厌氧与缺氧污泥对17β-雌二醇吸附性能的研究

雌二醇浓度为500～10 000　ng/L,采用活性污泥灭活吸附,考察了吸附平衡时间和pH值对吸附的影响.在10、20、30℃不同温度下建立了Freundlich吸附等温线,并计算了分配系数K_d.结果表明,厌氧与缺氧失活污泥对雌二醇的吸附都在30 min以内达到平衡;pH值在6～9范围内对吸附没有影响,pH大于9时随着pH值增加吸附量减少;两者在不同温度下对雌二醇的吸附都符合Freundlich吸附,都呈线性吸附,分配系数随温度升高而降低,厌氧失活污泥的分配系数K_d为629.2(10℃)＞534.9(20℃)＞405.6(30℃),缺氧失活污泥的分配系数K_d为601.2(10℃)＞491.3(20℃)＞360.1(30℃).另外,研究了厌氧与缺氧活性污泥的吸附等温线与分配系数,厌氧活性污泥的K_d大于缺氧活性污泥.厌氧(缺氧)活性污泥与灭活污泥对雌二醇的吸附未出现明显差别,厌氧污泥的吸附性能强于缺氧污泥.     

低剂量全氟辛酸对雄性黑斑蛙生殖毒效应及机理研究

针对新型环境有机污染物全氟辛酸(PFOA)对两栖动物的毒效应问题,以黑斑蛙(Rana nigromaculata)为实验对象,研究了低剂量PFOA暴露对雄性黑斑蛙生殖毒效应及机理.结果表明,在0.001～1mg.L-1低剂量体外暴露20d条件下,PFOA能够显著诱导黑斑蛙精子发生畸形,相对于对照组,精子畸形率呈现明显的剂量-效应关系.酶联免疫试剂盒检测发现,除0.001mg.L-1诱导组外,0.01、0.1和1mg.L-1暴露组的血清雄性激素睾酮和雌性激素雌二醇含量分别显著降低(p<0.01,F=288.7)和上升(p<0.01,F=289.0),说明PFOA作用下黑斑蛙体内性激素水平受到改变.采用荧光定量PCR技术进行进一步的分子生物学检测,发现与性激素水平密切相关的两个基因P450芳香化酶和类固醇激素合成因子(SF-1)均增强表达(0.001mg.L-1诱导组,p<0.05;0.01、0.1和1mg.L-1暴露组,p<0.01,F=140.8).全氟辛酸对两栖类动物的雄性生殖毒效应机理主要是通过介导与性激素分泌相关的两个重要基因P450芳香化酶和类固醇激素合成因子,使其表达上调,从而一方面抑制睾酮的产生,另一方面促进性激素雌二醇的分泌.在0.001mg.L-1的体外暴露剂量下,PFOA就能够明显诱导黑斑蛙精子产生畸形毒性及增强P450芳香化酶和SF-1基因的表达(p<0.05),因此,为保护两栖动物种群,在制订PFOA地表水环境质量标准时应当考虑其下限不能低于0.001mg.L-1.     

Effect of Light on Biodegradation of Estrone, 17β‐Estradiol,and 17α‐Ethinylestradiol in Stream Sediment

Biodegradation of [A‐ring ¹⁴C] Estrone (E1), 17β‐estradiol (E2), and 17α‐ethinylestradiol (EE2) to ¹⁴CO₂ was investigated under light and dark conditions in microcosms containing epilithon or sediment collected from Boulder Creek, Colorado. Mineralization of the estrogen A‐ring was observed in all sediment treatments, but not epilithon treatments. No difference in net mineralization between light and dark treatments was observed for ¹⁴C‐E2. Net mineralization of ¹⁴C‐E1 and ¹⁴C‐EE2 was enhanced in light treatments. Extents of ¹⁴CO₂ accumulation and rates of mineralization were significantly greater for E2 than E1 under dark conditions, but were comparable under light conditions. These results indicate substantial differences in the uptake and metabolism of E1 and E2 in the environment and suggest biorecalcitrance of E1 relative to E2 in light‐limited environments. The extent of ¹⁴CO₂ accumulation and rate of mineralization for EE2 in dark treatments were less than half of that observed for E2 and generally lower than for E1, consistent with previous reports of EE2 biorecalcitrance. However, ¹⁴CO₂ accumulation and rates of mineralization were comparable for EE2, E2, and E1 under light conditions. These results indicate photoactivation and/or phototransformation/photodegradation processes can substantially enhance heterotrophic biodegradation of estrogens in sunlit environments and may play an important role in estrogen transport and attenuation.     

