Preparation of metal‐organic framework UiO‐66‐incorporated polymer monolith for the extraction of trace levels of fungicides in environmental water and soil samples

Abstract

A zirconium terephthalate metal‐organic framework‐incorporated poly(N‐vinylcarbazole‐co‐divinylbenzene) monolith was fabricated in a capillary by a thermal polymerization method. The optimized monolith had a homogeneous structure, good permeability, and stability. The monolith could be used for the effective enrichment of fungicides through π‐π interactions, electrostatic forces, and hydrogen bonds. The potential factors that affect the extraction efficiency, including ionic strength, solution pH, sample volume, and eluent volume, were investigated in detail. The monolith‐based in‐tube solid‐phase microextraction coupled with ultra‐high‐performance liquid chromatography and high‐resolution Orbitrap mass spectrometry was performed for the analysis of five fungicides (pyrimethanil, tebuconazole, hexaconazole, diniconazole, and flutriafol) in environmental samples. Under the optimized conditions, the linear ranges were 0.005–5 ng/mL for pyrimethanil, 0.01–5 ng/mL for flutriafol, and 0.05–5 ng/mL for other fungicides, respectively, with coefficients of determination ≥0.9911. The limits of detection were 1.34–14.8 ng/L. The columns showed good repeatability (relative standard deviations ≤9.3%, n = 5) and desirable column‐to‐column reproducibility (relative standard deviations 5.3–9.4%, n = 5). The proposed method was successfully applied for the simultaneous detection of five fungicides in water and soil samples, with recoveries of 90.4–97.5 and 84.0–95.3%, respectively.

Fabric phase sorptive extraction for the determination of 17 multiclass fungicides in environmental water by gas chromatography‐tandem mass spectrometry

“…As can be seen, LOQs were between 1 and 9 ng/L for most compounds, excluding fenhexamid, iprodione, and folpet which showed LOQs of 100, 115, and 165 ng/L, respectively. Table 4 shows a comparison between the developed FPSE-GC-MS/MS methodology and other reported methodologies based on microextraction techniques for the determination of fungicides in water, such as SPME, SBSE, µSPE, BAµE, or HF-LPME [11,[13][14][15][16][17]. As can be seen, the proposed FPSE-GC-MS/MS methodology provides LODs similar or lower than other microextraction techniques.…”

“…In last years, the new trends regarding sample preparation for the determination of fungicides in waters are aimed to move toward the "Green Chemistry Principles," and several microextraction techniques with a minimum or nonorganic solvent consumption have been proposed for their extraction from water. Solid-phase microextraction (SPME), stir-bar sorptive extraction (SBSE), micro-solid-phase extraction (µSPE), bar-adsoptive microextraction (BAµE), or hollow fiber-liquid-phase microextraction (HF-LPME) [11][12][13][14][15][16][17] have been successfully employed.…”

Recent Applications and Newly Developed Strategies of Solid-Phase Microextraction in Contaminant Analysis: Through the Environment to Humans

“…Their application as SPME coating for soil analysis has been extensively investigated in recent years, both as regards the use of new structural variants and their synthesis. After their preparation, these SPME fibers were successfully used in the analysis of trace levels of fungicides [93], PAHs [19,[94][95][96], PCBs [97,98], polybrominated diphenyl ethers (PBDEs) [99].…”

Defective Zr‐based metal–organic frameworks as sorbent for the determination of fungicides in environmental water samples by rapid dispersive micro‐solid‐phase extraction coupled to liquid chromatography/mass spectrometry

“…Among various MOFs, Zr‐based MOFs have been reported as promising candidates for aqueous pretreatment due to their exceptional structural stability in aqueous media, specially the UiO‐66 series [18,19]. In recent years, Zr‐terephthalate UiO‐66 has been studied as effective sorbents for the extraction of fungicides, progestogens, insecticides, and domoic acid [20–23].…”