Skip to main content
Log in

Amine-functionalized MIL-101(Fe) for highly selective and efficient extraction of phenoxy carboxylic acid herbicides from environmental water and rice samples

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Phenoxy carboxylic acid herbicides (PCAs) are widely used in agricultural production. However, due to their potential threat to human health, it is necessary to develop efficient analysis method for monitoring PCA concentration in environment and food samples. Based on dispersive micro-solid phase extraction (D-μ-SPE) with amine-functionalized metal–organic framework MIL-101(Fe)-NH2, a selective, sensitive, and cost-efficient method was proposed for the extraction of PCAs from environmental water and rice samples in this study. From the perspective of adsorption kinetics and isotherms, interaction mechanisms between MIL-101(Fe)-NH2 and PCAs were investigated. Key parameters of D-μ-SPE procedure including adsorbent dosage, solution pH, ionic strength, eluting solution, and washing solutions were optimized. Using of small amount of MIL-101(Fe)-NH2 could achieve desirable extraction effect due to its large surface area and multiple interactions with PCAs. Under the optimized D-μ-SPE conditions, calibration curves of 8 PCAs were linear within a concentration range of 0.05–5 ng/mL for water samples (r2 > 0.9898) and 0.5–50 ng/g for rice samples (r2 > 0.9879). Limits of detection of water and rice samples were as low as 0.004–0.008 ng/mL and 0.05–0.1 ng/g, respectively. The recoveries of 8 PCAs ranged from 83.0 to 109.3%. Both inter- and intra-day relative standard deviations were less than 10.3%. Our proposed method was successfully employed in actual environmental water and rice samples.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • Amini S, Amiri M, Ebrahimzadeh H, Seidi S, Hejabri kandeh S (2021) Synthesis of magnetic Cu/CuFe2O4@MIL-88A(Fe) nanocomposite and application to dispersive solid-phase extraction of chlorpyrifos and phosalone in water and food samples. J Food Compos Anal 104:104128

    CAS  Google Scholar 

  • Barbosa ADS, Julião D, Fernandes DM, Peixoto AF, Freire C, de Castro B, Granadeiro CM, Balula SS, Cunha-Silva L (2017) Catalytic performance and electrochemical behaviour of metal–organic frameworks: MIL-101(Fe) versus NH2-MIL-101(Fe). Polyhedron 127:464–470

    CAS  Google Scholar 

  • Bauer S, Serre C, Devic T, Horcajada P, Marrot J, Férey G, Stock N (2008) High-throughput assisted rationalization of the formation of metal organic frameworks in the iron(III) aminoterephthalate solvothermal system. Inorg Chem 47:7568–7576

    CAS  PubMed  Google Scholar 

  • Boontongto T, Burakham R (2019) Evaluation of metal-organic framework NH2-MIL-101(Fe) as an efficient sorbent for dispersive micro-solid phase extraction of phenolic pollutants in environmental water samples. Heliyon 5:e02848

    PubMed  PubMed Central  Google Scholar 

  • Carbone V, Velkov T (2013) Interaction of phthalates and phenoxy acid herbicide environmental pollutants with intestinal intracellular lipid binding proteins. Chem Res Toxicol 26:1240–1250

    CAS  PubMed  Google Scholar 

  • Darunte LA, Oetomo AD, Walton KS, Sholl DS, Jones CW (2016) Direct air capture of CO2 using amine functionalized MIL-101(Cr). ACS Sustain Chem Eng 4:5761–5768

    CAS  Google Scholar 

  • Elaiwi FA, Sirkecioglu A (2019) Amine-functionalized metal organic frameworks MIL-101(Cr) adsorbent for copper and cadmium ions in single and binary solution. Sep Sci Technol 55:3362–3374

    Google Scholar 

  • Gecgel C, Simsek UB, Gozmen B, Turabik M (2019) Comparison of MIL-101(Fe) and amine-functionalized MIL-101(Fe) as photocatalysts for the removal of imidacloprid in aqueous solution. J Iran Chem Soc 16:1735–1748

    CAS  Google Scholar 

  • Ghambarian M, Behbahani M, Esrafili A, Sobhi HR (2017) Application of a dispersive solid-phase extraction method using an amino-based silica-coated nanomagnetic sorbent for the trace quantification of chlorophenoxyacetic acids in water samples. J Sep Sci 40:3479–3486