MTBE与雌二醇对螺旋鱼腥藻的联合毒性

以螺旋鱼腥藻(Anabaena spiroides)为实验材料,采用每天测定数据,连续跟踪10d的方法,研究了甲基叔丁基醚(Methyl tert-buty1 ether,MTBE)与雌二醇对螺旋鱼腥藻的单一毒性以及在不同毒性单位配比下的联合毒性,选用毒性单位(TU)、相加指数(AI)、混合毒性指数(MTI)和毒性增大指数(TEI)进行联合毒性评价.结果表明,MTBE与雌二醇共存时,在实验周期(10d)内,其联合作用方式基本表现为协同作用.此外,MTBE和雌二醇的单一毒性和联合毒性数据随着培养时间的变化而产生剧烈变化,毒性数据在培养时间3～7d比较平稳,在4～5d最佳.     

The OECD Validation Program of the H295R Steroidogenesis Assay for the Identification of In Vitro Inhibitors and Inducers of Testosterone and Estradiol Production. Phase 2: Inter-Laboratory Pre-Validation Studies (8 pp)

Background, Goals and Scope In response to concerns that have been raised about chemical substances that may alter the function of endocrine systems and result in adverse effects on human health, an OECD initiative was undertaken to develop and validate in vitro and in vivo assays to identify chemicals that may interfere with endocrine systems of vertebrates. Here we report on studies that were conducted to develop and standardize a cell-based screening assay using the H295R cell line to prioritize chemicals that may act on steroidogenic processes in humans and wildlife. These studies are currently ongoing as part of the ‘Special Activity on the Testing and Assessment of Endocrine Disruptors’ within the OECD Test Guidelines Program to review, develop, standardize, and validate a number of in vitro and in vivo toxicological assays for testing and assessment of chemicals concerning their potential to interact with the endocrine system of vertebrates. Study Design Six laboratories from five countries participated in the pre-validation studies. Each laboratory tested the effects of three model chemicals on the production of testosterone (T) and estradiol (E2) using the H295R Steroidogenesis Assay. Chemicals tested were well described inducers or inhibitors of steroidogenic pathways (forskolin, prochloraz and fadrozole). All experiments were conducted in 24 well plates following standard protocols. Six different doses per compound were analyzed in triplicate per plate. A quality control (QC) plate was run in conjunction with the chemical exposure plate to account for inter-assay variation. Each chemical exposure was conducted two or three times. Results All laboratories successfully detected increases and/or decreases in hormone production by H295R cells after exposure to the different model compounds and there was good agreement in the pattern of response for all groups. Forskolin increased both T and E2 while fadrozole and prochloraz decreased production of both hormones. All chemicals affected hormone production in a dose-dependent manner with the exception of fadrozole which caused maximum inhibition of E2 at the two least concentrations tested. Some inter-laboratory differences were noted in the alteration of hormone production measured in chemically exposed cells. However, with the exception of the production of T measured at one laboratory in cells exposed to forskolin, the EC₅₀s calculated were comparable (coefficients of variation 34–49%) for all hormones. Discussion and Perspectives The results indicated that the H295R Steroidogenesis Assay protocol was robust, transferable and reproducible among all laboratories. However, in several instances that were primarily related to one laboratory there were unexplained minor uncertainties related to the inter-laboratory hormone production variation. Based on the findings from this Phase 2 prevalidation study, the H295R Steroidogenesis Assay protocol is currently being refined. The next phase of the OECD validation program will test the refined protocol among the same group of laboratories using an extended set of chemicals (∼30) that will include positive and negative chemical controls as well as a broad spectrum of different potential inducers and inhibitors of steroidogenic pathways. Submission Editor: Dr. Carsten Brühl (bruehl@uni-landau.de)     

二氧化锰氧化降解乙炔基雌二醇的动力学研究

研究了化学合成的新生态δ-MnO2对乙炔基雌二醇(EE2)的氧化降解动力学,并且考察了δ-MnO2投加重、EE2初始浓度、初始pH值等因素对EE2降解动力学的影响.结果表明:EE2对新生态水合δ-MnO2的氧化作用具有较强的反应感受性,且在pH值一定和δ-MnO2充分过量的条件下,EE2氧化降解的反应动力学并不是简单的...     

