Removal of contaminants present in water and wastewater by cyclodextrin-based adsorbents: A bibliometric review from 1993 to 2022.

Cyclodextrin (CD), a cyclic oligosaccharide from enzymatic starch breakdown, plays a crucial role in pharmaceuticals, food, agriculture, textiles, biotechnology, chemicals, and environmental applications, including water and wastewater treatment. In this study, a statistical analysis was performed using VOSviewer and Citespace to scrutinize 2038 articles published from 1993 to 2022. The investigation unveiled a notable upsurge in pertinent articles and citation counts, with China and USA contributing the highest publication volumes. The prevailing research focus predominantly revolves around the application of CD-based materials used as adsorbents to remove conventional contaminants such as dyes and metals. The CD chemistry allows the construction of materials with various architectures, including cross-linked, grafted, hybrid or supported systems. The main adsorbents are cross-linked CD polymers, including nanosponges, fibres and hybrid composites. Additionally, research efforts are actually concentrated on the synthesis of CD-based membranes, CD@graphene oxide, and CD@TiO2. These materials are proposed as adsorbents to remove emerging pollutants. By employing bibliometric analysis, this study delivers a comprehensive retrospective review and synthesis of research concerning CD-based adsorbents for the removal of contaminants from wastewater, thereby offering valuable insights for future large-scale application of CD-based adsorption materials.

A Strategy to Valorize a By-Product of Pine Wood (Pinus pinaster) for Copper Removal from Aqueous Solutions.

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.

Field-Crop Soils in Eastern France: Coldspots of Azole-Resistant Aspergillus fumigatus.

Triazole fungicides are widely used to treat fungal pathogens in field crops, but very few studies have investigated whether fields of these crops constitute hotspots of azole resistance in Aspergillus fumigatus. Soil samples were collected from 22 fields in two regions of eastern France and screened for triazole residues and azole-resistant A. fumigatus (ARAf). Real-time quantitative PCR (qPCR) was used to quantify A. fumigatus in these soil samples. All the plots contained tebuconazole at concentrations from 5.5 to 19.1 ng/g of soil, and 5 of the 22 plots also contained epoxiconazole. Only a few fungal isolates were obtained, and no ARAf was detected. A. fumigatus qPCR showed that this fungal species was, on average, 5000 times more common in soil from flowerbeds containing ARAf than in soil from field crops. Thus, field-crop soils do not appear to promote A. fumigatus development, even if treated with azole fungicides, and cannot be considered hotspots of resistance. Indeed, our results suggest that they are instead a coldspot of resistance and highlight how little is known about the ecological niche of this species.

Chitosan as an Outstanding Polysaccharide Improving Health-Commodities of Humans and Environmental Protection.

Public health, production and preservation of food, development of environmentally friendly (cosmeto-)textiles and plastics, synthesis processes using green technology, and improvement of water quality, among other domains, can be controlled with the help of chitosan. It has been demonstrated that this biopolymer exhibits advantageous properties, such as biocompatibility, biodegradability, antimicrobial effect, mucoadhesive properties, film-forming capacity, elicitor of plant defenses, coagulant-flocculant ability, synergistic effect and adjuvant along with other substances and materials. In part, its versatility is attributed to the presence of ionizable and reactive primary amino groups that provide strong chemical interactions with small inorganic and organic substances, macromolecules, ions, and cell membranes/walls. Hence, chitosan has been used either to create new materials or to modify the properties of conventional materials applied on an industrial scale. Considering the relevance of strategic topics around the world, this review integrates recent studies and key background information constructed by different researchers designing chitosan-based materials with potential applications in the aforementioned concerns.

Removal of an Azo Dye from Wastewater through the Use of Two Technologies: Magnetic Cyclodextrin Polymers and Pulsed Light.

