| Environmental hormones are defined as exogenous agents that interfere with the endocrine system of humans and wildlife. These compounds existed in environment can affect the reproductive and developmental of human and animal. Those chemicals may enter human and wild life through the food chain’s bioaccumulation and lead to various diseases. Among these compounds, steroidal and phenolic environmental hormones with estrogen properties have attracted the most attention due to their potential adverse effects on the normal reproduction and development of environmentally exposed organisms. Up until now, most studies on the presence of steroid hormones in the environment have focused on the estrogens. Limit researches were investigated the androgens and progestogens in water, sediment and biological samples. The impact on water environment of androgens and progestogens should be received more attention due to their excretion masses in human and livestock urine are several times even hundred times higher than those of estrogens. In this paper, we choosed 4-tert-octylphenol (4-t-OP), 4-cumylphenol (4-CP),4-nonylphenol (4-NP),bisphenol A (BPA), oestrone (E1),17β-oestradiol (E2), oestriol (E3),17α-ethynylestradoil (EE2), dihydrotestosterone (DIHYDRO), androstenedione (AND), testosterone (TEST), progesterone (PROG) as the target compounds. Develop an accelerated solvent extraction (ASE)-automated gel permeation chromatography (GPC)-solid-phase extraction (SPE)-gas chromatography (GC)-mass spectrometry (MS) analytical method for the simultaneous determination of target environmental hormones in water, sediment and biological samples. The objective of this study was used the optimized method to investigate the bioaccumulation characteristic and tissue distribution of steroidal and phenolic environmental hormones in wild fish collected from Dianchi and Erhai Lake.(1) An improved method was developed for the simultaneous determination of four phenolic and eight steroidal hormons in water, sediment and biological samples. The most effective extraction of the target hormons was achieved by using ASE and the parameters have been optimized as follows:extraction solvent-ethyl acetate, extraction -3 cycles, static extraction time-5 min and extraction temperature-80℃ and 60℃ for sediment and biological samples, respectively. The clean-up of extracts was carried out by GPC on a Biobeads S-X3 column with cyclohexane/ethyl acetate (1:1, v/v) as mobile phase. Target compounds were eluted in the fraction from 7-14 min retention time. Moreover, the cleanest extracts were obtained by solid phase extraction with Sep-Pak C18 cartridges after the elution with 15 mL ethyl acetate. The final sample extracts were derivatised using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA)/trimethyliodosilane (TMIS)/dithioerythreitol (DTE) ((1000:2:5; v/v/w)) as derivatisation reagent, derivatizated at 50℃ for 40 min, then detected by GC-MS. The mean recoveries vary from 60.28% to 95.46% for the target compounds with a relative standard deviation (RSD) less than 10%. The limit of detection (LOD) values was ranged from 0.3 to 0.8 ng/L in water samples,0.5 to 1 ng/g in sediments and 0.5 to 1 ng/g in biological samples. The method was validated by spiking experiments which showed good recovery and reproducibility. The proposed method was successfully applied to detect the target EDCs in environmental samples taken from the Laoyu River and local market in Yunnan, China. The developed method is a promising approach for the analysis of phenolic and steroidal hormons in water, sediment and biological samples.(2) The distribution and bioaccumulation of phenolic and steroidal hormons were studied in various tissues of wild fish species from Erhai Lake, China. In carp muscle tissue, concentrations of phenols and steroids were ND-22.9 ng/g and ND-3.3 ng/g, respectively. In crucian carp muscle tissue, concentrations of phenols and steroids were ND-15.6 ng/g and ND-2.9 ng/g, respectively. For the phenols, the steroids pollution was lighter. All sampling sites, the concentration of target compounds in fish from S1, S2 and S3 (near the rivers with high concentration of target compounds) were significant higher than other sites. An interspecies difference in concentrations was evident due to their feeding preference, general behavior and trophic level. Indeed, it was found that the concentration levels of fish muscle were follow the rules of crucian carp>carp, and the bioaccumulation of fish tissue follow the rules of liver> gill>muscle. The field BCF values of phenols and steroids from 26 to 235, and follow the rule of 4-NP>4-t-OP>4-CP>BPA and EE2>E2>PROG>E1>TEST>DIHYDRO>E3>AND. These rules were consistent with the compounds octanol-water partition coefficient. The TDI range of fish muscle from Erhai Lake was from 0.3 to 14.45 ng/kg body weight/day. BPA and 4-NP had potential risk to the human health due to the TDI breach EU levels.(3) The distribution and bioaccumulation of phenolic and steroidal hormons were studied in various tissues of wild fish species from Dianchi Lake, China. In muscle tissue, concentrations of phenols and steroids were ND-63 ng/g and ND-6.3 ng/g, respectively. The concentrations of target compounds in fish muscle caged in Dianchi Lake were very lowest. In carp muscle tissue caged in Dianchi, concentrations of BPA was ND-6.6 ng/g, it was high than another target compounds. But for others, little kinds compounds could detect, another lower than the detection limit and the bioaccumulation rules were consistent with the wildfish from Erhai and Dianchi Lake. For the phenols, steroids were found at lower levels. All sampling sites, the concentration of target compounds in fish collected from S1 and S2 (close to Kunming city) were significant higher than other sites. Indeed, it was found that the concentration levels were follow the rules of silvery white fish> carp>chub> crucian carp and the concentrations of steroids and phenols in the fish tissue follow the rules of liver> gill>muscle. The rules were consistent with the Erhai Lake. Compared with Dianchi Lake, the pollution of target compounds in Erhai Lake was slightly.(4) The concentration of target compounds in liver, gill and muscle of crucian carp, chub and carp caged in Dianchi Lake increased and indicated concentration accumulating with the age add. The GSI, HSI and Vtg levels showed that the low concentrations of target coumpounds in caged area had no significant effect on the normal growth of fish caged in Dianchi Lake. But the concentrations of fish muscles in Dianchi and Erhai Lake water. The concentration of target compounds in fish collected from Erhai and Dianchi Lake were lower than were higher than caged. The result showed that the pollution of phenolic and steroidal environmental hormones cannot be neglected in Erhai and Dianchi Lake. The field BCF values of phenols and steroids were from 0 to 263. The estimated concentrations of androgens and progestagens in water from Dianchi Lake, the concentrations of DIHYDRO, AND, TEST and PROG were 9.34 ng/L,8.26 ng/L,3.72 ng/L and 1.54 ng/L, respectively. The TDI range of fish muscle from Dianchi Lake was from 0 to 37.36 ng/kg body weight/day.4-NP and BPA breach EU levels had potential risk to the human health. |
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