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

• Published in: Journal of Chromatography A Vol. 1436; pp. 42 - 50
• Main Authors: Rocío-Bautista, Priscilla, Pino, Verónica, Ayala, Juan H., Pasán, Jorge, Ruiz-Pérez, Catalina, Afonso, Ana M.
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 04.03.2016
• Subjects: Beverages - analysis; Chromatography, High Pressure Liquid - methods; Dispersive micro solid-phase extraction; Environmental waters; Extraction; Fruit - chemistry; Fruit-tea infusions; Fruits; Infusion; Limit of Detection; Liquid chromatography; Magnetic nanoparticles; Magnetite Nanoparticles - chemistry; Metal-organic frameworks; Organometallic Compounds - chemistry; Polycyclic aromatic hydrocarbons; Polycyclic Aromatic Hydrocarbons - analysis; Solid Phase Extraction - methods; Solvents; Tap water; Tea; Waste water; Waste Water - analysis; Water Pollutants, Chemical - analysis; Fruit-tea infusions; Polycyclic aromatic hydrocarbons; Metal-organic frameworks; Dispersive micro solid-phase extraction; Magnetic nanoparticles; Environmental waters
• ISSN: 0021-9673; 1873-3778
• DOI: 10.1016/j.chroma.2016.01.067

•The composite MOF HKUST-1+Fe3O4 MNPs is prepared by simple mixing.•The material (25mg) is used in a magnetic-assisted extraction method and UHPLC-FD.•The composite was a suitable sorbent for PAHs in waters and fruit tea infusions.•The overall M-d-μSPE-UHPLC-FD method was optimized and validated.•LODs ∼low ngL−1 were obtained for heavy PAHs only requiring 20mL of sample. A hybrid material composed by the metal-organic framework (MOF) HKUST-1 and Fe3O4 magnetic nanoparticles (MNPs) has been synthetized in a quite simple manner, characterized, and used in a magnetic-assisted dispersive micro-solid-phase extraction (M-d-μSPE) method in combination with ultra-high-performance liquid chromatography (UHPLC) and fluorescence detection (FD). The application was devoted to the determination of 8 heavy polycyclic aromatic hydrocarbons (PAHs) in different aqueous samples, specifically tap water, wastewaters, and fruit tea infusion samples. The overall M-d-μSPE-UHPLC-FD method was optimized and validated. The method is characterized by: its simplicity in both the preparation of the hybrid material (simple mixing) and the magnetic-assisted approach (∼10min extraction time), the use of low sorbent amounts (20mg of HKUST-1 and 5mg of Fe3O4 MNPs), and the low organic solvent consumption in the overall M-d-μSPE-UHPLC-FD method (1.5mL of acetonitrile in the M-d-μSPE method and 2.8mL of acetonitrile in the UHPLC-FD run). The resulting method has high sensitivity, with LODs down to 0.8ngL−1; adequate intermediate precision, with relative standard deviation values (RSD) always lower than 6.3% (being the range 5.9–9.0% in tap water for a spiked level of 45ngL−1, 6.1–14% in wastewaters for a spiked level of 45ngL−1, and 7.2–17% in fruit tea infusion samples for a spiked level of 45ngL−1); and adequate relative recoveries, with average values of 82% in tap water, and 94% and 75% in wastewater and fruit tea infusion samples, respectively, if using the proper matrix-matched calibration.