It is well-established that aquatic wildlife is exposed to natural and synthetic endocrine disrupting compounds which are able to interfere with the hormonal system. Although advanced oxidation processes (AOPs) have shown to be effective, their application is limited by a relatively high operational cost. In order to reduce the cost of energy consumed in the AOPs, widely available solar energy instead of UV light may be applied either as photocatalytic oxidation or as photosensitized oxidation. The main goal of the present study was to investigate the sunlight photodegradation of paraben mixture. Two processes, namely the photocatalytic oxidation with modified TiO₂ nanoparticles and photosensitized oxidation with photosensitive chitosan beads, were applied. The oxidants were identified as singlet oxygen and hydroxyl radicals for photosensitized and photocatalytic oxidation, respectively. The toxicity, as well as ability to water disinfection of both processes under natural sunlight, has been investigated. Application of sunlight for the processes led to degradation of parabens. The efficiency of both processes was comparable. Despite the fact that singlet oxygen is weaker oxidant than hydroxyl radicals, the photosensitized oxidation seems to be more promising for wastewater purification, due to the possibility of chitosan bead reuse and more effective water disinfection. Graphical Abstract ᅟ

A magnetic glycine-grafted chitosan sorbent (Gly) was functionalized to produce a hydrazide derivative (HGly). The two sorbents were tested in batch mode for the sorption of a series of 10 metal ions present in the groundwater collected in three wells in the Wadi (valley) Nasib mining area (SW Sinai, Egypt). HGly is much more efficient for metal recovery than Gly. Under selected experimental conditions (sorbent dosage 1.5 g L⁻¹), the sorption efficiency is not sufficient for achieving the standard levels for drinking water: the most problematic metal ions in terms of drinkability remain aluminum (too high metal concentration in the groundwater), cadmium, and chromium for the three wells (and nickel in the case of only one well). Increasing the sorbent dosage improves the treatment efficiency. The sorbent (HGly) was tested in fixed-bed columns. The breakthrough curves were compared for the different metals for the groundwater collected in the most contaminated of the three wells. The levels of metal concentration in the treated groundwater are too high for direct use in irrigation. However, they are consistent with the standards for livestock drinking water (based on FAO recommendations, Food and Agriculture Organization of the United Nations). The metals can be readily desorbed using 0.5 M HCl solutions with a relatively high concentrating effect (i.e., 50 times). The re-use of the sorbent for three successive cycles of sorption/desorption cycles shows a progressive but weak decrease in sorption and desorption performances.

Equilibrium sorption studies of anionic species of arsenite, As(III) ions and arsenate As(V) ions onto two biosorbents, namely, chitosan and nanochitosan, have been investigated and compared. The results and trends in the sorption behavior are novel, and we have observed during the sorption process of the As(III) and As(V) on chitosan, a slow process of desorption occurred after an initial maximum adsorption capacity was achieved, before reaching a final but lower equilibrium adsorption capacity. The same desorption trend, however, is not observed on nanochitosan. The gradual desorption of As(III) and As(V) in the equilibrium sorption on chitosan is attributed to the different fractions of the dissociated forms of arsenic on the adsorbent surface and in solution and the extent of protonation of chitosan with the changing of solution pH during sorption. The change of solution pH during the sorption of arsenite ions on chitosan was also influenced by the interaction between the buffering effect of the arsenite species in the aqueous medium and the physical properties of chitosan. The final equilibrium adsorption capacity of chitosan for As(III) and As(V) was found to be around 500 and 8000 μg/g, respectively, whereas the capacities on nanochitosan are 6100 and 13,000 μg/g, respectively.

It is well established that aquatic wildlife in marine and freshwater of the European Union is exposed to natural and synthetic endocrine disruptor compounds (EDCs) which are able to interfere with the hormonal system causing adverse effects on the intact physiology of organisms. The traditional wastewater treatment processes are inefficient on the removal of EDCs in low concentration. Moreover, not only the efficiency of treatment must be considered but also toxicological aspects. Taking into account all these aspects, the main goal of the study was to investigate the photochemical decomposition of hazardous phenolic compounds under simulated as well as natural sunlight from the toxicity point of view. The studies were focused on photodegradation of 2,4-dichlorophenol as well as mixture of phenol, 2-chlorophenol and 2,4-dichlorophenol. Photosensitized oxidation process was carried out in homogeneous and heterogeneous system. V. fischeri luminescence inhibition was used to determine the changes of toxicity in mixture during simulated and natural irradiation. The photodegradation was carried out in three kinds of water matrix; moreover, the influence of presence of inorganic matter on the treatment process was investigated. The experiments with natural sunlight proved applicability of photosensitive chitosan for visible-light water pollutant degradation. The results of toxicity investigation show that using photosensitive chitosan for visible-light, the toxicity of reaction mixture towards V. fischeri has significantly decreased. The EC₅₀ was found to increase over the irradiation time; this increase was not proportional to the transformation of the parent compounds.

