Quantification of trace heavy metals in environmental water, soil and atmospheric particulates with their bioaccessibility analysis

In this work, sulfhydryl (SH) functionalized magnetic covalent organic framework (COF) was synthesized by using 4-aldehyde phenyl butadiyne (DEBD) and 1,3,5-tris(4-aminophenyl) benzene (TAPB) as the monomers and ethanedithiol as the modifier, with the aid of thiol-alkyne "click" reaction. The prepared Fe₃O₄@COF_TAPB-DEBD@SH exhibited relatively strong magnetism (32.8 emu g^-1), good stability and selectivity to target analytes with a high sulfhydryl content (0.24 mmol g^-1). Based on Fe₃O₄@COF_TAPB-DEBD@SH, a method combining magnetic solid phase extraction with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the quantitative analysis of trace metals. Under the optimal conditions, the method merited fast desorption kinetics (<2 min), adsorption kinetics (<20 min), fast phase separation (<1 min), high enrichment factor (100), and the detection limits for Cd, Hg, Pb and Bi were determined to be 1.18, 0.51, 4.91 and 0.39 ng L^-1, respectively. A good resistance to complex matrices was demonstrated for the method in the analysis of soil, atmospheric particles and simulated pulmonary fluids samples. Certified reference materials (coal fly ash GBW08401 and soil GBW07427) were employed to validate the accuracy of the method. Four target metals in the range of 12.9-215 ng L^-1, 0.06-24.6 μg g^-1 and 0.52-33.1 ng m^-3 were found in local water, soil and atmospheric particulates (PM), respectively. Additionally, artificial lysosome solution and gamble's solution were used to simulate human pulmonary fluid and the bioaccessibility of Cd, Hg, Pb and Bi in PM_2.5 was evaluated to be 58.6-73.1 % and 1.3-7.1 %, respectively.