城区大气和塑料大棚空气中酞酸酯的分析

本文报道了济南市大气飘尘和塑料蔬菜大棚空气中酞酸酯的污染情况，探讨了大气飘尘中酞酸酯随季节变化和昼夜更替的变化情况。     

邻苯二甲酸丁基苄酯对小鼠睾丸能量代谢相关酶的影响

为了从生殖细胞能量代谢角度探讨邻苯二甲酸丁基苄酯(BBP)对雄性小鼠生殖损伤的机制,以昆明系雄性小白鼠为实验对象,研究了BBP对小鼠睾丸组织能量代谢相关酶的影响.实验设0、125、250、500、1000mg·kg-1(质量分数)5组浓度梯度,连续灌胃染毒30d后,采用分光光度法检测小鼠睾丸组织匀浆中乳酸脱氢酶(LDH)、琥珀酸脱氢酶(SDH)、Ca-Mg-ATPase酶的活性以及睾丸脏器系数.结果发现,1)与对照组相比,高浓度染毒组(500、1000mg·kg-1)LDH、SDH和Ca-Mg-ATPase活性均极显著降低(p<0.01);而低浓度染毒组(125mg·kg-1)3种酶活性均无显著变化(p>0.05);中浓度染毒组(250mg·kg-1)LDH没有显著变化(p>0.05),而SDH、Ca-Mg-ATPase均显著降低(p<0.05,p<0.01).2)染毒30d后,各染毒组睾丸脏器系数略有下降,但与对照组相比,差异均未达到显著水平(p>0.05).以上结果表明,较高水平的BBP不仅可以干扰睾丸组织有氧代谢及无氧代谢的产能过程,还可以干扰生殖细胞对能量的利用,提示能量代谢的障碍可能是BBP对雄性生殖细胞产生损伤的原因之一.     

Bioanalytical and instrumental analysis of thyroid hormone disrupting compounds in water sources along the Yangtze River

Thyroid hormone (TH) agonist and antagonist activities of water sources along the Yangtze River in China were surveyed by a green monkey kidney fibroblast (CV-1) cell-based TH reporter gene assay. Instrumental analysis was conducted to identify the responsible thyroid-active compounds. Instrumentally derived l-3,5,3′-triiodothyronine (T₃) equivalents (T₃-EQs) and thyroid receptor (TR) antagonist activity equivalents referring to dibutyl phthalate (DBP-EQs) were calculated from the concentrations of individual congeners. The reporter gene assay demonstrated that three out of eleven water sources contained TR agonist activity equivalents (TR-EQs), ranging from 286 to 293 ng T₃/L. Anti-thyroid hormone activities were found in all water sources with the TR antagonist activity equivalents referring to DBP (Ant-TR-EQs), ranging from 51.5 to 555.3 μg/L. Comparisons of the equivalents from instrumental and biological assays suggested that high concentrations of DBP and di-2-ethylhexyl phthalate (DEHP) were responsible for the observed TR antagonist activities at some locations along the Yangtze River.     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.     

邻苯二甲酸二丁酯降解过程的单体同位素分析

研究对比了邻苯二甲酸二丁酯（DBP）在不同降解过程（水解、UV/H₂O₂光解、直接光解、过硫酸钾光氧化）中的碳、氢同位素组成变化、分馏特征及二维同位素（Δδ²H-Δδ¹³C）的相关性.水解反应中DBP分子产生了显著的碳同位素分馏,未发现氢同位素分馏,而且碳同位素富集因子ε_C为（-2.7±0.4）‰,表明DBP水解时发生C-O键断裂,氢原子不参与反应.而UV/H₂O₂光解和直接光解反应（pH值分别为2、7和10）中,DBP分子呈现了相似的二维同位素相关性Λ值[（9±2）~（11±2）],推测经历了相同的反应过程.过硫酸钾光氧化降解时,明显偏大的Λ值（31±3）说明反应可能发生C-H键断裂.结果表明：二维单体同位素分析（2D-CSIA）技术可以有效区分DBP的水解、光解、光氧化3种不同类型的降解过程,有助于分析其降解路径.     

DIDP通过线粒体-Caspase途径诱导昆明小鼠肝脏损伤的研究

为探究DIDP（Di-iso-decyl phthalate,邻苯二甲酸二异癸酯）对肝脏的影响及其可能的分子机制,以昆明小鼠为研究对象,选用Res（resveratrol,白藜芦醇）为抗氧化剂,分别设置对照组,0.15、1.5、15、150 mg/（kg·d）DIDP组,Res组,150 mg/（kg·d）DIDP+Res组,灌胃染毒9 d后,对小鼠肝脏切片进行HE染色观察,并检测ROS（reactive oxygen,活性氧）、GSH（glutathione,谷胱甘肽）、MDA（malondialdehyde,丙二醛）、Cyt-C（cytochromec,细胞色素C）、Caspase-3和血清中的ALT（alanine aminotransferase,丙氨酸氨基转移酶）含量.结果表明:与对照组相比,15、150 mg/（kg·d）DIDP组小鼠血清中ALT含量极显著上升（P < 0.01）;HE染色结果显示,15、150 mg/（kg·d）DIDP组小鼠出现肝细胞水肿、肝索紊乱、肝窦以及肝中央静脉扩张等现象;15、150 mg/（kg·d）DIDP组小鼠肝脏ROS含量显著上升（P < 0.05）,GSH含量显著下降（P < 0.05）,150 mg/（kg·d）DIDP组小鼠肝脏MDA含量极显著上升（P < 0.01）;1.5、15、150 mg/（kg·d）DIDP组小鼠肝脏中c（Cyt-C）极显著上升（P < 0.01）;15、150 mg/（kg·d）DIDP组小鼠肝脏中Caspase-3表达量极显著上升（P < 0.01）.DIDP染毒剂量的增加对肝脏的各种损伤程度呈上升趋势,Res可减轻上述DIDP对肝脏造成的各种损伤.研究显示,15、150 mg/（kg·d）DIDP可诱导肝脏组织氧化应激水平上升,进而造成线粒体损伤,导致细胞凋亡,造成肝功能受损,因此,线粒体-Caspase途径可能是DIDP诱导肝脏损伤的潜在机制之一.      

