The ongoing development of nanotechnology has raised concerns regarding the potential risk of nanoparticles (NPs) to the environment, particularly aquatic ecosystems. A relevant aspect that drives NP toxicity is represented by the abiotic and biotic processes occurring in natural matrices that modify NP properties, ultimately affecting their interactions with biological targets. Therefore, the objective of this study was to perform an ecotoxicological evaluation of CeO₂NPs with different surface modifications representative of NP bio-interactions with molecules naturally occurring in the water environment, to identify the role of biomolecule coatings on nanoceria toxicity to aquatic organisms. Ad hoc synthesis of CeO₂NPs with different coating agents, such as Alginate and Chitosan, was performed. The ecotoxicity of the coated CeO₂NPs was assessed on the marine bacteria Aliivibrio fischeri, through the Microtox® assay, and with the freshwater crustacean Daphnia magna. Daphnids at the age of 8 days were exposed for 48 h, and several toxicity endpoints were evaluated, from the molecular level to the entire organism. Specifically, we applied a suite of biomarkers of oxidative stress and neurotoxicity and assessed the effects on behaviour through the evaluation of swimming performance. The different coatings affected the hydrodynamic behaviour and colloidal stability of the CeO₂NPs in exposure media. In tap water, NPs coated with Chitosan derivative were more stable, while the coating with Alginate enhanced the aggregation and sedimentation rate. The coatings also significantly influenced the toxic effects of CeO₂NPs. Specifically, in D. magna the CeO₂NPs coated with Alginate triggered oxidative stress, while behavioural assays showed that CeO₂NPs coated with Chitosan induced hyperactivity. Our findings emphasize the role of environmental modification in determining the NP effects on aquatic organisms.

In this current work, the magnetic composite microsphere containing glutamine modified chitosan and silica coated Fe3O4 nanoparticles (CS-Gln-MCM) has been successfully prepared and extensively characterized, which is a kind of biodegradable materials. CS-Gln-MCM shows enhanced removal efficiency for both acid green 25 (AG25), an amphoteric dye, and mercury ions (Hg²⁺) from water in the respective while measured pH range compared with chitosan magnetic composite microsphere (CS-MCM) without modification. It is due to the fact that the grafted amino acid provides a variety of additional adsorption active sites and diverse adsorption mechanisms are involved. In AG25 and Hg²⁺ aqueous mixture, the modified adsorbents bear preferential adsorption for AG25 over Hg²⁺ in strong acidic solutions ascribed to multiple interactions between AG25 and CS-Gln-MCM, such as hydrogen bonding and electrostatic interactions. While, in weak acidic conditions, an efficient simultaneous removal is observed for different adsorption effects involved in aforementioned two pollutants. Besides, CS-Gln-MCM illuminates not only short equilibrium time for adsorption of each pollutant less than 20.0 min but also rapid magnetic separation from water and efficient regeneration after saturated adsorption. Therefore, CS-Gln-MCM bears great application potentials in water treatment.

In this study, we treated harmful Microcystis aeruginosa cyanobacteria using chitosan-modified nanobubbles. The chitosan-modified nanobubbles (255 ± 19 nm) presented a positive zeta potential (15.36 ± 1.17 mV) and generated significantly (p < 0.05) more hydroxyl radicals than the negatively charged nanobubbles (−20.68 ± 1.11 mV). Therefore, the interaction between the positively charged chitosan-modified nanobubbles and negatively charged M. aeruginosa (−34.81 ± 1.79 mV) was favored. The chitosan-modified nanobubble treatment (2.20 × 10⁸ particles mL⁻¹) inactivated 73.16% ± 2.23% of M. aeruginosa (2.00 × 10⁶ cells mL⁻¹) for 24 h without causing significant cell lysis (≤0.25%) and completely inhibited the acute toxicity of M. aeruginosa toward Daphnia magna. The inactivation was correlated (r² = 0.97) with the formation of reactive oxygen species (ROS) in M. aeruginosa. These findings indicated that the hydroxyl radicals generated by the chitosan-modified nanobubbles disrupted cell membrane integrity and enhanced oxidative stress (ROS formation), thereby inactivating M. aeruginosa. Moreover, the penetration of the chitosan-modified nanobubbles and cell alterations in M. aeruginosa were visually confirmed. Our results suggested that the chitosan-modified nanobubble treatment is an eco-friendly method for controlling harmful algae. However, further studies are required for expanding its practical applications.