Water pollution by dyes is a huge environmental problem; there is a necessity to produce new decolorization methods that are effective, cost-attractive, and acceptable in industrial use. Magnetic cyclodextrin polymers offer the advantage of easy separation from the dye solution. In this work, the ß-CD-EPI-magnetic (ß-cyclodextrin-epichlorohydrin) polymer was synthesized, characterized, and tested for removal of the azo dye Direct Red 83:1 from water, and the fraction of non-adsorbed dye was degraded by an advanced oxidation process. The polymer was characterized in terms of the particle size distribution and surface morphology (FE-SEM), elemental analysis (EA), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), infrared spectrophotometry (IR), and X-ray powder diffraction (XRD). The reported results hint that 0.5 g and pH 5.0 were the best conditions to carry out both kinetic and isotherm models. A 30 min contact time was needed to reach equilibrium with a qmax of 32.0 mg/g. The results indicated that the pseudo-second-order and intraparticle diffusion models were involved in the assembly of Direct Red 83:1 onto the magnetic adsorbent. Regarding the isotherms discussed, the Freundlich model correctly reproduced the experimental data so that adsorption was confirmed to take place onto heterogeneous surfaces. The calculation of the thermodynamic parameters further demonstrates the spontaneous character of the adsorption phenomena (ΔG° = −27,556.9 J/mol) and endothermic phenomena (ΔH° = 8757.1 J/mol) at 25 °C. Furthermore, a good reusability of the polymer was evidenced after six cycles of regeneration, with a negligible decline in the adsorption extent (10%) regarding its initial capacity. Finally, the residual dye in solution after treatment with magnetic adsorbents was degraded by using an advanced oxidation process (AOP) with pulsed light and hydrogen peroxide (343 mg/L); >90% of the dye was degraded after receiving a fluence of 118 J/cm2; the discoloration followed a pseudo first-order kinetics where the degradation rate was 0.0196 cm2/J. The newly synthesized ß-CD-EPI-magnetic polymer exhibited good adsorption properties and separability from water which, when complemented with a pulsed light-AOP, may offer a good alternative to remove dyes such as Direct Red 83:1 from water. It allows for the reuse of both the polymer and the dye in the dyeing process.

Sorption of 4-n-nonylphenol, 4-n-octylphenol, and 4-tert-octyphenol on cyclodextrin polymers.

Alkylphenols are industrial pollutants commonly present in wastewater. They are difficult to eliminate by conventional treatment processes, ending up in the sludge of wastewater treatment plants. In this study, we propose to use cross-linked cyclodextrin-based polymers (ECP) as sorbents to treat three alkylphenols, namely, one nonylphenol (4-n-NP) and two octylphenols (4-n-OP and 4-tert-OP), present in aqueous solution by a batch method. The experiments were carried out with five cyclodextrin polymers (α-ECP, ß-ECP, γ-ECP, α,ß,γ-ECP, and HP-ß-ECP). Sorption results showed that all polymers, with the exception of α-ECP, had high sorption capacities between 60 and 100% of the alkylphenols in the concentration range studied (between 25 and 100 µg/L). In all cases, HP-ß-ECP has shown the highest removals, regardless of the structure of the molecule. The order obtained was HP-ß-ECP >> ß-ECP ~ α,ß,γ-ECP >> γ-ECP > α-ECP. The 4-tert-OP compound was the best adsorbed, regardless the material and the solution studied. Sorption results also indicated that (i) the sorption efficiency decreased with the increasing of alkylphenol concentration; (ii) sodium chloride had a strong negative effect on the sorption process; and (iii) the performance remained unchanged after five sorption-regeneration cycles. The main sorption mechanism of alkylphenols occurring in ECP was the inclusion within the cyclodextrin cavities. The obtained results proved that cyclodextrin polymers could serve as efficient sorbents for the removal of alkylphenols from real effluents.

Use of Chènevotte, a Valuable Co-Product of Industrial Hemp Fiber, as Adsorbent for Pollutant Removal. Part I: Chemical, Microscopic, Spectroscopic and Thermogravimetric Characterization of Raw and Modified Samples.

FINEAU (2021-2024) is a trans-disciplinary research project involving French, Serbian, Italian, Portuguese and Romanian colleagues, a French agricultural cooperative and two surface-treatment industries, intending to propose chènevotte, a co-product of the hemp industry, as an adsorbent for the removal of pollutants from polycontaminated wastewater. The first objective of FINEAU was to prepare and characterize chènevotte-based materials. In this study, the impact of water washing and treatments (KOH, Na2CO3 and H3PO4) on the composition and structure of chènevotte (also called hemp shives) was evaluated using chemical analysis, X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray computed nanotomography (nano-CT), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, solid state NMR spectroscopy and thermogravimetric analysis. The results showed that all these techniques are complementary and useful to characterize the structure and morphology of the samples. Before any chemical treatment, the presence of impurities with a compact unfibrillated structure on the surfaces of chènevotte samples was found. Data indicated an increase in the crystallinity index and significant changes in the chemical composition of each sample after treatment as well as in surface morphology and roughness. The most significant changes were observed in alkaline-treated samples, especially those treated with KOH.