The present study explores the innocuous, biocompatible, and extremely competent molecularly imprinted chitosan/RTIL electrospun nanofibers having average diameter of 30 nm for the expulsion of thorium (IV) ions from the mimicked effluent waste. The extended Flory–Huggins theory and three-dimensional molecular modeling have been effectively premeditated via Materials Studio software for enumerating the inter-miscibility and compatibility (Chi parameter (χ) = 1.019, mixing energy (Eₘᵢₓ) = 0.603 kcal/mol) of the chitosan/RTIL (1-butyl-3-methylimidazolium tetrafluoroborate). The maximum adsorption efficiency is found to be 90% at a neutral pH of 7, and a temperature of 298 K within 120 min. The adsorption process was extensively studied by two-parameter adsorption isotherms like Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich (D–R) and three-parameter models like Redlich–Paterson and Sips isotherm. Pseudo-second-order kinetics model (R² = 0.982) and Langmuir isotherm (R² = 0.994) bestowed the best fitting on chitosan/RTIL nanofibers for the adsorption of Th (IV) ions. The thermodynamic study reveals the spontaneity and exothermic nature of the reaction. The experimental analysis conjoint with isotherm and kinetic models, and simulation study establish the applicability of chitosan/RTIL nanofibers for the expulsion of Th (IV) and other toxic metal ions from the effluents. Graphical abstract Ion-imprinted electrospun nanofiber for expulsion of thorium (IV) ion

Dehydrochlorination of lindane is commonly conducted in homogeneous alkaline solutions, possessing a series of problems such as corrosion and poor recyclability. In order to overcome the pervasive problems concerning homogeneous catalysts, heterogeneous catalysts have been increasingly employed in the applications. In this study, nitrogen-doped porous carbons (NPCs) were developed by a simple way in which chitosan and ZnCl₂ were employed as the precursor and activation agent, respectively. NPCs exhibited high surface area (1111–1497 m²/g) and large porosity (0.464–0.621 cm³/g), resulting in a great adsorption affinity to lindane and the by-products. As solid bases, NPCs displayed an enhanced catalytic activity on lindane dehydrochlorination. This was closely related to the amount of pyridinic nitrogen on the pore surface, which could be tuned by the synthesis temperature. The optimal removal efficiency of lindane was up to 99.9% in presence of A800 (a NPC catalyst) at moderate pH (9.0) and mild temperature (45 °C) after incubation for 24 h. The rate constant for A800 suspension was improved by 2–3 orders of magnitude in comparison with that obtained in homogeneous solution at moderate pH (9.0) and mild temperatures (25–45 °C). The reusability of the material was evaluated by cycling for three times without noticeably reduced catalytic activity. This study provides a novel strategy to achieve partial dechlorination of chlorinated organic pollutants.

This comparative study investigates pre-concentration/separation procedure for the magnetic solid phase extraction of Hg(II) species by a new green materials: naked magnetic chitosan flakes coated Fe₃O₄ micro-particles (NMCFs) and magnetic chitosan flakes coated Fe₃O₄ micro-particles embedded ethylenediaminetetraacetic-disodium (MCFs-EDTA-Na₂) in a batch process. The sorption procedure was optimized by using model solutions containing mercury(II) ions in chloride medium. The influence of experimental parameters like pH, time reaction, initial Hg(II) concentration, and ionic strength was investigated. The SEM micrograph indicates a good dispersion of magnetite micro-particles onto chitosan flakes. The FTIR spectrum reveals that EDTA-Na₂ moieties have been successfully cross-linked onto magnetic chitosan flakes. Vibration magneto-metric measurements confirm the paramagnetic (without remanence) behavior of NMCFs and MCFs-EDTA-Na₂. The experimental sorption data show that Hg(II) ions extraction yield decreases in acidic medium in both NMCFs and MCFs-EDTA-Na₂. The found optimum pH values are near 4.5 using NMCFs and 4.7 when the Hg(II) ion sorption occurs onto MCFs-EDTA-Na₂ micro-particles. The results also showed that Hg(II) ion sorption kinetic was very fast at the initial stage of contact time. The maximal sorption capacity was found to be 454 ± 13 mg g⁻¹, under optimum conditions, using NMCFs and 495 ± 14 mg g⁻¹ when MCFs-EDTA-Na₂ was used.

