Aminoguanidine modified magnetic graphene oxide as a robust nanoadsorbent for efficient removal and extraction of chlorpyrifos residue from water
Graphical Abstract
Introduction
Pesticides are inevitable agrochemicals in modern agriculture, used widely for several decades to improve crop production. However, the excessive consumption of these agrochemicals has raised severe environmental concerns due to their off-site migration and damaging effects [3]. For example, chlorpyrifos (O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate) is an organophosphorus pesticide that is widely used in soil to control Diptera, Homoptera, and Lepidoptera or consumed in different crops such as fruit (e.g., pome, stone, citrus), bananas, vines, and vegetables [46]. However, excessive exposure to chlorpyrifos can cause neurological effects [9], growth disorders [30], brain cell replication [14], intracellular oxidative stress [15], and thereby disrupting normal cellular development & differentiation [20], and autoimmune disorders [28]. Additionally, exposure to chlorpyrifos during pregnancy may cause mental disorders in children. Therefore, eliminating chlorpyrifos from water systems is a challenge that needs to be addressed immediately [51]. Several efforts have been developed on the removal of these agrochemicals from the soil and water resources.
In addition, various techniques have been reported based on modified nanoparticles. A stabilization agent of L-cysteine synthesized the CuS NPs and Cu2S (nano leaves) NLs. Then CuS@L-Cys NPs and Cu2S@L-Cys NLs used for the photodegradation of methyl orange as a model dye [24], [25]. Additionally, the Effects of temperature and reaction time were studied on the morphologies of synthesized Cu2S@L-Cys NLs [24], [25]. The pristine Fe2TiO5, pristine TiO2, and Fe2TiO5-TiO2 hetero-structure yolk-shell hollow spheres as FTYS-HS were constructed for photocatalytic water oxidation [65]. For photocatalytic H2 production, CdS nanosheets and multi-layered MoS2 nanocrystals were applied [27]. In addition, Researchers illustrated the antibacterial activity of nanomaterials for degradations. For example, ZnO@Ni NPs were assisted as the control for the degradation rate of the composite plastic [26]. A series of g-C3N4 hybridized Sn doped ZnO novel nanocomposites were prepared. Among them, the Sn doped ZnO/50% g-C3N4 NCs exhibited the most effective and high antibacterial susceptibility [61]. Another nanomaterial named g-C3N4/Cr-ZnO hybrid composite exhibited photocatalytic methylene blue degradation and excellent antibacterial activity [53].
Furthermore, Zn(II)-based metal-organic framework [Zn(TDC)(4-BPMH)]n·n(H2O) was designed and synthesized for adsorption enhancement of 2,4-dichlorophenol and amoxicillin [1]. Bi2MoO6 HMSs were via carbon spheres. And then, their photocatalytic wastewater purification under visible light irradiation was proved [2]. In the other study, the Sudan black B dye was used as a sensitizer for obtaining visible-light-active TiO2 for different pollutants [55].
The treatment techniques for pesticide removal are divided into three main groups: physical, chemical, and biological degradation. Each of them is subdivided into various techniques: sand filtration, chlorination, oxidation, ion exchange, adsorption, or microorganism treatment [56]. The adsorption technique is the most efficient because of the simple procedure, no pre-treatment necessities, eco-friendly, no toxic byproducts, and low cost. Accordingly, thrust to develop efficient approaches, applying nanomaterial-based adsorption is of high interest, promising to be cost-effective and based on the ease of preparation and operation.
Graphene oxide (GO) is known as a potential two-dimensional structured material with a high surface area. It is rich in manipulable functionalities, e.g., hydroxyl (OH), carboxylic acid (CO2H), and epoxide () groups, which are so vital to give unique merits to the surface of GO for versatile applications [13], [4], [57], [7], [8]. Despite the ease of the absorption on the GO surface, the expansion of the practical applicability of GO as an adsorbent has been restricted because of the challenging collection of GO from the solution regarding its high hydrophilicity [38].
Different surface modifications have been tried to facilitate GO recyclability and improve adsorption capacity and efficiency to overcome this limitation. Magnetic graphene oxide is a hybrid material composed of graphene oxide and a magnetic material, such as magnetic iron oxide [12], [34], [63].
Recently magnetic graphene oxide, constructing its highly efficient and useful combination of the pivotal properties of GO and magnetic nanoparticles, has attracted significant attention. As one of the hottest materials in chemistry and material sciences, magnetic graphene oxide has been studied extensively due to its fantastic thermal, mechanical, chemical properties, efficient and straightforward recyclability, and unique potential technical applications [40], [6].
