三唑酮在水环境中的环境行为、毒性效应及生态风险

三唑酮是目前应用最广泛的三唑类广谱杀菌剂之一,在我国的使用量有逐年增长的趋势。本研究综述了三唑酮在水环境中的环境行为、毒性效应及其对我国部分水体的生态风险。三唑酮使用后被土壤吸附和解吸,经雨水淋溶作用进入地表或地下水环境,在丰水期检出率与检出浓度较高,目前我国地表水中三唑酮最高检出浓度为12μg·L-1。三唑酮在环境中的半衰期为15~43.3 d,能够在水生生物体内累积代谢,在不同浓度下对不同类群、不同生命阶段的水生生物表现出不同的毒性效应,对应着多条有害结局路径,其中最重要的是通过抑制细胞色素P450酶活性干扰机体内激素水平,影响水生生物繁殖和生长发育,导致种群密度降低。在目前已知的暴露水平下,三唑酮对我国地表水具有潜在的生态风险,特别是丰水期稻田附近的地表水风险尤其需要关注。     

Ecotoxicological Classification of the Berlin River System Using Bioassays in Respect to the European Water Framework Directive

Bioassays as well as biochemical responses (biomarkers) in ecosystems due to environmental stress provide us with signals (environmentally signalling) of potential damage in the environment. If these responses are perceived in this early stage in ecosystems, the eventual damage can be prevented. Once ecosystem damage has occurred, the remedial action processes for recovery could be expensive and pose certain logistical problems. Ideally, “early warning signals” in ecosystems using sensing systems of biochemical responses (biomarkers) would not only tell us the initial levels of damage, but these signals will also provide us with answers by the development of control strategies and precautionary measures in respect to the European Water Framework Directive (WFD). Clear technical guidelines or technical specifications on monitoring are necessary to establish and characterise reference conditions for use in an ecological status classification system for surface water bodies. For the Ecotoxicological Risk Assessment (ERA) of endocrine effects we used an approach of the exposure – dose – response concept. Based on the “Ecototoxicological Classification System of Sediments” that uses pT-values to classify effects in different river systems, we transferred the bio-monitoring data to the five-level ecological system of the WFD. To understand the complexity of the structure of populations and processes behind the health of populations, communities and ecosystems an ERA should establish links between natural factors, chemicals, and biological responses so as to assess causality. So, our ecological monitoring assessment has incorporated exposure & effects data.     

Northern Rivers Ecosystem Initiative: Distribution and Effects of Contaminants

In response to a number of recommendations following the Northern Rivers Basin Studies (NRBS) contaminant program, the Northern Rivers Ecosystem Initiative (NREI) focused considerable attention on assessing contaminants from specific sources including pulp mill effluents, atmospheric transport of mercury and the Alberta oil sands operations. NRBS identified a number of major contaminants of concern including polychlorinated biphenyls, dioxins and furans, mercury and various hydrocarbons. Together, the NRBS and the NREI studies have demonstrated major declines in the levels of dioxins and furans over the last decade as pulp and paper mills have changed their process and treatment strategies in response to new Federal regulations. Polychlorinated biphenyls however, continue to be a concern for the region as their levels have not declined in fish and sediments over the course of these studies. Higher levels in sediments downstream of Grande Prairie and Hinton were identified, but the source of these contaminants remains unknown. Chlorinated pesticides were also investigated, and although toxaphene, DDT and other chlorinated organic pesticides were detected in fish tissue, they were present at very low levels. Studies on the oil sands industry in northern Alberta demonstrated limited impacts on the Athabasca River to date, although studies did identify slight to moderate impacts of natural oil seeps on fish and benthic communities in tributary streams. NREI studies also identified endocrine active compounds in the three pulp and paper mill effluents tested, but endocrine disruptive effects in wild fish were minimal. Municipal sewage effluents also contain endocrine active compounds and it is recommended that monitoring continue around these point sources.     