Serratia sp. W4-01 was immobilized in chitosan-activated carbon beads and used for diesel oil removal. The type and concentration of chitosan, activated carbon content, and bead diameter were investigated as factors affecting diesel oil removal. The results showed that 2% (w/v) squid pen chitosan beads modified with 1% activated carbon (w/v) and with a 3-mm diameter had a good spherical shape and strength as well as diesel oil removal capability. The immobilized W4-01 cells removed more than 40% of diesel oil after 7 days when the initial diesel oil concentration was 100 to 400 mg L⁻¹, whereas 29–36% of diesel oil was removed after 14 days when the initial concentration was 800 to 1000 mg L⁻¹. Additionally, the immobilized cells maintained the ability to remove diesel oil over a pH range of 5–11. The addition of a biosurfactant increased the diesel oil removal from 62 to 75%. The reusability tests revealed that the ability of immobilized cells to remove diesel oil was enhanced after reuse, and 50–90% of diesel oil was removed during 2 to 12 reuse cycles. The stability and survival of W4-01 cells was confirmed by scanning electron microscopy and confocal laser scanning microscopy. The results of this study showed the potential use of W4-01 cells immobilized in chitosan-activated carbon beads for future applications in remediating diesel contamination.

Discharges of huge quantities of leather solid wastes by leather industries and the increased use of synthetic packaging films have raised serious concerns on account of their environmental impacts. The paper focuses on the development and characterization of potential environmentally friendly composite films using collagen hydrolysate (CH) extracted from leather solid wastes and chitosan (C) to assess the feasibility of producing polymeric materials suitable for applications in packaging and wrapping purposes. Solid collagen-based protein hydrolysate was extracted from chromium-tanned leather wastes and analyzed to determine its chemical properties. With the goal of improving the physico-chemical performance of CH, three types of composite films (CH75/C25, CH50/C50, CH25/C75) were prepared with increasing concentrations of C, and some of their physical and functional properties were characterized. The results indicated that the addition of C caused increase (p < 0.05) in the thickness, tensile strength (TS), elasticity modulus (EM), and water vapor permeability (WVP), leading to stronger films as compared with CH film, but significantly (p < 0.05) decreased the elongation at break (EAB) and solubility of films (p < 0.05). The light barrier measurements present low values of transparency at 600 nm of the CH/C films, indicating that the films are very transparent and they have excellent barrier properties against UV light. The structural properties investigated by FTIR and DSC showed total miscibility between both polymers. Scanning electron micrographs revealed that CH/C composite films showed a compact homogeneous structure. These results demonstrate the potential application of CH/C composite films in packaging industry.

The performance of synthesized cast and electrospun polyvinyl alcohol/chitosan/zinc oxide/aminopropyltriethoxylsilane (PVA/chitosan/ZnO-APTES) nano-adsorbents were compared in removal of Cd(II) and Ni(II) ions from wastewater. The adsorbents were characterized by SEM, BET, FTIR and TGA analyses. Furthermore, the swelling investigations were carried out to study the adsorbent stability in aqueous solution. The effect of several parameters such as contents of ZnO-NH₂, contact time, initial Cd(II) and Ni(II) concentration and temperature on the adsorption capacity was investigated in a batch mode. In comparison with cast adsorbent, nanofiber adsorbent indicated the better adsorption performance. The experimental data well fitted the double-exponential kinetic model. In single metal ion system, the maximum adsorption capacity of nanofiber for Cd(II) and Ni(II) ions is estimated to be 1.239 and 0.851 mmol/g, respectively, much higher than qₘ of cast adsorbent for Cd(II) (0.625 mmol/g) and Ni(II) (0.474 mmol/g) ions. Thermodynamic parameters were investigated to identify the nature of adsorption process. In binary system of Cd(II)-Ni(II) ions, the inhibitory effect of competitive Cd(II) ion on the Ni(II) adsorption was greater than the inhibitory effect of competitive on the Cd(II) adsorption. The selectivity adsorption of both nanofiber and cast adsorbents was in order of Cd(II) > Ni(II).