Biosorbents from Plant Fibers of Hemp and Flax for Metal Removal: Comparison of Their Biosorption Properties.

Lignocellulosic fibers extracted from plants are considered an interesting raw material for environmentally friendly products with multiple applications. This work investigated the feasibility of using hemp- and flax-based materials in the form of felts as biosorbents for the removal of metals present in aqueous solutions. Biosorption of Al, Cd, Co, Cu, Mn, Ni and Zn from a single solution by the two lignocellulosic-based felts was examined using a batch mode. The parameters studied were initial metal concentration, adsorbent dosage, contact time, and pH. In controlled conditions, the results showed that: (i) the flax-based felt had higher biosorption capacities with respect to the metals studied than the hemp-based felt; (ii) the highest removal efficiency was always obtained for Cu ions, and the following order of Cu > Cd > Zn > Ni > Co > Al > Mn was found for both examined biosorbents; (iii) the process was rapid and 10 min were sufficient to attain the equilibrium; (iv) the efficiency improved with the increase of the adsorbent dosage; and (v) the biosorption capacities were independent of pH between 4 and 6. Based on the obtained results, it can be considered that plant-based felts are new, efficient materials for metal removal.

Contributions of Dexter French (1918-1981) to cycloamylose/cyclodextrin and starch science.

Professor Dexter French (1918-1981) was an American chemist and biochemist at Iowa State College (University in 1959). He devoted his career to advance knowledge of polysaccharides and oligosaccharides, in particular starch, cyclodextrins, and enzymes. Cyclodextrins are oligosaccharides obtained from starch and are typically cage molecules with a hydrophobic cavity that can encapsulate other compounds nowadays the basis for many industrial applications. Since the 1960s, he has been recognized as an outstanding authority in the field of starches and cyclodextrins and has inspired researchers in laboratories around the world. This review, on the fortieth anniversary of his death, commemorates his remarkable contribution to starch and cyclodextrin chemistry. Firstly, we give an overview of his personal life and career. Secondly, we highlight some of the results on starch and cyclodextrins from Professor French and his group. A third part discusses his impact on the modern chemistry of cyclodextrins and starch.

Removal of Mercury Ions from Aqueous Solutions by Crosslinked Chitosan-based Adsorbents: A Mini Review.

Abatement of mercury emissions in air and waters has become a global challenge due to the toxicity of mercury species for life, yet actual remediation techniques are limited. In particular, adsorption of mercury ions onto solids is widely used but most adsorption techniques are not specific, and in turn, removal efficiency is lower. Adsorbents developed so far include activated carbon, clay, bentonite, cellulose and chitosan. Chitosan derivatives have recently attracted research attention for water purification because their molecular frames contain a large amount of -NH2 and -OH groups that can chelate with metal ions specifically. This manuscript reviews recent advances in chitosan-based adsorbents designed to remove mercury ions from wastewater. Focus is placed on their design, synthesis, characterization, adsorption properties, adsorption mechanisms and applications.

Environment-Friendly Approach toward the Treatment of Raw Agricultural Wastewater and River Water via Flocculation Using Chitosan and Bean Straw Flour as Bioflocculants.

Currently, there is a growing concern regarding water remediation from agricultural and domestic wastewaters. Among water treatment methods, flocculation is a widely used approach. In this study, the bioflocculation of wastewaters from Sinaloa (Mexico) was examined using two bioflocculants: chitosan and bean straw flour (BSF). The jar-test results showed that chitosan exhibited high effectiveness in pollutant removal from different sampling zones (agricultural wastewater and river water). Additionally, this bioflocculant reduced remarkably the concentration of Mn and Fe. On the other hand, BSF showed high effectiveness in pollutant removal for a specific type of wastewater, being highly competitive as compared to chitosan. Besides, BSF led to 40% of Mn removal from highly contaminated river water samples. For both biomaterials, bioflocculation was driven by charge neutralization and sweep flocculation mechanisms. For a given agricultural wastewater sample, both bioflocculants performed better than the commercial poly(aluminum chloride) for pH regulation and Fe removal.

Hemp to limit diffusion of difenoconazole in vegetable garden soils.

