2022
Cited by 7 | Viewed by 1524
Abstract
The focus of this work was on developing a green, low-cost, and efficient biosorbent based on the biological structure and properties of MT and applying it to the remediation of cationic dyes in dye wastewater. The adsorption performance and mechanism of MT on [...] Read more.
The focus of this work was on developing a green, low-cost, and efficient biosorbent based on the biological structure and properties of MT and applying it to the remediation of cationic dyes in dye wastewater. The adsorption performance and mechanism of MT on methylene blue (MB) and crystal violet (CV) were investigated by batch adsorption experiments. The results demonstrated that the highest adsorption values of MT for MB (411 mg/g) and CV (553 mg/g) were greatly higher than the reported values of other biosorbents. In addition, the adsorption behaviors of methylene blue (MB) and crystal violet (CV) by MT were spontaneous exothermic reactions and closely followed the pseudo-second-order (PSO) kinetics and Langmuir isotherm. Further, the depleted MT was regenerated using pyrolysis mode to convert depleted MT into MT-biochar (MBC). The maximum adsorption of Cu2+ and Pb2+ by MBC was up to 320 mg/g and 840 mg/g, respectively. In conclusion, this work presented a new option for the adsorption of cationic dyes in wastewater and a new perspective for the treatment of depleted biosorbents. Full article
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Review

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22 pages, 5118 KiB  
Review
Agricultural Solid Wastes Based Adsorbent Materials in the Remediation of Heavy Metal Ions from Water and Wastewater by Adsorption: A Review
by Tushar Kanti Sen
Molecules 2023, 28(14), 5575; https://doi.org/10.3390/molecules28145575 - 21 Jul 2023
Cited by 9 | Viewed by 3507
Abstract
Adsorption has become the most popular and effective separation technique that is used across the water and wastewater treatment industries. However, the present research direction is focused on the development of various solid waste-based adsorbents as an alternative to costly commercial activated carbon [...] Read more.
Adsorption has become the most popular and effective separation technique that is used across the water and wastewater treatment industries. However, the present research direction is focused on the development of various solid waste-based adsorbents as an alternative to costly commercial activated carbon adsorbents, which make the adsorptive separation process more effective, and on popularising the sustainable options for the remediation of pollutants. Therefore, there are a large number of reported results available on the application of raw or treated agricultural biomass-based alternatives as effective adsorbents for aqueous-phase heavy metal ion removal in batch adsorption studies. The goal of this review article was to provide a comprehensive compilation of scattered literature information and an up-to-date overview of the development of the current state of knowledge, based on various batch adsorption research papers that utilised a wide range of raw, modified, and treated agricultural solid waste biomass-based adsorbents for the adsorptive removal of aqueous-phase heavy metal ions. Metal ion pollution and its source, toxicity effects, and treatment technologies, mainly via adsorption, have been reviewed here in detail. Emphasis has been placed on the removal of heavy metal ions using a wide range of agricultural by-product-based adsorbents under various physicochemical process conditions. Information available in the literature on various important influential physicochemical process parameters, such as the metal concentration, agricultural solid waste adsorbent dose, solution pH, and solution temperature, and importantly, the adsorbent characteristics of metal ion removal, have been reviewed and critically analysed here. Finally, from the literature reviewed, future perspectives and conclusions were presented, and a few future research directions have been proposed. Full article
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28 pages, 3637 KiB  
Review
Effective Usage of Biochar and Microorganisms for the Removal of Heavy Metal Ions and Pesticides
by Soumya K. Manikandan, Pratyasha Pallavi, Krishan Shetty, Debalina Bhattacharjee, Dimitrios A. Giannakoudakis, Ioannis A. Katsoyiannis and Vaishakh Nair
Molecules 2023, 28(2), 719; https://doi.org/10.3390/molecules28020719 - 11 Jan 2023
Cited by 24 | Viewed by 4505
Abstract
The bioremediation of heavy metal ions and pesticides is both cost-effective and environmentally friendly. Microbial remediation is considered superior to conventional abiotic remediation processes, due to its cost-effectiveness, decrement of biological and chemical sludge, selectivity toward specific metal ions, and high removal efficiency [...] Read more.
The bioremediation of heavy metal ions and pesticides is both cost-effective and environmentally friendly. Microbial remediation is considered superior to conventional abiotic remediation processes, due to its cost-effectiveness, decrement of biological and chemical sludge, selectivity toward specific metal ions, and high removal efficiency in dilute effluents. Immobilization technology using biochar as a carrier is one important approach for advancing microbial remediation. This article provides an overview of biochar-based materials, including their design and production strategies, physicochemical properties, and applications as adsorbents and support for microorganisms. Microorganisms that can cope with the various heavy metal ions and/or pesticides that enter the environment are also outlined in this review. Pesticide and heavy metal bioremediation can be influenced by microbial activity, pollutant bioavailability, and environmental factors, such as pH and temperature. Furthermore, by elucidating the interaction mechanisms, this paper summarizes the microbe-mediated remediation of heavy metals and pesticides. In this review, we also compile and discuss those works focusing on the study of various bioremediation strategies utilizing biochar and microorganisms and how the immobilized bacteria on biochar contribute to the improvement of bioremediation strategies. There is also a summary of the sources and harmful effects of pesticides and heavy metals. Finally, based on the research described above, this study outlines the future scope of this field. Full article
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