壬基酚聚氧乙烯醚在污水处理过程中的迁移转化行为

用正相色谱－质谱联用法（NPLC－MS）分离分析高聚合度的NPnEO(n＞2）,用气相色谱－质谱联用方法（GC－MS）测定其中的NP,NP1EO和NP2EO浓度,对NPnEO在城市污水处理厂的迁移转化行为进行了研究。在污水处理厂的进水中,检测出NP和NPnEO(n=1-23）,总浓度为174nmol/L,其中NP2EO的浓度最高,为89．6nmol/L;其次分别为NP（42．2nmol/L）和NP1EO（12．2nmol/L）;出水中同样检测出NP和NPnEO(n=1-18),其中NP2EO的浓度最高,为37．2nmol/L;其次分别为NP（6．64nmol/L）和NP1EO（0．135nmol/L)。在城市污水处理过程中,NPnEO从高聚合度降妥成低聚合度,NP和NPnEO的总去降率为71％。另外,NP和NPnEO在污泥及污泥过滤水中的分配表明污泥对NPnEO有明显的吸附作用,并近似符合Dubinin-Astakhov等温吸附。     

辛基酚的体内类雌激素活性评价

利用体内大鼠子宫增重试验检测辛基酚（OP）的类雌激素活性，并对其观测终点及影响因素进行了初步研究。结果显示，OP经大鼠体内染毒，可引起大鼠子宫湿重、子宫内皮细胞厚度、子宫腺数量明显增加，具有明显的类雌激素活性。三条染毒途径检测敏感度腹腔染毒＞经皮下染毒＞经灌胃染毒。     

Human exposure to a mixture of endocrine disruptors and serum levels of thyroid hormones: A cross-sectional study

Exposure to endocrine disruptors (EDCs) could disrupt thyroid hormone homeostasis. However, human epidemiological studies reported inconsistent observations, and scarce information on the effect of a mixture of chemicals. The aim of the present study was to examine the associations of multiple chemicals with thyroid hormones among adults from China. We measured serum levels of thyroid hormones and urinary levels of 11 EDCs, including six phthalate metabolites, bisphenol A (BPA), bisphenol F (BPF), bisphenol S (BPS), perchlorate, and thiocyanate among 177 healthy adults without occupational exposure. Associations of multiple urinary analytes with serum thyroid hormones were examined by performing general linear regression analysis and bayesian kernal machine regression analysis. These EDCs were detected in almost all samples. After adjusting for various covariates, we observed only BPF significantly associated with total thyroxin (TT4) (β=-0.27, 95% confidence interval (CI) [-0.41, -0.14]), total triiodothyronine (TT3) (β=-0.02 95% CI [-0.03, -0.01]), free T4 (fT4) (β=-0.02, 95% CI [-0.03, -0.01]), and free T3 (fT3) (β=-0.04, 95% CI [-0.07, -0.01]), and mono-(2-ethyl-5-oxohexyl) phthalate (MEOHP) and monoethyl phthalate (MEP) positively associated with TT4 (β=0.24, 95% CI [0.01, 0.48]) and fT4 (β=0.02, 95% CI [0.01, 0.04]), respectively. Moreover, we observed significant dose-response relationships between TT4 and the mixture of 11 EDCs, and BPF was the main contributor to the mixture effect, suggesting the priority of potential effect of BPF on disrupting thyroid function under a real scenario of human exposure to multiple EDCs. Our findings supported the hypothesis that human exposure to low levels of EDCs could alter thyroid hormones homeostasis among non-occupational healthy adults.     

四川妇女血清中多溴联苯醚的浓度水平与组成特征

用气相色谱-质谱的选择离子法测定四川省妇女血清中多溴联苯醚的质量浓度,并对其组成特征及主要来源进行了研究.在被测的11种多溴联苯醚当中,BDE-209是主要成分,质量浓度从0.12～2.38μg.L-1,中值为0.63μg.L-1,占多溴联苯醚总量的质量分数为63.57%～90.34%,其次是BDE-66、-99和-100,其它多溴联苯醚几乎没有检出,表明污染主要来自十溴联苯醚,其次是四溴和五溴联苯醚.实验结果与其它国家的数据相比,表明多溴联苯醚对普通妇女的污染在四川还处于一个较低的水平.     