泥沙腐殖质荧光特性及其与双酚A和类固醇吸附的关系

用批处理的方法测定了泥沙碱性可提取腐殖质对双酚A(BPA)和两种典型类固醇(17β-雌二醇(E2)和17α-乙炔基雌二醇(EE2))的吸附规律,分析了泥沙碱性可提取腐殖质的荧光光谱特征;探讨了腐殖质荧光光谱特征与BPA、E2和EE2吸附的关系.结果表明,泥沙碱性可提取腐殖质占泥沙总有机碳含量的9.3%～27.1%,BPA、E2和EE2三种物质的标化分配系数logKoc(hs)值变化范围分别为:3.14～4.09、3.47～4.33和3.65～4.32,其平均值大小顺序为EE2＞E2＞BPA,与3种物质辛醇水分配系数大小顺序一致.不同泥沙碱性可提取腐殖质的荧光光谱都有2个特征峰,其位置分别在Ex/Em=(310～330nm)/(390～400 nm)(α)和Ex/Em=(250～260nm)/(400～450nm)(α');2个特征峰峰强度比值(Iα'/Iα)变化范围为0.46～1.64;而且,泥沙中富里酸的荧光光谱与碱性可提取腐殖质的类似.腐殖质荧光光谱特征峰α由相对稳定、高分子量的芳香性类富里酸物质产生,随着芳香性类富里酸物质含量的增加Iα'/Iα值减小,因此,BPA、E2和EE2三种物质的logKoc(hs)与Iα'/Iα值间存在线性关系.     

Evaluation of the fish short term reproduction assay for detecting endocrine disrupters

In a fish testing strategy, positive results of the fish short term reproduction assay (FSTR), often trigger a definitive test like the fish sexual development test (FSDT) or the fish full life cycle test (FFLC), entailing ethical and economic problems. This study analysed 137 studies encompassing 35 chemicals with different modes of actions (MOAs). Variability is quantified for MOA endpoints vitellogenin (VTG) and secondary sex characteristics (SSCs) as well as for apical endpoints. Two MOA endpoints could indicate estrogenic, anti-estrogenic, androgenic, anti-androgenic and steroidogenesis activities. Great variability, however, has been observed for chemicals with anti-androgenic and steroidogenesis activities, suggesting that TG229/230 may not be sensitive enough to detect these types of chemicals and may produce false negatives. Changes in apical endpoints like fecundity are not limited to endocrine disrupting chemicals (EDCs). Non-EDCs could induce the similar effects on these apical endpoints. If elucidating MOA is needed, targeted in vitro MOA tests are suggested. Positive in vitro MOA results trigger a definitive test, which could be used for confirmation of the MOA in vivo and for deriving a no observed effect concentration (NOEC). Based on positive MOA results of TG229, a definitive test such as the FSDT or the FFLC is still needed, because the current TG229 has limitation on the derivation of a NOEC. An extended TG229 with more power to detect reproduction effects, as recently proposed in the OECD test guideline program, would improve the possibility to derive a NOEC and increase its usefulness in risk assessment.     

Effects of parabens on apoptosis induced by serum-free medium

Alkyl esters of p-hydroxybenzoic acids (parabens), an endocrine disrupter, are used as preservatives in cosmetics and foods. In this study, to understand the relationship between parabens and differentiation in infants, the effects of parabens on apoptosis induced by serum deprivation in PC12 cells were investigated. In addition, apoptosis-related factors were assayed. As results, a tendency toward enhancement of apoptosis was observed in the cells cultured in the serum-free medium with methylparaben, and this tendency was suggested to be related to the contents of BAD, a pro-apoptotic protein. Butylparaben did not show any tendency to enhance apoptosis.     

