Embedment of Ag(I)-organic frameworks into silica gels for microextraction of polybrominated diphenyl ethers in soils

Three Ag(I)-organic frameworks, [Ag5(pydc)2(CN)]n, {[Ag4(pydc)2]CH3CN}n, and [Ag(4,4′-bpy)NO3]n, were synthesized and embedded into silica gels to form metal-organic-framework (MOF)-embedded gels for the microextraction of polybrominated diphenyl ethers (PBDEs) in soils. Despite the great differences in the structures of the organic ligands, all three Ag(I)-organic frameworks were found to effectively accumulate and concentrate PBDEs from sample solutions prepared with contaminated soil and purified water, indicating the important roles of Ag centers in PBDE extraction. Under the optimal experimental conditions (MOF mass, water volume, temperature, extraction time, and back-extraction time) for PBDE extraction from sample solutions, the detection limits of seven PBDEs (BDE-28, 47, 99, 100, 153, 154, and 183) ranged from 0.01 to 2.6 ng g−1 for [Ag5(pydc)2(CN)]n, 0.20-0.64 ng g−1 for {[Ag4(pydc)2]CH3CN}n, and 0.60-3.08 ng g−1 for [Ag(4,4′-bpy)NO3]n. The reproducibilities of the three methods were all satisfactory with relative standard deviations (RSDs) in the range of 2.2-9.6%, 5.3-10.4%, and 6.9-9.4% for [Ag5(pydc)2(CN)]n, {[Ag4(pydc)2]CH3CN}n, and [Ag(4,4′-bpy)NO3]n, respectively. The use of Ag(I)-organic frameworks for the microextraction of PBDEs was validated using both certified reference soils and field-contaminated soils, and the proposed methods are recommended as rapid and environmentally friendly alternatives for the extraction and determination of PBDEs in soils.