沉积物中雌激素及壬基酚、辛基酚、双酚A的测定

近些年来雌激素及烷基酚类化合物由于其对水生生物的内分泌干扰作用越来越受到广泛关注.沉积物作为环境中有机污染物的重要储存库,研究目标物在其中的浓度分布对于探明此类物质在环境中的迁移转化具有重要意义.但沉积物中基质组成复杂而雌激素又痕量存在,这增加了前处理的难度.本研究从雌激素及烷基酚类化合物的理化性质入手,采用碱液提取、液液萃取和LC-MS/MS分析测定沉积物样品中的雌激素及壬基酚、辛基酚、双酚A.结果表明,经过优化的方法对7种目标物的回收率介于61.9%～93.7%之间.该方法能有效去除沉积物中那些不溶于强碱和既溶于酸又溶于碱的有机污染物,同时操作简单、成本低,但回收率高、检出限低,可广泛适用于河流沉积物样品及土壤样品的前处理.     

内分泌干扰物在城市污水处理厂中的行为和归趋：综述

内分泌干扰物作为一类新型污染物,由于其在环境水体中微量的浓度即可对野生动物产生内分泌干扰效应,因此引起了人们的广泛关注.本文以两类主要内分泌干扰物(即类固醇雌激素和酚类内分泌干扰物)作为研究对象,综述了它们在城市污水处理厂中的浓度水平以及相应的去除效率,并探讨了不同生物处理工艺、运行操作条件等对去除效率的影响.此外,通...     

崇明典型水生生物中雌激素含量和分布特征

采用超高效液相色谱串联质谱系统(UHPLC-MS2)检测崇明岛9种典型水生生物体中5种典型雌激素的含量,包括雌酮(E1)、雌二醇(E2)、雌三醇(E3)、炔雌醇(EE2)和双酚A(BPA).并探讨其分布特征,进行初步健康风险评价.结果表明,9种典型水生生物中雌激素总量(以dw计)为1.1~7.38 ng·g-1,平均为4.25 ng·g-1.雌激素脂肪含量(以lw计)在5.01~83.41 ng·g-1之间,平均值为40.75 ng·g-1,雌激素脂肪含量水平表现为鱼类>虾类>蟹类.鱼类和蟹类,虾类之间雌激素脂肪含量差异性显著,蟹类和虾类之间不存在显著差异性.从检出率和检出含量看,甾醇类雌激素(E1、E2、E3和EE2)的残留明显低于酚类雌激素(BPA).E1、E2、E3和EE2的检出率小于66.67%,平均干重含量为0.17~0.69ng·g-1,而BPA的检出率高达100%,检出的平均干重含量为2.60 ng·g-1.健康风险评估结果表明,崇明岛水产品中雌激素对健康影响不大.     

Toxic masking and synergistic modulation of the estrogenic activity of chemical mixtures in a yeast estrogen screen (YES)

Background, aim and scope

Estrogenic and non-estrogenic chemicals typically co-occur in the environment. Interference by non-estrogenic chemicals may confound the assessment of the actual estrogenic activity of complex environmental samples. The aim of the present study was to investigate whether, in which way and how seriously the estrogenic activity of single estrogens and the observed and predicted joint action of estrogenic mixtures is influenced by toxic masking and synergistic modulation caused by non-estrogenic chemical confounders.

Materials and methods

The yeast estrogen screen (YES) was adapted so that toxicity and estrogenicity could be quantified simultaneously in one experimental run. Mercury, two organic solvents (dimethyl sulfoxide (DMSO) and 2,4-dinitroaniline), a surfactant (LAS-12) and the antibiotic cycloheximide were selected as toxic but non-estrogenic test chemicals. The confounding impact of selected concentrations of these toxicants on the estrogenic activity of the hormone 17ß-estradiol was determined by co-incubation experiments. In a second step, the impact of toxic masking and synergistic modulation on the predictability of the joint action of 17ß-estradiol, estrone and estriol mixtures by concentration addition was analysed.

