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Official websites use. Share sensitive information only on official, secure websites. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. Worldwide industrialization has grown at a rapid pace, contaminating water resources, particularly with phenolic pollutants that pose a risk to aquatic systems and human health. The goal of this study is to create an inexpensive magnetic composite that can effectively remove nitrophenol o-NP using adsorptive means. In this instance, a nonanyl chitosan N-Cs derivative was synthesized and then combined with activated petroleum coke AP-coke and magnetic Fe 3 O 4 to boost its adsorbability towards o-NP and to facilitate its separation. The equilibrium adsorption data coincided with the Langmuir, Freundlich, and Temkin isotherm models, with a maximum adsorption capacity of Besides, the developed adsorbent preserved satisfactory adsorption characteristics after reuse for five successive cycles. These findings hypothesize that the constructed magnetic composite could efficiently remove nitrophenols from polluted water with high performance and ease-separation. Recently, scientific researchers have shown considerable anxiousness regarding the effects of phenolic chemicals on human life and the aquatic environment 1. Petroleum refineries, petrochemical, coke oven plants, steel mills, synthetic resins, pharmaceuticals, coal gas, paints, mine discharge and plywood industries are considered the major sources of phenolic waste 2 , 3. A possible cause of their existence in the water is the breakdown of naturally occurring organic compounds brought about by internal and industrial waste disposal as well as overflows from agricultural areas. Under physical, chemical, and biological interactions, these phenolic compounds have the tendency to change into other, more hazardous moieties than their original ones 4 , 5. Particularly, when phenol and nitrite ions mix in water, o-nitrophenol and p-nitrophenol are created, since the reaction happens across a broad pH range and is affected by UV radiation sunlight 2 , 4 , 6. Specifically, o-Nitrophenol o-NP or 2-NP is a chemical compound with notable implications for both aquatic ecosystems and human well-being Abd El-Monaem et al. Within aquatic habitats, o-NP presents a hazard to the intricate balance of ecosystems, proving toxic to diverse organisms such as fish, invertebrates, and algae. Its introduction can disrupt ecosystem processes, resulting in diminished biodiversity and compromised nutrient cycles Ma et al. Regarding human health, exposure to o-NP may arise through ingestion, inhalation, or skin contact, eliciting immediate symptoms such as skin, ocular, and respiratory irritation 7. Prolonged exposure to o-NP is also linked to potential carcinogenic effects, with research indicating an elevated likelihood of specific cancers such as bladder cancer. Besides, o-NP falls under the classification of endocrine-disrupting chemicals EDCs , capable of perturbing hormonal systems and fostering conditions conducive to reproductive and developmental disorders 8. Therefore, techniques that are both economical and efficient are required to rid water bodies of these harmful substances. To remove nitrophenols, a number of approaches have been used, including the Fenton process, catalytic reduction, acoustic cavitation, catalytic ozonation, adsorption, biological treatment with or without oxygen, and acoustic catalytic breakdown 10 — Due to its low cost, easy processing, great performance, low energy consumption, and ability to produce treated wastewater of the highest quality on a small- and large-scale without secondary pollution, adsorption has grown in popularity among environmentalists 16 , Many adsorbent materials have been used as effective adsorbents, including silica, carbon-based materials, natural clays, MOFs materials, organic wastes, and polysaccharides 18 — Because polysaccharide-based adsorbents are abundant, environmentally friendly, biodegradable, non-toxic, and have the ability to interact chemically and physically with a wide range of molecules, they have garnered significant interest in recent decades for the purposes of extracting, purifying, and separating chemicals from water 22 , Chitosan Cs is a kind of polysaccharide created by simple deacetylation of chitin, which considered the main constituent of the exoskeleton of crab shells 24 , The existence of reactive hydroxyl and amine groups along the chitosan backbone allows various physical and chemical modification processes such as Schiff base formation, crosslinking, grafting and composite formation for widen its application range 26 — Owing to its excellent advantages including low-cost production, eco-friendly, non-toxicity, ease of modification and biodegradability chitosan has been employed as potential