At present, the simultaneous removal of organic dyes and heavy metals in complex wastewater has raised considerable concern, owing to their striking differences in physicochemical properties. Adsorption, as one of the few removal methods, has attracted extensive attention and gained popularity. Herein, a versatile EDTA and chitosan bi-functionalized magnetic bamboo biochar adsorbent (ECMBB) was synthesized for coinstantaneous adsorption of methyl orange (MO) and heavy metals (Cd(II) and Zn(II)). In this case, the as-synthesized ECMBB composites inherited favorable anionic MO removal performance from bamboo biochar (BB) obtained at 700 °C through electrostatic attraction, hydrogen bonding and π-π interaction, also enhanced the binding of cationic metals by introducing amino groups of chitosan and carboxyl groups of EDTA. In the unitary system, the removal of MO, Cd(II) and Zn(II) by three as-prepared adsorbents can be well illuminated by pseudo-second-order kinetic model and Langmuir isotherm theory. The saturated capture amounts of ECMBB at 25 °C are 305.4 mg g⁻¹ for MO, 63.2 mg g⁻¹ for Cd(II) and 50.8 mg g⁻¹ for Zn(II), which, under the same conditions, are 1.3, 2.6 and 2.5 times those of chitosan-modified magnetic bamboo biochar (CMBB) and 1.9, 6.1 and 5.4 times those of magnetic bamboo biochar (MBB), respectively. Remarkably, in MO-metal binary system, coexisting MO visibly enhanced the adsorption of Cd(II) and Zn(II), while coexisting heavy metals had no significant impact on MO adsorption. Furthermore, ECMBB exhibited no significant loss in adsorption efficiency even after eight adsorption-desorption experiments. This study lays the foundation for fabricating desired integrative biochar adsorbents in the simultaneous purification of organic and metallic pollutants from complex wastewater.

To develop more green, practical and efficient biochar amendments for acidic soils, chitosan-modified biochar (CRB) and alginate-modified biochar (ARB) were prepared, and their effects on promoting soil pH buffering capacity (pHBC) and immobilizing cadmium (Cd) in the paddy soils were investigated through indoor incubation experiments. The results of Fourier transform infrared spectroscopy and Boehm titration indicated that the introduction of chitosan and sodium alginate effectively amplified the functional groups of the biochar, and improved acid buffering capacity of the biochar. Since there was a plateau region between pH 4.5 and 5.5 in acid-base titration curve of the CRB, adding this biochar to acidic paddy soils apparently improved the pHBC and enhanced the acidification resistance of the paddy soils. The addition of ARB enhanced the reduction reactions during submerging and weakened the oxidation reactions during draining, thus retarded the decline of paddy soil pH during drainage. Furthermore, the pH of the paddy soils with ARB addition was higher at the end of draining, which reduced the activity of soil Cd. Considering the environmental sustainability of chitosan and sodium alginate and convenience of preparation method, biochars modified with these two materials provided alternatives for acidic paddy soil amelioration and heavy metal immobilization. However, the additional experiments should be conducted under field conditions to confirm practical application effects in the future.

In this study, an electrokinetic technique for remediation of Pb²⁺, Zn²⁺ and Cu²⁺ contaminated soil was explored using sodium alginate (SA) and chitosan (CTS) as promising biodegradable complexing agents. The highest Cu²⁺ (95.69%) and Zn²⁺ (95.05%) removal rates were obtained at a 2 wt% SA dosage, which demonstrated that SA significantly improved the Cu²⁺ and Zn²⁺ removal efficiency during electrokinetic process. The abundant functional groups of SA allowed metal ions desorption from soil via ion-exchange, complexation, and electrolysis. Pb²⁺ ions were difficult to remove from soil by SA due to the higher gelation affinity with Pb²⁺ than Cu²⁺ and Zn²⁺, despite the Pb²⁺ exchangeable fraction partially transforming to the reducible and oxidizable fractions. CTS could complex metal ions and migrate into the catholyte under the electric field to form crosslinked CTS gelations. Consequently, this study proved the suitability of biodegradable complexing agents for treating soil contaminated with heavy metals using electrokinetic remediation.

Among the seafood used globally, shellfish consumption is in great demand. The utilization of these shellfish such as prawn/shrimp has opened a new market for the utilization of the shellfish wastes. Considering the trends on the production of wealth from wastes, shrimp shell wastes seem an important resource for the generation of high value products when processed on the principles of a biorefinery. In recent years, various chemical strategies have been tried to valorize the shrimp shell wastes, which required harsh chemicals such as HCl and NaOH for demineralization (DM) and deproteination (DP) of the shrimp wastes. Disposal of chemicals by the chitin and chitosan industries into the aquatic bodies pose harm to the aquatic flora and fauna. Thus, there has been intensive efforts to develop safe and sustainable technologies for the management of shrimp shell wastes. This review provides an insight about environmentally-friendly methods along with biological methods to valorize the shrimp waste compared to the strategies employing concentrated chemicals. The main objective of this review article is to explain the utilization shrimp shell wastes in a productive manner such that it would be offer environment and economic sustainability. The application of valorized by-products developed from the shrimp shell wastes and physical methods to improve the pretreatment process of shellfish wastes for valorization are also highlighted in this paper.

