中国南海流沙湾中雄激素、糖皮质激素和孕激素的污染特征及其生态风险评价

近年来,类固醇激素在淡水水体中不断被检出,但是其在海水中的污染特征研究相对较少.本文对中国南海流沙湾进行样品采集,通过高效液相色谱与质谱联用技术(UPLC-MS/MS),研究了33种类固醇激素的污染特征及空间分布.结果表明,在海水和沉积物中均检出7种类固醇激素,含量范围为0. 003(甲羟孕酮,MP)～9. 023(去氢孕酮,DGT) ng·L~(-1)和0. 017(1,4-雄烯二酮,ADD)～9. 281(雄烯二酮,AED) ng·g~(-1).在海水中,类固醇激素浓度高低顺序为合成类高于天然类,丰水期高于枯水期,养殖区高于非养殖区.在沉积物中,类固醇激素在时空分布上无明显差异.海洋环境中类固醇激素的主要来源为水产养殖人为饲料添加和废水排放.生态风险评价结果表明,AED处于低风险,其他类固醇激素处于无风险.相关性分析表明,海洋环境中类固醇激素的含量分布规律与盐度、水温、颗粒物(SS)和化学需氧量(COD)有关.本研究有助于认识流沙湾地区类固醇激素的污染特征,并为其生态风险评价和管控提供科学依据.     

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis（trimethylsily）trifluoroacetamide （BSTFA） and N-methyl-N（trimethylsily） trifluoroacetamide （MSTFA） are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone （El） and 17α-ethinylestradiol （EE2）. In this study, three trimethylsilyl （TMS） steroid derivatives, mono- and di-trimethylsilyl EE2 and mono-trimethylsilyl El, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz （TMSI） in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.     

典型雌激素在微塑料上的吸附特征及位点能量分布

微塑料(MPs)和雌激素是目前备受关注的新型污染物,MPs可作为环境中雌激素的载体而产生复合污染.为了解聚乙烯(PE)为代表的MPs对典型雌激素的吸附特性,采用批平衡吸附实验法,借助X射线光电子能谱(XPS)和傅里叶红外光谱(FTIR)等研究不同体系下PE对6种典型雌激素的吸附行为和位点能量分布情况.结果表明,在不同初始浓度(100μg·L^-1和1000μg·L^-1),PE对目标雌激素的吸附过程更符合准二级动力学模型,初始浓度的增加会影响吸附平衡时间和雌激素吸附量占比.在单一体系(单一雌激素)和复合体系(6种雌激素共存)中,雌激素在PE上的吸附更符合Freundlich模型(R²>0.94).等温吸附实验结果及XPS和FTIR表征结果表明,吸附过程主要受范德华力和疏水分配作用影响;单一己烯雌酚(DES)体系中出现的C—O—C官能团和单一炔雌醇(17α-EE2)体系中出现的C—O—C及■官能团,表明化学键合作用对合成雌激素在MPs上的吸附有一定的影响,而对天然雌激素基本没有影响.与单一体系相比,复合体系中各雌激素的吸...     

固相萃取-超高效液相色谱-串联质谱法测定水中6种雌激素

建立了固相萃取-超高效液相色谱-串联质谱(SPE-UPLC-MS-MS)同时检测水样中6种雌激素(壬基酚、双酚A、雌酮、17α-雌二醇、17α-乙炔雌二醇、雌三醇)的方法.样品采用SPE小柱富集后,用90％乙腈-0.1％氨水混合溶液洗脱浓缩定容.在梯度洗脱条件下,6种雌激素用三重四极杆串联质谱检测.该方法显示出良好的线性关系(r ＞0.999)和精密度(RSD＜ 10％),方法检出限为1.3 ～5.2 ng/L.该方法成功应用于地表水、地下水和废水样品中6种雌激素分析,样品加标回收率为76.8％～117％.该方法准确、灵敏、无需衍生,可用于同时测定水样中的6种雌激素.