水环境中26种类固醇激素的分析方法研究

建立了固相萃取-超高效液相-串联质谱法同时测定水环境中26种类固醇激素的分析方法。明确了取样体积为500 m L,Cleanert PEP为富集柱,乙酸乙酯为洗脱剂,甲醇为溶剂进行提取操作。选择了正离子模式,以0. 1%甲酸/甲醇-水为流动相,负离子模式以0. 1%氨水/乙腈-水为流动相,试样经AcquityTMUPLC BEH C18色谱柱分离后,选用质谱检测模式进行定性、定量分析。通过方法验证,26种类固醇激素的方法检出限为0. 3～1. 5 ng/L,测定下限为1. 2～6. 0 ng/L,代表性样品测定结果的相对标准偏差为2. 6%～13. 7%(n=6),加标回收率为71. 2%～121%。该方法操作便捷,灵敏度高,精密度和准确度良好,可适用于水环境中多种痕量、超痕量类固醇激素的定性定量分析。     

类固醇雌激素分析方法研究进展

类固醇雌激素因其对野生动物、人类健康及生态环境安全造成危害而受到全世界的普遍关注,并成为环境科学和生态毒理学研究的重点和热点之一.针对4种典型的类固醇雌激素(雌激素酮、17-β-雌二醇、雌三醇和17-α-乙炔基雌二醇),对其羟基和酮基衍生化技术、水和固体样品的前处理技术及仪器检测方法进行了综述,总结了类固醇雌激素分析方法的研究动态和进展.     

Excretion of manure-borne estrogens and androgens and their potential risk estimation in the Yangtze River Basin

The Yangtze River is the longest river in China, and the river basin spans one fifth of the area of the whole country. Based on statistical data, the excretion of manure-borne steroid hormones, including steroid estrogens(SEs) and steroid androgens(SAs), in 10 provinces of China within the region has been estimated. The potential environmental and ecological risk of manure-borne steroid estrogens to the surface water in this region was also assessed. The manure-borne SE and SA excretions in the 10 provinces and municipalities vary in the order: Sichuan Hunan Hubei Yunnan Jiangsu Anhui Jiangxi Chongqing Qinghai Shanghai. The highest increase of manure-borne SEs(1434.3 kg)and SAs(408.5 kg) was found in Hunan and Hubei provinces, respectively, and the total excretion in 2013 was 65% more than 15 years earlier in these two provinces. However, the emissions in Anhui and Shanghai decreased in this 15 year period of time. Swine urine,chicken feces, cattle urine, and laying hen feces were considered the dominant sources of manure-borne E1, βE2, αE2, and SAs, respectively. Although Jiangsu province did not have the largest excretion of manure-borne SEs, it had the highest level of predicted17β-estradiol equivalency(EEQs) value of 16.65 ng/L in surface water because of the limited surface water resources. According to the lowest observable effect level of 10 ng/L for17β-estradiol, the manure-borne SEs in Jiangsu province might potentially pose ecological risk to its wild aquatic organisms.     

东北三省畜禽养殖类固醇激素排放及其潜在污染风险

以东北三省畜禽养殖数量统计数据和养殖结构分析为基础,对黑龙江、吉林和辽宁省畜禽养殖类固醇激素排放量进行了估算,并初步探讨了畜禽粪便中类固醇激素对当地水体的潜在污染风险.结果表明,由于养殖数量的增加,东北三省畜禽粪便所排放的类固醇激素量均持续增大.在1998～2008年的10 a间,辽宁、吉林和黑龙江三省的类固醇激素排放量分别增长了2 272.7、1 951.1和1 634.8 kg,并且省会城市沈阳、长春和哈尔滨的增长最为明显.东北三省各城市中畜禽粪便类固醇雌激素排放量最大的是长春,达到874.7 kg;哈尔滨和沈阳的排放量在各自省份中也是最大,分别为652.7 kg和603.1 kg·辽宁省的畜禽类固醇激素排放总量在东北三省为最多,所排放类固醇雌激素的雌二醇等当量浓度EEQs预测值也最高,达到17.1ng·L-1.如果以英国环保署(Environment Agency,United Kingdom)建议的最低可观测效应浓度10 ng·L-1为参考依据,辽宁省在目前的畜禽养殖规模和结构下,所排放的粪便类固醇雌激素极有可能会对地表水体中的水生生物产生内分泌干扰效应.     