    CAS  PubMed  Google Scholar 

  • Ghiasi A, Malekpour A, Mahpishanian S (2020) Metal-organic framework MIL101 (Cr)-NH2 functionalized magnetic graphene oxide for ultrasonic-assisted magnetic solid phase extraction of neonicotinoid insecticides from fruit and water samples. Talanta 217:121120

    CAS  PubMed  Google Scholar 

  • Hamidi S, Taghvimi A, Mazouchi N (2019) Micro solid phase extraction using novel adsorbents. Crit Rev Anal Chem. https://doi.org/10.1080/10408347.2019.1684235

    Article  PubMed  Google Scholar 

  • He X, Zhou Y, Yang W, Li S, Liu T, Wang T, Hou X (2019) Microwave assisted magnetic solid phase extraction using a novel amino-functionalized magnetic framework composite of type Fe3O4-NH2@MIL-101(Cr) for the determination of organochlorine pesticides in soil samples. Talanta 196:572–578

    CAS  PubMed  Google Scholar 

  • Hou X, Tang S, Guo X, Wang L, Liu X, Lu X, Guo Y (2018) Preparation and application of guanidyl-functionalized graphene oxide-grafted silica for efficient extraction of acidic herbicides by Box–Behnken design. J Chromatogr A 1571:65–75

    CAS  PubMed  Google Scholar 

  • Ji Z, Cheng J, Song C, Hu N, Zhou W, Suo Y, You J (2019) A highly sensitive and selective method for determination of phenoxy carboxylic acids from environmental water samples by dispersive solid-phase extraction coupled with ultra high performance liquid chromatography-tandem mass spectrometry. Talanta 191:313–323

    CAS  PubMed  Google Scholar 

  • Jin J, Yang Z, Xiong W, Zhou Y, Xu R, Zhang Y, Cao J, Li X, Zhou C (2019) Cu and Co nanoparticles co-doped MIL-101 as a novel adsorbent for efficient removal of tetracycline from aqueous solutions. Sci Total Environ 650:408–418

    CAS  PubMed  Google Scholar 

  • Karaman C, Karaman O, Show P-L, Orooji Y, Karimi-Maleh H (2021) Utilization of a double-cross-linked amino-functionalized three-dimensional graphene networks as a monolithic adsorbent for methyl orange removal: equilibrium, kinetics, thermodynamics and artificial neural network modeling. Environ Res. https://doi.org/10.1016/j.envres.2021.112156

    Article  PubMed  Google Scholar 

  • Khezeli T, Daneshfar A (2015) Dispersive micro-solid-phase extraction of dopamine, epinephrine and norepinephrine from biological samples based on green deep eutectic solvents and Fe3O4@MIL-100 (Fe) core-shell nanoparticles grafted with pyrocatechol. RSC Adv 5:65264–65273

    CAS  Google Scholar 

  • Khezeli T, Daneshfar A (2017) Development of dispersive micro-solid phase extraction based on micro and nano sorbents. Trac Trends Anal Chem 89:99–118

    CAS  Google Scholar 

  • Li N, Chen J, Shi Y-P (2017) Magnetic polyethyleneimine functionalized reduced graphene oxide as a novel magnetic solid-phase extraction adsorbent for the determination of polar acidic herbicides in rice. Anal Chim Acta 949:23–34

    CAS  PubMed  Google Scholar 

  • Liang L, Wang X, Sun Y, Ma P, Li X, Piao H, Jiang Y, Song D (2018) Magnetic solid-phase extraction of triazine herbicides from rice using metal-organic framework MIL-101(Cr) functionalized magnetic particles. Talanta 179:512–519

    CAS  PubMed  Google Scholar 

  • Lin Y, Kong C, Chen L (2012) Direct synthesis of amine-functionalized MIL-101(Cr) nanoparticles and application for CO2 capture. RSC Adv 2:6417–6419

    CAS  Google Scholar 

  • Lin Y, Kong C, Chen L (2016) Amine-functionalized metal-organic frameworks: structure, synthesis and applications. RSC Adv 6:32598–32614

    CAS  Google Scholar 

  • Lu P, Deng DY, Ni XD (2012) Application of NaClO-treated multiwalled carbon nanotubes as solid phase extraction sorbents for preconcentration of trace 2,4-dichlorophenoxyacetic acid in aqueous samples. J Sep Sci 35:2307–2312