Triazole molecules are used to manage invasive aspergillosis, a fungal infection mainly due to Aspergillus fumigatus. A. fumigatus is not a phytopathogen, but, as it is widespread in soils, triazole fungicides have an unintended impact on it, selecting resistant populations' in environment. Thus, to maintain our ability to control fungal infections, whether in human health or agriculture, reduce the impact of the use of triazoles in the environment is important, notably limiting their diffusion in soils. Here we tested a hemp-based material as adsorbent to limit the spread of difenoconazole, a triazole fungicide, in vegetable soils. We studied the effects of contact time, material dose, difenoconazole concentration, and organic content of the soil using batch mode and percolation methods. Batch experiments showed that the material exhibited high adsorption capacities toward difenoconazole. Removal from the soil water increased from 46.6% using 0.35 g hemp per kg of soil to 77.0% using 1.75 g hemp per kg, for a contact time of 15 min and an initial difenoconazole concentration of 1.2 mg/L. For a contact time of 240 min, the removal was 93.5%. Percolation experiments showed that the quantity of difenoconazole removed was greater than the amount obtained by batch method: 41.9% of removal with only one passes of solution at a concentration of 12 mg/L is obtained through percolation technique whereas, with similar conditions, only 20% of removal is obtained by batch method, i.e. after 1 min of contact. The removal was strongly dependent on the number of passes: the values increased from 57.0% to 91.0% with increasing the number of passes from 1 to 15. Addition of hemp to soils allows to remove efficiently the difenoconazole fungicide from soil water. Hemp-based felt is a new and safe adsorbent that can be applied in agriculture to limit crop contamination.

Determination of azole fungal residues in soils and detection of Aspergillus fumigatus-resistant strains in market gardens of Eastern France.

Medical azole antifungals are major compounds used to prevent and to treat invasive aspergillosis (IA). Azole fungicides, called DMI (14-alpha demethylase inhibitors), are also widely used for crop protection and have been reported to be linked to azole-resistant A. fumigatus (aR-Af) development in the environment. The aim of this study was to determine whether or not market gardens that spray DMIs in Eastern France are also affected by the presence of aR-Af. Forty aR-Afs were detected in soils in only two of the four market gardens using DMIs, with 23% (7/30) and 10% (3/30) of soils containing aR-Af. A total of 87.5% of these isolates had the TR34/L98H mutation and 22.5% the TR46/Y121F/T289A mutation on the cyp51A gene. Analyses of residual azole concentrations in soils showed the presence of difenoconazole for up to 2 years after spraying, but only in soils of market gardens where aR-Af was detected. It is very important to identify professional activities that could lead to aR-Af development and to develop preventive measures for at-risk patients living near professional activities using DMIs. We have to better understand why, in some cases, the use of DMI is not linked to aR-Af. Measures should be taken to avoid the use of DMI conferring cross-resistance to preserve the efficiency of human therapeutics.

Simultaneous removal of five triazole fungicides from synthetic solutions on activated carbons and cyclodextrin-based adsorbents.

In this study, an adsorption-oriented process for the removal of fungicides from polycontaminated aqueous solutions was applied. To remove triazole fungicides from aqueous mixtures of propiconazole (PROPI), tebuconazole (TEBU), epoxiconazole (EPOXI), bromuconazole (BROMU) and difenoconazole (DIFENO), several materials used as adsorbents were compared using batch experiments, namely two conventional activated carbons (ACs) and five nonconventional cross-linked cyclodextrin (CD)-based materials (α-CDP, ß-CDP, γ-CDP, αßγ-CDP mixture, and hydroxypropyl-ß-CDP). This article presents the abatements obtained. As expected, ACs exhibited the highest levels of triazole fungicide removal: the treatment lowered the five azoles by more than 99%, and adsorption was non-selective. Concerning CD-based materials employed for the first time for the removal of fungicides from polycontaminated aqueous solutions, results were interesting in particular for hydroxypropyl-ß-CDP: 1 g of adsorbent placed in 1 L of solution containing 1 mg of each of five triazoles (5 mg in total) was able to remove over half of the fungicide amount (2.97 mg). The order obtained was the following: BROMU << PROPI ≅ EPOXI < TEBU << DIFENO. This indicates that, in the mixture studied, strong competition prevailed among fungicides for the binding sites.