类固醇类内分泌干扰物羟基衍生化条件的优化

以N-甲基-N-三甲基硅基三氟乙酰胺(MSTFA)为衍生化试剂,采用气相色谱-质谱联用技术(GC-MS)系统研究了4种类固醇类内分泌干扰物雌酮(E1)、17β-雌二醇(E2)、雌三醇(E3)、17α-乙炔基雌二醇(EE2)的羟基衍生化,主要考察了MSTFA用量、衍生化温度、衍生化时间对类固醇类内分泌干扰物衍生化效果的影响以及衍生化产物的稳定性、标准曲线、仪器检出限等.结果表明:100μl浓度为0.01μg.μl-1的标准混合溶液,MSTFA的最佳用量为20μl;最佳衍生化条件为70℃下反应30min;衍生化产物的稳定性较好,在-20℃下放置48h,相对响应因子(RRF)基本没有降低;在优化的实验条件下,各待测物具有良好的线性相关性,E1和E2的仪器检出限为0.1pg.μl-1,EE2和E3的仪器检出限为1pg.μl-1.     

新型溴代阻燃剂TBB和TBPH混合物对罗非鱼甲状腺激素和生理生化指标的影响

为了研究新型溴代阻燃剂FM550的生态风险,以罗非鱼为模式生物,配制添加不同浓度FM550(0、10、100和400ng·g~(-1))的饲料,将罗非鱼暴露56 d后,研究不同暴露剂量条件下FM550对罗非鱼甲状腺激素以及血清生理生化指标的影响。研究表明,经不同浓度的FM550暴露56 d后,罗非鱼的基础生长数据并无显著变化,但罗非鱼的甲状腺激素水平发生改变,具体表现为高剂量的FM550暴露可以使罗非鱼血清中的三碘甲状腺原氨酸(T3)、游离三碘甲状腺原氨酸(FT3)含量降低,四碘甲状腺原氨酸(T4)、游离四碘甲状腺原氨酸(FT4)含量升高。同时,FM550的暴露还可以导致罗非鱼的脂代谢改变,具体变化为血清总胆固醇(TC)、甘油三酯(TG)含量降低,高密度脂蛋白(HDL-C)含量升高,低密度脂蛋白(LDL-C)含量降低。不同剂量的FM550暴露对罗非鱼的全血生化指标并无影响。     

Role of water chemistry on estrone removal by nanofiltration with the presence of hydrophobic acids

Hydrophobic acid organic matter (HpoA) extracted from treated effluent has been known to improve the rejection of steroid hormone estrone by reverse osmosis (RO) and nanofiltration (NF) membranes. In this study, the effects of solution chemistry (solution pH and ionic strength) on the estrone rejection by NF membrane with the presence of HpoA were systematically investigated. Crossflow nanofiltration experiments show that the presence of HpoA significantly improved estrone rejection at all pH and ionic strength levels investigated. It is consistently shown that the “enhancement effect” of HpoA on estrone rejection at neutral and alkaline pH is attributed to the binding of estrone by HpoA macromolecules via hydrogen bonding between phenolic functional groups in feed solutions, which leads to an increase in molecular weight and appearance of negative charge. The membrane exhibited the best performance in terms of estrone rejection at pH 10.4 (compared to pH 4 and pH 7) as a result of strengthening the electrostatic repulsion between estrone and membrane with the presence of HpoA. At neutral pH level, the ability of HpoA macromolecules to promote estrone rejection became stronger with increasing ionic strength due to their more extended conformation, which created more chances for the association between estrone and HpoA. The important conclusion of this study is that increasing solution pH and salinity can greatly intensify the “enhancement effect” of HpoA. These results can be important for NF application in direct/indirect potable water reuse.     

甾体雌激素废水中优势降解菌的分离及特性

从某避孕药生产厂污水处理站好氧池活性污泥中通过富集驯化,分离到一株降解甾体雌激素(3-甲氧基-17a羟基-1,3,5(10),8(9)-雌甾-4-烯,简称MHE)的细菌ZY3菌株.经形态及16SrDNA序列分析初步鉴定,该菌株属于Raoultella属(Raoultellasp.).经过对ZY3菌株以MHE为唯一碳源生长和降解特性的分析表明,ZY3菌株利用MHE生长的最适温度和pH值分别为35℃和10.0,72h内的最适降解浓度为10mg/L.加入营养物质麦芽糖和蛋白胨能促进菌株对底物的降解,在72h内降解率达到了87%和85%.