    CAS  PubMed  Google Scholar 

  • Mousavi KZ, Yamini Y, Karimi B, Seidi S, Khorasani M, Ghaemmaghami M, Vali H (2019) Imidazolium-based mesoporous organosilicas with bridging organic groups for microextraction by packed sorbent of phenoxy acid herbicides, polycyclic aromatic hydrocarbons and chlorophenols. Microchim Acta 186:239

    Google Scholar 

  • Namieśnik J (2000) Trends in environmental analytics and monitoring. Crit Rev Anal Chem 30:221–269

    Google Scholar 

  • Nuhu AA, Basheer C, Alhooshani K, Al-Arfaj AR (2012) Determination of phenoxy herbicides in water samples using phase transfer microextraction with simultaneous derivatization followed by GC-MS analysis. J Sep Sci 35:3381–3388

    CAS  PubMed  Google Scholar 

  • Oller-Ruiz A, Garrido I, Viñas P, Campillo N, Fenoll J, Hernández-Córdoba M (2018) Reliable analysis of chlorophenoxy herbicides in soil and water by magnetic solid phase extraction and liquid chromatography. Environ Chem Lett 16:1077–1082

    CAS  Google Scholar 

  • Pawliszyn J, Lord HL (2010) Handbook of sample preparation. Wiley

    Google Scholar 

  • Peng M-M, Han Y-Q, Xia H, Hu X-Z, Zhou Y-X, Peng L-J, Peng X-T (2018) Rapid and sensitive detection of the phenoxy acid herbicides in environmental water samples by magnetic solid-phase extraction combined with liquid chromatography-tandem mass spectrometry. J Sep Sci 41:2221–2228

    CAS  PubMed  Google Scholar 

  • Pereiro IR, Irimia RG, Cano ER, Torrijos RC (2004) Optimisation of a gas chromatographic–mass spectrometric method for the determination of phenoxy acid herbicides in water samples as silyl derivatives. Anal Chim Acta 524:249–256

    Google Scholar 

  • Płotka-Wasylka J, Szczepańska N, de la Guardia M, Namieśnik J (2015) Miniaturized solid-phase extraction techniques. TrAC Trends Anal Chem 73:19–38

    Google Scholar 

  • Rocio-Bautista P, Pino V, Ayala JH, Pasan J, Ruiz-Perez C, Afonso AM (2016) A magnetic-based dispersive micro-solid-phase extraction method using the metal-organic framework HKUST-1 and ultra-high-performance liquid chromatography with fluorescence detection for determining polycyclic aromatic hydrocarbons in waters and fruit tea infusions. J Chromatogr A 1436:42–50

    CAS  PubMed  Google Scholar 

  • Sack C, Vonderbrink J, Smoker M, Smith RE (2015) Determination of acid herbicides using modified QuEChERS with fast switching ESI+/ESI- LC-MS/MS. J Agric Food Chem 63:9657–9665

    CAS  PubMed  Google Scholar 

  • SANTE/12682/2019 (2019) Analtical quality control and method validation procedures for pesticide residues analysis in food and feed. SANTE/12682/2019

  • Sarker M, Song JY, Jhung SH (2018) Carboxylic-acid-functionalized UiO-66-NH2: a promising adsorbent for both aqueous- and non-aqueous-phase adsorptions. Chem Eng J 331:124–131

    CAS  Google Scholar 

  • Seebunrueng K, Phosiri P, Apitanagotinon R, Srijaranai S (2020) A new environment-friendly supramolecular solvent-based liquid phase microextraction coupled to high performance liquid chromatography for simultaneous determination of six phenoxy acid herbicides in water and rice samples. Microchem J 152:104418

    CAS  Google Scholar 

  • Tabani H, Khodaei K, Bide Y, Zare FD, Mirzaei S, Fakhari AR (2015) Application of pH-sensitive magnetic nanoparticles microgel as a sorbent for the preconcentration of phenoxy acid herbicides in water samples. J Chromatogr A 1407:21–29

    CAS  PubMed  Google Scholar 

  • Tan SC, Lee HK (2019) A hydrogel composite prepared from alginate, an amino-functionalized metal-organic framework of type MIL-101(Cr), and magnetite nanoparticles for magnetic solid-phase extraction and UHPLC-MS/MS analysis of polar chlorophenoxy acid herbicides. Microchim Acta 186:545

    CAS  Google Scholar 

  • Trujillo-Rodríguez MJ, Nan H, Anderson JL (2018) Expanding the use of polymeric ionic liquids in headspace solid-phase microextraction: determination of ultraviolet filters in water samples. J Chromatogr A 1540:11–20

