Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography

Priscilla Rocío-Bautista; Verónica Pino; Jorge Pasán; Irene López-Hernández; Juan H Ayala; Catalina Ruiz-Pérez; Ana M Afonso

doi:10.1016/j.talanta.2017.12.012

Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography

Talanta. 2018 Mar 1:179:775-783. doi: 10.1016/j.talanta.2017.12.012. Epub 2017 Dec 7.

Authors

Priscilla Rocío-Bautista¹, Verónica Pino², Jorge Pasán³, Irene López-Hernández⁴, Juan H Ayala⁵, Catalina Ruiz-Pérez⁶, Ana M Afonso⁷

Affiliations

¹ Department of Chemistry, Analytical Chemistry Division, University of La Laguna, Tenerife 38206 Spain. Electronic address: procio@ull.edu.es.
² Department of Chemistry, Analytical Chemistry Division, University of La Laguna, Tenerife 38206 Spain. Electronic address: veropino@ull.edu.es.
³ X Ray and Molecular Materials Lab (MATMOL), Physics Department, University of La Laguna, Tenerife 38206 Spain. Electronic address: jpasang@ull.edu.es.
⁴ Department of Chemistry, Analytical Chemistry Division, University of La Laguna, Tenerife 38206 Spain. Electronic address: irelopher@gmail.com.
⁵ Department of Chemistry, Analytical Chemistry Division, University of La Laguna, Tenerife 38206 Spain. Electronic address: jayala@ull.edu.es.
⁶ X Ray and Molecular Materials Lab (MATMOL), Physics Department, University of La Laguna, Tenerife 38206 Spain. Electronic address: caruiz@ull.edu.es.
⁷ Department of Chemistry, Analytical Chemistry Division, University of La Laguna, Tenerife 38206 Spain. Electronic address: aafonso@ull.edu.es.

PMID: 29310307
DOI: 10.1016/j.talanta.2017.12.012

Abstract

Five metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5(Zn), MIL-53(Al), UiO-64 and MOF-74(Zn) are synthesized, characterized, and utilized in a miniaturized solid-phase extraction method under dispersive mode (D-µSPE) for the determination of six pollutants of different nature, including one polycyclic aromatic hydrocarbon, two hormones, two drugs, and one disinfectant, from environmental waters (tap water and wastewater). A discussion of possible interactions justifying the partitioning of target analytes to the MOFs is included, considering not only the analytes' physicochemical characteristics but also those of MOFs: metal nature, structural environment of MOF pores, pore size and pore aperture widths, among others. MIL-53(Al) is selected for its versatility and high extraction efficiency for the target compounds. The D-µSPE method using MIL-53(Al) is optimized and used in combination with high-performance liquid chromatography (HPLC) with diode array detector (DAD) or liquid-chromatography with time-of-flight mass spectrometric detector (LC-TOF). Under optimum conditions, only 5mg of MIL-53(Al) are required for 10mL of water, with the aid of 5min of vortex and 5min of centrifugation. Elution is accomplished with 200µL of acetonitrile (3 times), and evaporation down to 100µL before LC injection. Detection limits down to 0.040μgL^-1 for triclosan and 0.013μgL^-1 for atrazine are obtained for the entire method using HPLC-DAD and LC-TOF, respectively. The method, operating at low spiked levels (2µgL^-1 for HPLC-DAD and 0.7µgL^-1 for LC-TOF), is also characterized for average relative recoveries of 109% and 105%; relative standard deviation values lower than 8.7% and 7.5%; and average extraction efficiencies of 41.2% and 49.1%; using HPLC-DAD and LC-TOF, respectively; while demonstrating adequate analytical performance with complex samples such as wastewaters.

Keywords: Dispersive miniaturized solid-phase extraction; Environmental waters; Metal-organic frameworks; Pollutants; Sample preparation.