Results

Each of the non-estrogenic chemicals reduced the apparent estrogenicity of both single estrogens and their mixtures if applied at high, toxic concentrations. Besides this common pattern, a highly substance- and concentration-dependent impact of the non-estrogenic toxicants was observable. The activity of 17ß-estradiol was still reduced in the presence of only low or non-toxic concentrations of 2,4-dinitroaniline and cycloheximide, which was not the case for mercury and DMSO. A clear synergistic modulation, i.e. an enhanced estrogenic activity, was induced by the presence of slightly toxic concentrations of LAS-12. The joint estrogenic activity of the mixture of estrogens was affected by toxic masking and synergistic modulation in direct proportion to the single estrogens, which allowed for an adequate adaptation of concentration addition and thus unaffected predictability of the joint estrogenicity in the presence of non-estrogenic confounders.

Discussion

The modified YES proved to be a reliable system for the simultaneous quantification of yeast toxicity and estrogen receptor activation. Experimental results substantiate the available evidence for toxic masking as a relevant phenomenon in estrogenicity assessment of complex environmental samples. Synergistic modulation of estrogenic activity by non-estrogenic confounders might be of lower importance. The concept of concentration addition is discussed as a valuable tool for estrogenicity assessment of complex mixtures, with deviations of the measured joint estrogenicity from predictions indicating the need for refined analyses.

Conclusions

Two major challenges are to be considered simultaneously for a reliable analysis of the estrogenic activity of complex mixtures: the identification of known and suspected estrogenic compounds in the sample as well as the substance- and effect-level-dependent confounding impact of non-estrogenic toxicants.

Recommendations and perspectives

The application of screening assays such as the YES to complex mixtures should be accompanied by measures that safeguard against false negative results which may be caused by non-estrogenic but toxic confounders. Simultaneous assessments of estrogenicity and toxicity are generally advisable.     

超高效液相色谱-串联质谱法同时分析地下水中24种内分泌干扰物

建立了基于超高效液相色谱-串联质谱法同时测定地下水中9种雌激素、5种雄激素、3种肾上腺皮质激素、4种酚类和3种非甾类激素共24种内分泌干扰物的方法。在活化后的MCX固相萃取柱中加入水样,再加入pH=5的水溶液淋洗,随后用碱化乙腈(4.5%,体积分数)洗脱。收集洗脱液并用氮气吹至近干后,用甲醇定容。采用Poroshell 120 Bonus-RP色谱柱(2.7 μm,100 mm×2.1 mm),以0.1%氨水溶液-乙腈为流动相进行梯度洗脱,实现液相分离。质谱检测采用MRM模式进行采集,通过正负离子模式切换同时进行测定,使用内标法定量。检测结果显示,目标物在线性范围内,决定系数R²均大于0.995,方法检出限为0.05~2.00 ng/L,加标回收率为68.8%~108%。该方法灵敏度高、准确度好,具有较强的实用价值。     

Temporal and spatial patterns of micropollutants in urban receiving waters

Based on a monitoring program over the course of a year, we characterize the temporal and spatial distribution of selected micropollutants in an urban watershed within the city of Leipzig, Germany. Micropollutants revealed a ubiquitous presence in untreated and treated wastewater, surface water and groundwater. The loads of 4-nonylphenol in the effluents of the municipal wastewater treatment plant followed a seasonal trend, whereas the loads of all other micropollutants were highly variable and not correlated to seasons. In the surface water, load seasonality of caffeine, galaxolide and tonalide resulted from a rapid removal with increased water temperature. The loads of 4-nonylphenol and of caffeine in the colder months increased when rainfall occurred. In the groundwater, complex spatial and temporal patterns were apparent and were related to varying input, retardation and removal processes. As a consequence, an assessment of micropollutants in urban waters should consider different micropollutants' temporal and spatial variability.