As an advantage, magnetic graphene oxide can easily be functionalized by various functionalities and could be separated from the reaction mixture by an external magnetic field due to its magnetic behavior. The application of functionalized magnetic graphene oxide in removing pollutants from aqueous solutions is of high interest because of its advantageous properties [60]. The removal of several pollutants such as cadmium ions and ionic dyes [18], arsenate [59], copper ions [22], and uranium ions [11] by magnetic graphene oxide composites have been reported. For more efficient adsorption of the pollutants, functionalization of magnetic graphene oxide by poly(vinyl alcohol) [38], EDTA [16], and other functionalities [62] has been investigated, and the results were advantageous in the removal of heavy metal ions and pesticides from industrial and biological wastewater [36], [52].
On the other hand, the main primary material for synthesizing Go is carbon. Recently, agro-wastes as continuous and renewable resource for mass production of nanomaterials have been gaining limelight as one of the most suitable strategies to effectively exploit them [43], [44], [45]. Hence, in this research, we used agro-wastes as a source of carbon [10], [50]. The husk and straw biomasses are two non-edible residuals of rice that, without integrated management, lead to serious environmental concerns.
In this study, rice agro-waste-derived graphene oxide (GO(R)) was prepared from the burnt remnants of rice husk. The aminoguanidine functional group was then grafted on the surface of magnetic graphene oxide as the terminal pendant Owing to the good properties of aminoguanidine in creating hydrogen and electrostatic bonds. It is referred to as aminoguanidine functionalized onto the surface of magnetic graphene oxide nano-sheets (AGu@mGO(R)). The efficiency of AGu@mGO(R) in the removal of chlorpyrifos pesticide was evaluated. This evaluation was based on AGu@mGO(R) efficiency in extracting chlorpyrifos from water or cucumber juice like a real sample. Moreover, the amount of extracted chlorpyrifos was quantified by HPLC-MS/MS method.
Section snippets
General remarks
Solvents, reagents, and chemicals were purchased from Merck, Sigma Aldrich, and Fluka chemical companies. Chlorpyrifos (99.9% purity) was purchased from Sigma Aldrich. Potassium hydroxide (anhydrous, ≥ 99.95%), sulfuric acid (H2SO4, 98%), sodium nitrate (NaNO3, 99%), potassium permanganate (KMnO4, 99%), hydrochloric acid (HCl, 37%), ferrous chloride (FeCl2, 98%), ferric chloride (FeCl3, 97%), toluene (99.5%), 3-chloropropyltrimethoxysilane (97%), ethanol (EtOH, 99.8%), aminoguanidine
Nano-absorbent studies
Aminoguanidine modified magnetic graphene oxide (AGu@mGO(R)) was synthesized and applied to remove chlorpyrifos from aqueous samples. For this purpose, the rice biomass-derived graphene oxide (GO(R)) was synthesized according to Hammer's modified method using the burnt remnants of rice husk and straw as a carbon resource. Then to achieve efficient, recyclable GO nanosheets, superparamagnetic iron oxide nanoparticles (SPION) were decorated on the RGO sheets. Therefore, Fe2+ and Fe3+ ions were
Conclusion
In this paper, a novel graphene oxide-based nanoadsorbent was synthesized from agricultural solid wastes and followed by surface modification. For improving the reusing process, the surface of graphene oxide was furnished using magnetic nanoparticles and then was functionalized by aminoguanidine (AGu) group to increase its efficiency due to the ability of guanidine in hydrogen bonds formation. The synthesized AGu@mGO(R) nanosheets were characterized by several characterization techniques and
Ethical approval
Not applicable.
Funding
This study was no supported.
Consent to participate
The authors declare their consent to participate in this article.
Consent to publish
The authors declare their consent to publish this article.
CRediT authorship contribution statement
Vahideh Mahdavi: Investigation, Data curation, Supervision, Resources, Conceptualization. Fatemeh Taghadosi: Data curation, Literature searching, Writing. Fariba Dashtestani: Software, Conducting risk assessment, Synthesis of nanomaterials. Saeed Bahadorikhalili: Software, Conducting risk assessment, Synthesis of nanomaterials. Amin Mousavi Khaneghah: Supervision, Resources, Writing – review & editing. Leila Maˈmani: Supervision, Resources, Writing – review & editing. Mahdi Moridi Farimani:
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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