Aminoguanidine modified magnetic graphene oxide as a robust nanoadsorbent for efficient removal and extraction of chlorpyrifos residue from water

https://doi.org/10.1016/j.jece.2021.106117Get rights and content

Highlights

  • Magnetic graphene-based nanoadsorbent was designed, synthesized, and characterized.

  • The nanoadsorbent was evaluated for removal and extraction of chlorpyrifos residues from water.

  • The cucumber was used as real sample for validation of the efficiency of nanoadsorbent in extraction of chlorpyrifos.

  • The chlorpyrifos removal was quantified by the HPLC-MS/MS method.

Abstract

In this paper, graphene-based nanoadsorbent is designed and synthesized through the functionalization of magnetic graphene oxide by aminoguanidine (denoted AGu@mGO(R)). The graphene oxide (GO) was first fabricated from rice husk biomasses and modified Hammer's method. Then, co-precipitation of Fe2+ and Fe3+ onto GO in primary media resulted in magnetic graphene oxide (mGO), which was subsequently functionalized by aminoguanidine to form AGu@mGO(R) nanoparticles. The fabricated graphene-based nanoadsorbent was characterized by several techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) analysis. AGu@mGO(R) efficiency was evaluated in removing chlorpyrifos, one of the most widely used pesticides from water and cucumber juice, as an actual sample. Different variables, including pH, concentration, temperature, exposure time, and amount of the adsorbent, were optimized on the efficiency of the adsorption activity of AGu@mGO(R) to obtain the most efficient pesticide removal. Isotherm, kinetic and thermodynamic of the adsorption processes were also evaluated. The chlorpyrifos desorption efficiency from AGu@mGO(R) was quantified by the HPLC-MS/MS method. The results showed the effective absorbent activity of AGu@mGO(R) on the removal of chlorpyrifos. Hence, this nonabsorbent would be used for the removal of the remained pesticide in agricultural wastewater. Additionally, the AGu@mGO(R) might be used for the quantification of pesticide residues in samples.

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 (single bondOH), carboxylic acid (single bondCO2H), 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.

References (64)

  • S.J. Garcia et al.

    Developmental neurotoxicity of chlorpyrifos: targeting glial cells

    Environ. Toxicol. Pharmacol.

    (2005)
  • X.-j. Hu et al.

    Removal of Cu (II) ions from aqueous solution using sulfonated magnetic graphene oxide composite

    Sep. Purif. Technol.

    (2013)
  • S. Iqbal et al.

    Effect of temperature and reaction time on the morphology of L-cysteine surface capped chalcocite (Cu2S) snowflakes dendrites nanoleaves and photodegradation study of methyl orange dye under visible light

    Colloids Surf. A Physicochem. Eng. Asp.

    (2020)
  • S. Iqbal et al.

    Shape and phase-controlled synthesis of specially designed 2D morphologies of L-cysteine surface capped covellite (CuS) and chalcocite (Cu2S) with excellent photocatalytic properties in the visible spectrum

    Appl. Surf. Sci.

    (2020)
  • M. Ismail et al.

    Advanced oxidation for the treatment of chlorpyrifos in aqueous solution

    Chemosphere

    (2013)
  • C. Jiang et al.

    A method for determination of [Fe3+]/[Fe2+] ratio in superparamagnetic iron oxide

    J. Magn. Magn. Mater.

    (2017)
  • L.P. Lingamdinne et al.

    A comprehensive review of applications of magnetic graphene oxide based nanocomposites for sustainable water purification

    J. Environ. Manag.

    (2019)
  • B. Liu et al.

    Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

    Chemosphere

    (2001)
  • G. Liu et al.

    Metal–organic framework preparation using magnetic graphene oxide–β-cyclodextrin for neonicotinoid pesticide adsorption and removal

    Carbohydr. Polym.

    (2017)
  • M. Lv et al.

    Non-covalent functionalized graphene oxide (GO) adsorbent with an organic gelator for co-adsorption of dye, endocrine-disruptor, pharmaceutical and metal ion

    Chem. Eng. J.

    (2018)
  • P. Mohammadi et al.

    Synthesis and characterization of Fe3O4@ SiO2 guanidine-poly acrylic acid nanocatalyst and using it for one-pot synthesis of 4H-benzo [b] pyrans and dihydropyrano [c] chromenes in water

    Mater. Chem. Phys.

    (2019)
  • W. Peng et al.

    A review on heavy metal ions adsorption from water by graphene oxide and its composites

    J. Mol. Liq.

    (2017)
  • M.A. Qamar et al.

    Highly efficient g-C3N4/Cr-ZnO nanocomposites with superior photocatalytic and antibacterial activity

    J. Photochem. Photobiol. A Chem.

    (2020)
  • S. Ramanaiah et al.

    Adsorptive removal of fluoride from aqueous phase using waste fungus (Pleurotus ostreatus 1804) biosorbent: kinetics evaluation

    Ecol. Eng.

    (2007)
  • I.A. Saleh et al.

    Removal of pesticides from water and wastewater: chemical, physical and biological treatment approaches

    Environ. Technol. Innov.

    (2020)
  • A. Sherlala et al.

    A review of the applications of organo-functionalized magnetic graphene oxide nanocomposites for heavy metal adsorption

    Chemosphere

    (2018)
  • M. Sher et al.

    Designing of highly active g-C3N4/Sn doped ZnO heterostructure as a photocatalyst for the disinfection and degradation of the organic pollutants under visible light irradiation

    J. Photochem. Photobiol. A Chem.

    (2021)
  • J. Sun et al.

    One-step synthesis of magnetic graphene oxide nanocomposite and its application in magnetic solid phase extraction of heavy metal ions from biological samples

    Talanta

    (2015)
  • H. Wang et al.

    Grafting of β-cyclodextrin to magnetic graphene oxide via ethylenediamine and application for Cr (VI) removal

    Carbohydr. Polym.

    (2014)
  • M. Waqas et al.

    Designing of a spatially separated hetero-junction pseudobrookite (Fe2TiO5-TiO2) yolk-shell hollow spheres as efficient photocatalyst for water oxidation reaction

    Appl. Catal. B Environ.

    (2017)
  • W. Xie et al.

    Guanidine post-functionalized crystalline ZIF-90 frameworks as a promising recyclable catalyst for the production of biodiesel via soybean oil transesterification

    Energy Convers. Manag.

    (2019)
  • S. Zeng et al.

    Enrichment of polychlorinated biphenyl 28 from aqueous solutions using Fe3O4 grafted graphene oxide

    Chem. Eng. J.

    (2013)
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