ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

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

Huixian Zhang, Xizhou Hu, Hong Xia, Youxiang Zhou, Lijun Peng, Jianyuan Wu, and Xitian Peng

Institute of Agricultural Quality Standards and Testing Technology Research, Hubei Academy of Agricultural Sciences/Hubei Key Laboratory of Nutritional Quality and Safety of Agro Products, Wuhan, People’s Republic of China

E-mail: wujianyuan@znhospital.cn

Received: 7 October 2021  Accepted: 25 January 2022

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.

Keywords: Dispersive micro-solid phase extraction; Amine-functionalized metal–organic framework; Phenoxy carboxylic acid herbicides; UHPLC-MS/MS; Rice; Water samples

Full paper is available at www.springerlink.com.

DOI: 10.1007/s11696-022-02103-5

Chemical Papers 76 (7) 4379–4392 (2022)