The Development Of Methods For The Analysis Of Environmental Endocrine Disruptors

Environmental endocrine disruptors (EEDs) are globally paid attention to since they exist extensively in the environment and disturb the normal body functions of human and animals. There are several kinds of typical EEDs, such as pharmaceutical and personal care products and their metabolites of triclosan (TCS), triclocarban (TCC) and methyl triclosan (M-TCS), organochlorine pesticides of hexachlorocyclohexanes (HCHs), dichloro-diphenyl-trichloroethanes (DDTs) and hexachlorobenzene (HCB), and brominated flame retardants and their metabolites of polybrominated diphenyl ethers (PBDEs), hydroxyl PBDEs (OH-PBDEs) and methoxyl PBDEs(MeO-PBDEs). This paper developed and optimized pretreatment methods for the analysis of these EEDs in different environmental matrices. Dispersive liquid phase microextraction method (DLLME) and temperature-controlled ionic liquid dispersive liquid phase microextraction (TIL-DLME) combined with ultra-high-pressure liquid chromatography (UHPLC) were established for the pre-concentration and determination of triclosan (TCS), triclocarban (TCC) and methyl-triclosan (M-TCS) in water samples. Under the optimized conditions, wide linear ranges, low limits of detection (LODs) and good correlation coefficients were acquired. In DLLME, TCS in domestic water was detected in the concentration of 2.08μg L^-1 and the spiked recoveries of the three target compounds were obtained in the range of 64.3-121% in real waters; In TIL-DLME, TCS in domestic water and TCC in reclaimed water were respectively detected in the concentrations of 1.01 and 0.126μg L^-1 and the spiked recoveries were got in the range of 58.9–92.4% in real waters. Another method was set up to simultaneously analyze PBDEs and OCPs in dust. In this method, silica-sulfuric silica column and gel permeation chromatography (GPC) were adopted to reduce the disturbance. After soxhlet extraction, the dust samples were loaded in the silica-sulfuric silica column and eluted with two kinds of selected organic solvents in order to avoid the disturbtion of the specific bump peaks in the retention time of DDTs in gas chromatography-electron capture detection (GC-ECD); GPC clean-up could effectively excluded the impurities and be available to detect PBDEs precisely by isotope dilution method with gas chromatography/mass spectrum-electron impact(GC/MS-EI). The spiked recoveries and the LODs of nine organochlorine pesticides were in the ranges of 65.8-115% and 0.002⁰.011 ng g^-1, respectively; The spiked recoveries and LODs of eight labeled PBDEs were in the ranges of 55.9-128% and 0.002-0.042 ng g^-1, respectively. A fourth developed method is the pretreatment and detection of PBDEs, TCS, OH-PBDEs, MeO-PBDEs and M-TCS in human blood and milk. Comparing to the published methods, which separated these compounds by liquid liquid extraction and multiple repeated clean-up procedures, this method showed the advantages of less materials consumption and simpler operation procedures. The spiked recoveries of blood and milk were in the ranges of 45.14-294.73% and 42.26-145.70%. The LODs of the method were in the range of 0.001 ng g^-1-0.144 ng g^-1. The established four methods were proved feasible to analyze specific EEDs in specific real samples.