The covalent organic framework based nylon membrane extraction coupled with UHPLC-MS/MS for highly efficiency determination of hexabromocyclododecanes in environmental water

Hexabromocyclododecanes (HBCDs) have given their adverse effects on environment and human health, and highly sensitive analysis of HBCDs in water is urgent. In this study, a new method for the determination of trace HBCDs in water was established by covalent organic framework (COF) based nylon membrane extraction (ME) coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The COF had been self-assembled onto the nylon membrane in a gentle strategy to fabricate COF nylon membrane. Several important ME parameters including the dosage of COF, pH, eluent condition and salinity were systematically investigated. The limits of detection and quantification were 0.011-0.014 and 0.038-0.047 ng/L for three HBCDs, respectively. The linear ranges were from 0.04 to 20 ng/L, and the relative standard deviations were 5.7-17.8 % (intra-day) and 5.2-14.1 % (inter-day). In addition, density functional theory (DFT) calculations on adsorption energy proved that the introduction of halogen bond (XB) made a key contribution to high extraction efficiency and excellent selectivity of COF nylon membrane for HBCDs. The 500 mL of samples, including tap water and reservoir water, could be extracted only in 23 min. The established method presented highly sensitive for ultra-trace analysis of HBCDs in environmental water.