炔雌醇和壬基酚在土壤中的吸附-解吸特征

通过吸附动力学研究和批量平衡试验,以炔雌醇(EE2)和壬基酚(NP)为代表,考察内分泌干扰物在3种不同性质的天然土壤中的吸附-解吸特征.结果表明,双室一级动力学模型比单室一级动力学模型更适合描述EE2、NP在土壤中的动态吸附过程.快吸附过程在吸附初期占据主导地位,之后慢吸附室的相对贡献逐渐增大,直至达到吸附平衡.土壤对NP的吸附速率是EE2的2.0～4.7倍.Freundlich模型和DA模型均能较好地拟合EE2与NP的吸附等温线,但DA模型拟合效果更佳.饱和吸附容量与土壤有机质含量呈显著正相关,EE2的饱和吸附容量(0.85～7.67μg·g-1)明显低于NP(10.47～110.15μg·g-1).吸附自由能计算表明,土壤对EE2和NP的吸附以物理作用为主.此外,3种受试土壤对EE2和NP的解吸附均存在滞后现象,需要预防其潜在的环境风险,其中有机质含量最高、比表面积最大的土样滞后性最明显.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.     

The effect of in utero exposure to dioxins and polychlorinated biphenyls on reproductive development in eight year-old children

We have previously reported on the effects of in utero exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) on thyroid function and growth hormone concentrations at birth and in two and five year-old children. Herein, we present our most recent follow-up examination findings for the same cohort of children at eight-years of age. A total of 56 children (23 boys, 33 girls) were examined. Bone age (BA), hormone concentrations, and indicators of reproductive development including Tanner, breast, genital, and armpit stages were assessed. Estradiol concentrations were significantly lower in children exposed to higher levels than median of PCDD/Fs + PCBs TEQ compared to the children exposed to levels lesser than median (P = 0.003). Girls exposed to higher levels than median of indicator PCBs had a significantly greater proportion in genital stage 1 and shorter fundi and uteri lengths, as compared to those exposed to low levels (P = 0.025 and P < 0.05, respectively). There was a significant negative relationship between estradiol concentrations and PCDD/Fs + PCB exposure level (P = 0.005). After adjusting for BA, there was a significant association between fundus length and indicator PCB exposure level (P = 0.034). Exposure to both high levels of ΣPCDD/Fs + PCBs TEQ and high levels of total PCBs was associated with decreased fundus length (P = 0.016) and uterus length (P = 0.016). In utero exposure to high levels of PCDD/Fs and PCBs may result in lower estradiol concentrations in eight year-old children and impaired reproductive development in girls.     

Dioxin levels in the breast milk and estradiol and androgen levels in the saliva of Vietnamese primiparae

Human exposure to polychlorinated dibenzodioxins (PCDD) and dibenzofurans (PCDF), especially 2,3,7,8 tetrachlorodibenzo-p-dioxin (TCDD), was investigated in Vietnam since initial severe adverse health effects were reported in the late 1970s. The purpose of this study was to determine the effects of dioxin exposure on steroid hormones of primiparae in an Agent Orange/dioxin hot-spot and a non-exposed area in Vietnam. Sixteen primiparae (8 at each site), all of whom were aged between 20 and 30 years with infants aged between 4 and 16 weeks, agreed to participate in this study. The mean dioxin levels in breast milk of primiparae from the hot-spot area, in terms of PCDD, PCDF, and PCDD?+?PCDF toxic equivalents (TEQ), were significantly higher than those for the non-exposed area. PCDD TEQ, PCDF TEQ, and PCDD?+?PCDF TEQ levels showed a significant correlation with dehydroepiandrosterone (DHEA), androstenedione (A-dione), and estradiol (E2) in the saliva of primiparae in a combination of hot-spot and non-exposed areas in Vietnam. The dose–response curve between salivary E2 or A-dione levels and dioxin levels was U-shaped in humans. This study provides an overview of studies regarding dioxin hot-spots and effects on human health and steroid hormone levels in particular, with a focus on the toxicity attributed to dioxins and furans. Furthermore, causal evidence regarding the effects of dioxins on endocrine disruption in humans is provided.