candidate in countless fields such as industrial, water treatment, pharmaceutical and medical fields 30 — Also, chitosan has been effectively used as adsorbent material for adsorptive removal of various noxious contaminates such as organic dyes, pharmaceutical residues and heavy metals Nevertheless, chitosan suffers from its limited surface area, weak mechanical properties and little adsorbability towards organic pollutants resultant from its higher hydrophilicity Petroleum coke AP-coke is a hydrophobic, carbonaceous, black solid material that mostly look like coal, while a tiny portion comprises carbonaceous fibers. It has vast proficiency to prepare various kinds of carbon-based materials like activated carbon 36 , carbon nanotubes. Activated carbon can be generated from PC, effectively applied for the removal of tetracycline 10 , phenols 11 , 37 , organic acids. Therefore, the modification of petroleum coke is essential for developing its pore structure, surface area, as well as removing the impurities. Furthermore, parameters affecting the adsorption process were investigated and optimized, such as contact time, o-NP concentration, adsorbent dosage, pH medium, and temperature. Chitosan M. Ferric chloride hexahydrate FeCl 3. The activation of petroleum coke P-coke was achieved by co-activation process Accurate 10 g of P-coke was added to nitric acid solution Nonanyl chitosan Schiff base derivative was prepared based on the authors previous work An exact quantity of nonanal 1. The resultant product exhibited an intense yellow color as a result of nonanyl chitosan Schiff base N-Cs formation. A precise quantity of the synthetized N-Cs Schiff base derivative 1. Then, 1. Hence, NaOH, as a strong base, is able to increase the pH of the mixture and can consequently react with the acidic deprotonated functional groups present in chitosan, such as amino and hydroxyl groups. Later, 0. An amount of 0. The adsorption process was performed in a shaking water bath at a constant speed of rpm. The N-Cs spectrum revealed the characteristic peaks of C—H wagging at wavenumbers and cm —1. The belonging bands to the wagging vibration of CH 2 manifested at cm —1 , while the band at cm —1 is attributed to the CH 3 vibration. In addition, the existing band at cm —1 corresponds to C—H out of the plane deformation The AP-coke spectrum elucidated bands at and cm —1 , which are accompanied by ether and hydroxyl, subsequently. The Fe 3 O 4 spectrum illustrated its distinguishing band at cm —1 , and the bands at and cm —1 corresponded to Fe-O stretching vibration. The bands at and cm —1 belong to OH bending and OH stretching vibration band manifested at cm —1 The N-Cs pattern denoted the amorphous character of N-Cs with a wide band at Similarly, the amorphous nature of AP-coke was evinced via its crystallographic pattern, where broadband appeared at The Fe 3 O 4 pattern depicts the distinguishing peaks of magnetite at In addition, the appearance of overlapping of the AP-coke and N-Cs peaks forms a broadband centered at The magnetism measurements clarified the superparamagnetic property of Fe 3 O 4 in which the coercivity was 8. This decline in the Fe 3 O 4 magnetism is due to the non-magnetic performance of AP-coke and N-Cs and the low proportion of Fe 3 O 4 in the composite It was found that the point of zero charges was 4. The composite has positive charges in a highly acidic medium and negative charges in alkaline media. The iron spectrum clarified the presence of ferrous species, where their distinctive peaks manifested at The oxygen spectrum depicted the peaks at The sulfur spectrum denoted the belonging peak to S—C at The nitrogen-spectrum Fig. S2 clarified the N-H peak at By analyzing N-Cs under the SEM, it was observed that it has a sponge-like morphology with a wrinkled and rough outer surface. The AP-coke morphology looks like irregular rocky shapes with quite uneven sizes. The Fe 3 O 4 image elucidated that its particles are almost spheroidal, with a tiny size on a nano-scale. The findings demonstrated that the adsorption process was quickly enhanced over the first 60 min with a maximum adsorption capacity of This phenomenon can be explained by an increase in the number of o-NP molecules that diffuse throughout the film fluid around the sufficient free adsorption sites of the adsorbent surface during the initial adsorption stage Nevertheless, there was no noticeable effect on the adsorption performance with increasing the contact time beyond min, since most of adsorption sites were saturated by o-NP molecules. The most important variable influencing the adsorption process is unquestionably pH. Thus, as shown in Fig. This finding may be explained by the fact that o-NP has a pKa of 7. On the other hand, as pH rose beyond 6, there was a noticeable decline in adsorption performance with increasing pH to 