BDE-28对斑马鱼核受体介导的内分泌干扰效应研究

2,4,4’-三溴联苯醚(BDE-28)在环境中普遍存在,且在长江流域多种水生生物中检出。目前,国内外对高溴代PBDEs(如BDE-47、BDE-99等)的水生脊椎动物内分泌干扰效应报道较多,而BDE-28的有关研究则相对较少。将斑马鱼胚胎暴露于2、20和200μg·L~(-1)的BDE-28后,借助q-RT-PCR方法对幼鱼8个重要受体包括雄激素受体(AR)、甲状腺激素受体(TR)、芳香烃受体(AhR)、雌激素受体(ER)、糖皮质激素受体(GR)、孕烷X受体(PXR)、盐皮质激素受体(MR)和过氧化物酶体增殖物激活受体(PPAR)相关基因的转录水平进行了研究。结果表明,BDE-28暴露可导致AR、TR和Ah R的基因下调,其中核心受体AR和TR在低中高3种浓度下的下调倍数分别为3.03、2.64、10.10和2.21、2.18、2.31,芳香烃受体基因2(ahr2)在暴露于2和20μg·L~(-1)的BDE-28后,下调倍数分别为12.65和9.23,而雌激素受体(er1)基因在低中高浓度显著上调,上调倍数分别为12.29、12.67和15.87,雌激素受体(er2a)基因在2和20μg·L~(-1)BDE-28下的上调倍数分别为10.83和17.19。进一步采用分子对接和分子动力学模拟的方法研究BDE-28与AR、TR、Ah R和ER之间的相互作用。结果显示,BDE-28与这些受体通过疏水和氢键等相互作用稳定结合,动力学模拟后骨架原子的均方根偏差(RMSD)在5 ns后较稳定。由此可知,BDE-28通过AR、TR、Ah R和ER受体介导产生内分泌干扰效应。     

过氧化物酶催化去除水体中酚类内分泌干扰物的研究进展

内分泌干扰物(EDCs)会干扰生物体的内分泌系统从而对人类、野生动物以及水生生物产生负面影响,这一问题已经引起了人们的广泛关注.广泛分布于自然环境中的辣根过氧化物酶(HRP)和木质素过氧化物酶(LiP),具有较强的催化氧化能力,能够催化去除雌激素、双酚A等多种具有内分泌干扰效应的污染物.本文在介绍辣根过氧化物酶(HRP)和木质素过氧化物酶(LiP)两种过氧化物酶的相关性质和催化氧化机理的基础上,从污染物结构与其催化去除效率关系的角度综述了过氧化物酶去除具有内分泌干扰效应的污染物的研究进展.为污水处理过程中过氧化物酶用于去除内分泌干扰物提供依据,并展望了其未来的发展方向.     

环境孕激素和糖皮质激素的生态毒理效应:进展与展望

孕激素和糖皮质激素的环境行为和生态毒理效应是即环境雌激素和雄激素之后近年来国内外环境激素研究的又一热点课题。由于广泛应用于临床医疗等,这两类物质通过污水处理厂不完全处理和人类农业或畜牧业活动的直接排放从而进入水体环境,进而对生态系统和人类健康产生潜在危害。环境监测数据显示,在地表水中,多种物质存在ng·L-1浓度水平;在污水处理厂进出水中,浓度水平更高,甚至达到数百ng·L-1。孕激素和糖皮质激素类物质主要通过激素受体途径发挥毒性效应,如孕激素受体(PR),糖皮质激素受体(GR)和盐皮质激素受体(MR)。对水生脊椎动物的内分泌系统干扰作用是目前研究的焦点。这两类物质能够影响脑垂体性腺轴转录水平和相应激素合成,影响性腺发育以及导致繁殖能力损伤。这一毒性效应甚至发生在环境浓度水平之下。除此之外,随着组学技术的广泛应用,更多的潜在毒性终点不断被发掘,如对昼夜节律系统和免疫应答的干扰作用。这些研究引导着对环境孕激素和糖皮质激素生态毒理学效应更加深入的理解。     

Sewage-induced alterations in the sex of Oreochromis mossambicus: A plausible cue of endocrine disruption

Oreochromis mossambicus collected from Koraiyar, a tributary of the river Cauvery exhibited variations in their external genital features such as enlarged male genital papilla among equal sized fish, branching or budding in existing male genitalia, development of imposex (male genital papilla in female fish) and increased gonado-somatic index (GSI) and elevated male sex ratio in the population. All these variations at different levels is observed in their external genitalia indicated that they were all prompted towards maleness. This ambiguous sexual characteristic might be caused by endocrine disrupting environmental androgenic or anti-estrogenic substances, perhaps, present in the agrochemicals and sewage-mixed Koraiyar water.