Treated wastewater phytotoxicity assessment using Lactuca sativa: Focus on germination and root elongation test parameters.

Sensitive and simple ecotoxicological bioassays like seed germination and root elongation tests are commonly used to evaluate the phytotoxicity of waste and industrial discharge waters. Although the tests are performed following national and international standards, various parameters such as the number of seeds per dish, the test duration or the type of support used remain variable. To be able to make a correct comparison of results from different studies, it is crucial to know which parameter(s) could affect ecotoxicological diagnosis. We tested four different control waters and three seed densities. No significant differences on either germination rate or root elongation endpoints were shown. Nevertheless, we found that the four lettuce cultivars (Appia, batavia dorée de printemps, grosse blonde paresseuse, and Kinemontepas) showed significantly different responses when watered with the same and different metal-loaded industrial discharge water. From the comparison, it is clear that a differential sensitivity scale occurs among not just species but cultivars.

Desulfurization: Critical step towards enhanced selenium removal from industrial effluents.

Selenium (Se) removal from synthetic solutions and from real Flue Gas Desulfurization (FGD) wastewater generated by a coal-fired power plant was studied for the first time using a commercial iron oxide impregnated strong base anion exchange resin, Purolite® FerrIX A33E. In synthetic solutions, the resin showed high affinity for selenate and selenite, while sulfate exhibited a strong competition for both oxyanions. The FGD wastewater investigated is a complex system that contains Se (∼1200 µg L-1), SO42- (∼1.1 g L-1), Cl- (∼9.5 g L-1), and Ca2+ (∼5 g L-1), alongside a broad spectrum of toxic trace metals including Cd, Cr, Hg, Ni, and Zn. The resin performed poorly against Se in the raw FGD wastewater and showed moderate to good removal of several trace elements such as Cd, Cr, Hg, and Zn. In FGD effluent, sulfate was identified as a powerful competing anion for Se, having high affinity for the exchange active sites of the resin. The desulfurization of the FGD effluent using BaCl2 led to the increase in Se removal from 3% (non-desulfurized effluent) to 80% (desulfurized effluent) by combined precipitation and ion exchange treatment. However, complete desulfurization using equimolar BaCl2 could not be achieved due to the presence of bicarbonate that acts as a sulfate competitor for barium. In addition to selenium and sulfate removal, several toxic metals were efficiently removed (Cd: 91%; Cr: 100%; Zn: 99%) by the combined (desulfurization and ion exchange) treatment.

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters.

In this study, a polymer, prepared by crosslinking cyclodextrin (CD) by means of a polycarboxylic acid, was used for the removal of pollutants from spiked solutions and discharge waters from the surface treatment industry. In spiked solutions containing five metals, sixteen polycyclic aromatic hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic groups and CD cavities, the adsorption mechanism involves four main interactions: ion exchange, electrostatic interactions and precipitation for metal removal, and inclusion complexes for organics removal. In industrial discharge waters, competition effects appeared, especially because of the presence of calcium at high concentrations, which competed with other pollutants for the adsorption sites of the adsorbent.

Unexpected toxic interactions in the freshwater amphipod Gammarus pulex (L.) exposed to binary copper and nickel mixtures.

To document the toxicity of copper and nickel in binary mixtures, freshwater amphipods Gammarus pulex were exposed to the metals given independently or as mixtures. Toxicity to Cu alone was relatively high: 96-h LC10 and LC50 were found at 91 and 196 µg L(-1), respectively. Toxicity to Ni alone was very low, with 96-h LC10 and LC50 of 44,900 and 79,200 µg L(-1), respectively. Mixture toxicities were calculated from single toxicity data using conventional models. Modeled toxicity was then compared with the measured toxicity of the binary mixture. Two kinds of mixtures were tested. Type I mixtures were designed as combinations of Cu and Ni given at the same effect concentrations, when taken independently, to identify possible interactions between copper and nickel. In type II mixtures, Cu concentrations varied from 0 to 600 µg L(-1) while the nickel concentration was kept constant at 500 µg L(-1) to mimic conditions of industrial wastewater discharges. Ni and Cu showed synergic effects in type I mixtures while type II mixtures revealed antagonistic effects. Low doses of Ni reduced Cu toxicity towards G. pulex. These results show that even for simple binary mixtures of contaminants with known chemistry and toxicity, unexpected interactions between the contaminants may occur. This reduces the reliability of conventional additivity models.