邻苯二甲酸二丁酯的微生物降解

通过驯化富集培养,从处理石化厂废水的活性污泥中分离出１株邻苯二甲酸酯降解菌ＦＳＩ,研究了邻苯二甲酸酯菌ＦＳＩ对邻苯二甲酸二丁酯的生物降解特性。邻苯二甲酸酯降解菌ＦＳＩ降解最适酸度为ｐＨ６．５～８．０,温度为２０～３５℃。菌株ＦＳＩ对邻苯二甲酸二丁酯的生物降解反应速率遵循一级反应动力学模式。试验结果表明,菌株ＦＳＩ对邻苯二甲本二丁酯具有高效降解作用。     

苯并芘和邻苯二甲酸二(2-乙基己基)酯复合暴露对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物共存情况下对长江上游三峡库区特有珍稀鱼类的环境风险,以稀有鮈鲫(Gobiocypris rarus)为对象,研究了多环芳烃和酞酸酯的代表物苯并芘(BaP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)单独及复合暴露而引起的内分泌干扰效应。将成年稀有鮈鲫暴露于不同浓度的BaP(0.1、1μg·L~(-1))、DEHP(10、100μg·L~(-1))和BaP+DEHP((0.1+10)、(1+100)μg·L~(-1))中28 d后,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与生殖相关基因的表达。结果表明:在雌鱼中,单独BaP或DEHP暴露对鱼体性激素含量、基因表达量无显著影响; BaP和DEHP复合暴露时,高浓度组睾酮(T)含量升高但雌二醇(E2)含量下降,fsh、vtg、 cyp17和17β-hsd基因表达量上调,cyp19a则下调,表现出协同毒性。因而雌鱼中性激素水平的改变可能与类固醇合成相关基因表达量的改变有关。而无论在单独暴露或是复合暴露情况下,对雄鱼体内性激素无显著影响。以上检测到的激素或基因表达量的改变主要发生在高剂量的复合暴露组中,而长江上游三峡库区水体中多环芳烃和酞酸酯含量低于暴露的最低浓度,因此推测,库区存在的多环芳烃和酞酸酯同时作用时不会对三峡库区上游水体中的鱼类产生生殖内分泌干扰效应。     

Dibutyl phthalate adsorption characteristics using three common substrates in aqueous solutions

• DBP adsorption was tested using three kinds of substrates in constructed wetlands. • The DBP adsorption capacity followed the order: steel slag>gravel>shell sand. • High temperatures increased the DBP adsorption capacity in the substrates. • DOM consistently inhibited the DBP adsorption onto steel slag and gravel. In recent years, the presence and adverse impacts of phthalic acid esters in aquatic environments have gained increasing attention. This work investigated the adsorption behavior of a typical phthalic acid ester, dibutyl phthalate (DBP), onto steel slag, gravel, and shell sand (substrates commonly used in constructed wetlands). The influence of dissolved organic matter (DOM) on DBP adsorption was investigated using humic acid as a proxy for DOM. The results demonstrated that the adsorption of DBP to three substrates reached equilibrium within 96 h, and the adsorption kinetics were well fitted by a pseudo-second-order model. The DBP adsorption isotherms were best fitted by the Langmuir adsorption model. The DBP adsorption capacity decreased in the order of steel slag>gravel>shell sand, with values of 656 mg/kg, 598 mg/kg, and 6.62 mg/kg at 25°C, respectively. DBP adsorbed to the surface of all substrates in a monolayer via an endothermic process. The DBP adsorption capacities of steel slag and gravel decreased as the DOM content increased. The DBP adsorption mechanisms to steel slag and gravel mainly involved the surface coordination of DBP with –OH or –COOH groups and electrostatic interactions. The results of this work suggest that steel slag and gravel may be ideal substrates for use in constructed wetlands to treat wastewater polluted with DBP.     

A miniature stainless steel net dumbbell-shaped stir-bar for the extraction of phthalate esters in instant noodle and rice soup samples

Abstract

This work reports the development of a very-simple-to-construct stir-bar extraction device so called “a dumbbell-shaped stainless steel stir-bar.” The extraction device was assembled from a rolled up stainless steel net filled with an XAD-2 sorbent and a metal rod to allow the use of a magnetic stirrer during extraction. The dumbbell-shaped stainless steel stir-bar was used to extract diethyl phthalate (DEP), dibutyl phthalate (DBP), and di(2-ethylhexyl) phthalate (DEHP) before analysis by a gas chromatograph equipped with an electron capture detector (GD-ECD). Under the optimal conditions, the developed method provided a good linearity from 10.0 to 1,000.0?ng mL^?1 for all three compounds. Limits of detection and limits of quantification were 9.37?±?0.29?ng mL^?1 and 31.22?±?0.95?ng mL^?1 for DEP, 5.73?±?0.31?ng mL^?1 and 19.1?±?1.0?ng mL^?1 for DBP and 3.30?±?0.06?ng mL^?1 and 11.0?±?0.19?ng mL^?1 for DEHP, respectively. Good recoveries in the range of 81.89?±?0.17 to 109.5?±?2.0% were achieved when the method was used to extract phthalate esters in five instant noodle and two rice soup samples.