12 as recorded by the lowest values of The strong repulsion forces between the negatively charged magnetic composite and the anionic o-NP at higher pHs may be responsible for those results. The results refereed that the adsorption capacity meaningfully increased from Indeed, the increase in the initial concentration of pollutant reinforces its driving force that overwhelms the mass transfer struggle and enhances the migration from the bulk solution to the surface of the adsorbent. Figure 5 B illustrates how the adsorption performance of o-NP is affected by an increase in the dose of the adsorbent. As anticipated, the removal percentage of o-NP increases from On contrary, as the dose was increased, the adsorption capacity value decreased from to These results could be explained by increasing the segmental motion of the adsorbent composite with rising temperature. This would increase the pace at which o-NP disperses over the adsorbent's exterior boundary layer, boosting the adsorption profile. Figure 6 A,B indicate that the o-NP adsorption is best modeled by Pseudo second order since the R 2 values of Pseudo second order at a wide scale of o-NP concentrations are higher than those of Pseudo first order and the SSE value of Pseudo second order are lower than of those of Pseudo first order, as elucidated in Table 1. Besides, the propinquity between the experimental equilibrium capacity of o-NP and the theoretical values that are derived from Pseudo second order is another clue to prove the suitability of Pseudo second order to represent the o-NP adsorption. Interestingly, Elovich model Fig. The Langmuir model defined that the maximal adsorption capacity of o-NP was The Temkin model Fig. S4 revealed new bands at and cm -1 , which correspond to NO 2 stretching In addition, the observed band at cm —1 attributes to the benzene ring Therefore, the electrostatic interaction could not contribute to the adsorption of o-NP in acidic and neutral media. Moreover, the iron species of the composite could attach to o-NP molecules by forming coordination bonds. These suggestions were inferred by the peaks shifting of the sulfur, oxygen, iron, and nitrogen spectra after the o-NP adsorption Figs. These suggestions are consistent with kinetic and isotherm results that implied the participation of chemical and physical pathways in the o-NP adsorption. A comparison study was executed between the fabricated magnetic composite with other reported adsorbents was presented in Table 3. These results suggest the potential applicability for adsorptive removal of o-NP. Actual wastewater samples were collected from the industrial drain of a pigment factory in Alexandria, Egypt. The specifications of the collected actual wastewater before and after the treatment process are listed in Table 4. The o-NP concentration in the actual wastewater sample was about The test of regeneration proceeded by adding 0. Surprisingly, the recycling test results Fig. Factors affecting the adsorption process were investigated through a series of batch adsorption studies. A sequence of adsorption isotherm and kinetic studies concluded that the adsorption of o-NP onto the composite surface was fitted to Langmuir, Freundlich, and Temkin isotherm models with a maximum adsorption capacity of Overall, the proposed magnetic composite's outstanding adsorption performance, better reusability and simple separation characteristic point to its potential application for the adsorptive removal of phenolic contaminants from aquatic systems. We want to thank the editor and anonymous reviewers for their valuable comments and suggestions for this paper. Aly M. Abdelhamed: Methodology, Formal analysis, and Writing—original draft. Ahmed M. Gehan M. The data sets used and analyzed during the current study are available from the corresponding author on reasonable request. Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This section collects any data citations, data availability statements, or supplementary materials included in this article. As a library, NLM provides access to scientific literature. Sci Rep. Find articles by Ahmed M Omer. Find articles by Abdelazeem S Eltaweil. Box: , Alexandria, Egypt. Find articles by Aly M Abdelhamed. Find articles by Gehan M El-Subruiti. Received Jan 16; Accepted Jun 5; Collection date Open in a new tab. Biochar from Hizikia fusiformis The specification of the actual wastewater before and after treatment. Parameters Specifications before treatment Specifications after treatment pH 9. Supplementary Information. Publisher's note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Similar articles. Add to Collections. Create a new collection. Add to an existing collection. Choose a collection Unable to load your collection due to an error Please try again. Add Cancel.

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