    PubMed  Google Scholar 

  • Wang T, Zhao P, Lu N, Chen H, Zhang C, Hou X (2016) Facile fabrication of Fe3O4/MIL-101(Cr) for effective removal of acid red 1 and orange G from aqueous solution. Chem Eng J 295:403–413

    CAS  Google Scholar 

  • Wang X, Qi P, Wang X, Zhang Q, Wang Z, Xu X, Xu H, Zhang H, Wang Q (2017) An efficient cleanup method coupled with gas chromatography and mass spectrometry for multi-pesticides residue analysis in complex plant matrices. J Sep Sci 40:2438–2450

    CAS  PubMed  Google Scholar 

  • Wu G, Ma J, Li S, Guan J, Jiang B, Wang L, Li J, Wang X, Chen L (2018) Magnetic copper-based metal organic framework as an effective and recyclable adsorbent for removal of two fluoroquinolone antibiotics from aqueous solutions. J Colloid Interf Sci 528:360–371

    CAS  Google Scholar 

  • Wu G, Ma J, Wang S, Chai H, Guo L, Li J, Ostovan A, Guan Y, Chen L (2020) Cationic metal-organic framework based mixed-matrix membrane for extraction of phenoxy carboxylic acid (PCA) herbicides from water samples followed by UHPLC-MS/MS determination. J Hazard Mater 394:122556

    CAS  PubMed  Google Scholar 

  • Xu G, Hou L, Li B, Wang X, Liu L, Li N, Zhao R-S (2021) Facile preparation of hydroxyl bearing covalent organic frameworks for analysis of phenoxy carboxylic acid pesticide residue in plant-derived food. Food Chem 345:128749

    CAS  PubMed  Google Scholar 

  • Yuan X, Liu C, Zhao J, Zhao P, Zhao L (2018) A novel magnetic multi-walled carbon nanotube-based magnetic solid-phase extraction combined with dispersive liquid-liquid microextraction method for the determination of four phenoxy carboxylic acid herbicides in food crops by using ultra-high performance liquid chromatography-tandem mass spectrometry. Anal Method 10:3263–3272

    CAS  Google Scholar 

  • Yuan X, Yuan Y, Gao X, Xiong Z, Zhao L (2020) Magnetic dummy-template molecularly imprinted polymers based on multi-walled carbon nanotubes for simultaneous selective extraction and analysis of phenoxy carboxylic acid herbicides in cereals. Food Chem 333:127540–127540

    CAS  PubMed  Google Scholar 

  • Zhang Y, Dai T, Zhang F, Zhang J, Chu G, Quan C (2016) Fe3O4@UiO-66-NH2 core-shell nanohybrid as stable heterogeneous catalyst for knoevenagel condensation. Chin J Catal 37:2106–2113

    CAS  Google Scholar 

  • Zhang H, Zheng D, Zhou Y, Xia H, Peng X (2020) Multifunctionalized magnetic mesoporous silica as an efficient mixed-mode sorbent for extraction of phenoxy carboxylic acid herbicides from water samples followed by liquid chromatography-mass spectrometry in tandem. J Chromatogr A 1634:461645

    CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This work was funded by Research and Development Program of Hubei Province of China (2020BBB078) and Natural Science Foundation of Hubei province (No. 2019CFB587, 2021CFB063). Great gratitude goes to linguistics Prof. Ping Liu from Huazhong Agriculture University, Wuhan, China, for her work at English editing and language polishing.

Author information

Authors and Affiliations

Authors

Contributions

HZ was involved in conceptualization, methodology, and writing-original draft. XH was involved in data curation, formal analysis, and investigation. XH: resources and methodology. YZ was involved in resources, writing—review, and editing. LP was involved in resources and supervision. JW was involved in conceptualization and writing—review and editing. XP was involved in conceptualization, supervision, funding acquisition, and writing—review and editing.

Corresponding author

Correspondence to Xitian Peng.

Ethics declarations

Conflict of 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.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 1056 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, H., Hu, X., Xia, H. et al. Amine-functionalized MIL-101(Fe) for highly selective and efficient extraction of phenoxy carboxylic acid herbicides from environmental water and rice samples. Chem. Pap. 76, 4379–4392 (2022). https://doi.org/10.1007/s11696-022-02103-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11696-022-02103-5

Keywords

Navigation