High removal efficiency and excellent recyclability are the fundamental qualities that an outstanding adsorbent used for organic dye removal should possess. In this study, two recyclable gels (sodium alginate/Ca/fiber: SCFA hydrogels; cellulose nanofiber/chitosan: CNFCS aerogels) were successfully fabricated using the facile method. Additionally, the as-prepared adsorbents were investigated using a series of characterizations. The adsorption behavior and anti-interference performance of the synthesized gels were compared by choosing methylene blue (MB) as the model pollutant. The kinetic behavior of the gels towards MB was consistent with the pseudo first-order model, and the SCFA hydrogels reached adsorption equilibrium faster than the CNFCS aerogels. The maximum adsorption capacity of MB on the SCFA hydrogels and CNFCS aerogels was 1335.0 and 164.5 mg g⁻¹ (pH = 7.0, dosage: 0.5 g/L; initial concentration from 15 to 180 mg L⁻¹), respectively. More specifically, we found that the co-existing anions had different effects on MB adsorption over the gels used for MB removal. Furthermore, for the SCFA hydrogels, co-existing natural organic matter (NOM) at low concentrations enhanced MB adsorption, and then stabilized as the concentration of NOM increased. However, this increasing trend was not observed for MB adsorption on CNFCS aerogels; these gels exhibited a slight decrease at first, and then showed no change. Nevertheless, both the gels exhibited superior regeneration and recycling abilities.

Physicochemical properties of nanoparticles influence their environmental fate and toxicity, and studies investigating this are vital for a holistic approach towards a comprehensive and adequate environmental risk assessment. In this study, we investigated the effects of size, surface coating (charge) of silver nanoparticles (AgNPs) – a most commonly-used nanoparticle-type, on the bioaccumulation in, and toxicity (survival, growth, cocoon production) to the earthworm Lumbricus rubellus. AgNPs were synthesized in three sizes: 20, 35 and 50 nm. Surface-coating with bovine serum albumin (AgNP_BSA), chitosan (AgNP_Chit), or polyvinylpyrrolidone (AgNP_PVP) produced negative, positive and neutral particles respectively. In a 28-day sub-chronic reproduction toxicity test, earthworms were exposed to these AgNPs in soil (0–250 mg Ag/kg soil DW). Earthworms were also exposed to AgNO3 at concentrations below known EC50. Total Ag tissue concentration indicated uptake by earthworms was generally highest for the AgNP_BSA especially at the lower exposure concentration ranges, and seems to reach a plateau level between 50 and 100 mg Ag/kg soil DW. Reproduction was impaired at high concentrations of all AgNPs tested, with AgNP_BSA particles being the most toxic. The EC50 for the 20 nm AgNP_BSA was 66.8 mg Ag/kg soil, with exposure to <60 mg Ag/kg soil already showing a decrease in the cocoon production. Thus, based on reproductive toxicity, the particles ranked: AgNP_BSA (negative) > AgNP_PVP (neutral) > Chitosan (positive). Size had an influence on uptake and toxicity of the AgNP_PVP, but not for AgNP_BSA nor AgNP_Chit. This study provides essential information on the role of physicochemical properties of AgNPs in influencing uptake by a terrestrial organism L. rubellus under environmentally relevant conditions. It also provides evidence of the influence of surface coating (charge) and the limited effect of size in the range of 20–50 nm, in driving uptake and toxicity of the AgNPs tested.

To remove benzo[a]pyrene (BaP) that has accumulated in the Jiaozhou Bay wetland sediment, two strains (JB1 and JB2) were selected from the BaP-contaminated the wetland sediment and immobilized in coal cinder and chitosan beads using entrapping and surface adsorption methods. Biodegradation of BaP in sediment was carried out in pots. The results showed that, supported by the coal cinder and chitosan beads, 71.9, 65.5, 58.9 and 66.1% of the BaP in the immobilized cells was degraded after 40d. These percentages were clearly higher than the 47.7% that degraded from free cells. Kinetic analysis indicated that the immobilized gel-beads might remove BaP by multiple control steps. Compared to the chitosan, coal cinder-entrapping beads exhibited a higher removal rate for BaP; however, the degradation rates from coal cinder- and chitosan-surface adsorption beads were almost the same. This result indicates that in addition to the BaP-degrading bacteria, carrier materials and immobilizing methods play an important role in determining the success of a biodegradation strategy.