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Trace mercury speciation in cells is critical to understand its cytotoxicity and cell protection mechanism. In this work, we fabricated a chip-based magnetic solid-phase microextraction (MSPME) system, integrating a cell lysis unit as well as a sample extraction unit, and online combined it with micro high-performance liquid chromatography (microHPLC)-inductively coupled plasma mass spectrometry (ICPMS) for the speciation of mercury in HepG2 cells. Magnetic nanoparticles with sulfhydryl functional group were synthesized and self-assembled in the microchannels for the preconcentration of mercury species in cells under an external magnetic field. The enrichment factors are ca. 10-fold, and the recoveries for the spiked samples are in the range of 98.3-106.5%. The developed method was used to analyze target mercury species in Hg(2+) or MeHg(+) incubated HepG2 cells. The results demonstrated that MeHg(+) entered into the HepG2 cells more easily than Hg(2+), and part of the MeHg(+) might demethylate into Hg(2+) in HepG2 cells. Besides, comprehensive speciation of mercury in incubated cells revealed different detoxification mechanisms of Hg(2+) and MeHg(+) in Hg(2+) or MeHg(+) incubated HepG2 cells.

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Regulatory requirements for the analysis of 24 elemental impurities (Li, V, Cr, Co, Ni, Cu, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Ba, Os, Ir, Pt, Au,...