Vertical distribution of nonylphenol and nonylphenol ethoxylates in sedimentary core from the Beipaiming Channel, North China

The vertical profiles of nonylphenol （NP） and nonylphenol ethoxylates （NPEOs） were investigated in a sediment core from the Beipaiming Channel, North China using high sensitive LC-MS and GC-MS metthods In this core, relatively high concentrations of NP and NPEOs occurred in the surface sediment （≤40 cm）, with the maximum value of NP and NPEOs reaching 3539 and 12735 mg/g, respectively, whereas, no NP or NPEOs were detected in deeper sediments （〉40 cm）. The high concentrations of NP and NPEOs in the surface layers suggested recent inputs in this area. NPEOs with short ethoxy chains （NPnEO, n=0-3） were dominant in the NPEO mixture with percentages from 54% to 78%, which were similar to the distribution of homolog NPEO in effluents from nearby sewage treatment plants （STPs）, indicating that the channel received the effluents from these STPs. The sewage treatment ratio was quite similar to that found in North America before the 1980s. Finally, the concentrations of NP and NPEOs were related to the total organic carbon （TOC） （p〈0.001）, suggesting that TOC was an important factor for vertical distribution of NPEOs and NP from the Beipaiming Channel.     

光电催化降解10-壬基酚聚氧乙烯醚

采用溶胶-凝胶法制备TiO₂薄膜光电极,以该电极为工作电极,铂丝作对电极,饱和甘汞电极为参比电极,对10-壬基酚聚氧乙烯醚的光电催化降解进行了研究.结果表明,该电极具有n型半导体的特征行为.在外加偏压为+0.6V,pH值为5,H₂O₂浓度为30mg/L的条件下对初始浓度为50mg/L的10-壬基酚聚氧乙烯醚溶液光照4h,降解率达53.26%.讨论了氧的存在、外加偏压、pH值等因素对光电催化反应的影响.     

烷基酚聚氧乙烯醚类物质的环境雌激素效应

随着环境污染的加剧,环境污染物的雌激素效应成为当前科学研究的一个热点,烷基酚聚氧乙烯醚（APEs）类物质即为具有雌激素效应的环境污染物之一、APEs为一类非离子表面活性剂在工业生产和家庭洗涤中应用广泛,APEs类物质进入环境后可以降解为一些中间代谢物,这些中间代谢物具有环境持久性,很难在环境中进一步降解．研究人员通过3种活体外生物评估法研究发现APEs的中间代谢物具有雌激素活性,可以诱导水体中雄性鱼类等生物的雌性化,同时对哺乳动物和人类健康也具有潜在危害,因此进行更加深入研究,确定APEs类物质对人体的危害,限制APEs的使用已成为当务之急     

1株异养脱氮菌降解壬基酚聚氧乙烯醚的研究

研究了异养脱氮菌Bacillus sp.LY降解壬基酚聚氧乙烯醚(NPEOs)的性能.结果表明,该菌株具有较强地降解NPEOs的能力,且在实现NPEOs降解去除的同时表现出一定的异养脱氮性能.降解14d后, Bacillus sp.LY对NPEOs去除率达95.6%,对体系中的总氮去除率为43.9%.该菌株对NPEOs的降解去除符合一级动力学特征,其降解速率常数为0.224d-1.该菌株通过无氧化过程的乙氧基链的逐渐缩短的途径降解去除NPEOs,可避免产生危害性更大的NPEOs的羧酸化产物(NPECs).在分别以氨态氮(NH4C1)、硝态氮(NaNO3)和亚硝态氮(NaNO2)3种不同氮素为氮源的条件下,菌株对NPEOs均具有一定的降解效果,其中以氨态氮为氮源时菌株对NPEOs降解效果最好.研究结果可为消除壬基酚聚氧乙烯醚与氮素复合污染提供理论依据.     

Biotransformation of nonylphenol ethoxylates during sewage treatment under anaerobic and aerobic conditions

Biotransformation of nonylphenol ethoxylates (NPEOs) during continuous anaerobic sewage treatment was compared with the aerobic treatment of sewage spiked with 23 μmol/L technical NPEOs over a period of 90 d. Immediate degradation of NPEOs was observed under both anaerobic and aerobic conditions, indicating that the enzymes and bacteria required for NPEO degradation existed abundantly in both aerobic and anaerobic sludge. Both treatments achieved high removal (＞92%) of the spiked NPEO9 mixture.Liquid chromatography-mass spectrometry (LC-MS) analysis showed that short-chain NPEOs (NPEO1-NPEO3) accumulated in anaerobic (2.01-2.56 μmol/L) and aerobic (1.62-2.03 μmol/L) effluents, with nonylphenol (NP) (0.24-0.31 μmol/L) as another group of metabolites in the anaerobic effluent, and nonylphenoxy carboxylates (NPECs) (2.79-3.30 μmol/L) in the aerobic effluent. Significant accumulation of NP in the anaerobic sludge and NPEO1-3 in the sludge of two reactors was observed. These results indicated that it was difficult to control these harmful metabolites in the conventional treatment processes. Denaturing gradient gel electrophoresis profiles of sludge samples support the speculation that the NPEO degradation bacteria might be the dominant indigenous species.     

壬基酚聚氧乙烯醚降解前后的激素效应和诱变活性

采用重组基因酵母和SOS/Umu试验研究了壬基酚聚氧乙烯醚(NP₁₀EO)经生物降解前后的雌激素活性和致突变活性.结果表明,在降解反应开始后的4d内降解产物的雌激素活性较低且不具有致突变性.随着降解时间的不断增加,降解产物的雌激素活性和致突变性不断增强.降解20d后,降解产物的雌激素活性相当于1nmol 17-β雌二醇的61.6%,诱变比值大于2,表明壬基酚聚氧乙烯醚的生物降解产物同时具有雌激素活性和致突变活性,且两者在产生时间和活性数值方面均是同步的和成正相关的.因此致突变活性很可能是此类降解产物对生物机体具有雌激素活性的基础.     

Degradation behaviors of nonylphenol ethoxylates by isolated bacteria using improved isolation method

Nonylphenol ethoxylate (NPEO)-degrading bacteria were isolated from activated sludge using an improved isolation method, and the corresponding degradation behaviours were investigated. Eight NPEO-degrading strains distributed in genera Pseudomonas, Sphingomonas, Sphingobium, Cupriavidus, Ralstonia, Achromobacter, and Staphylococcus were acquired. The latter five genera have never been reported for the degradation of NPEOs. Four degradation patterns were observed for the eight pure strains. In pattern A, NPE...     

水中壬基酚聚氧乙烯醚的测定及去除方法研究进展

随着内分泌干扰物的危害不断得到人们的重视,壬基酚聚氧乙烯醚的研究成为了水处理的热点。目前检测水样中壬基酚聚氧乙烯醚的主要方法是采用GC-MS和HPLC,预处理主要采用固相萃取。近年来倍受关注的深度处理工艺如活性炭、树脂吸附法,以及光催化降解和生物降解法能有效的去除水中的壬基酚聚氧乙烯醚。     

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。     

DEP对蚯蚓抗氧化酶系的影响及DNA损伤

邻苯二甲酸二乙酯(DEP)是一种常见的塑料添加剂,并因塑料制品大量广泛使用而进入土壤环境,但其对土壤动物的毒性及其机制并未完全阐明.本文以赤子爱胜蚓(Eisenia foetida)为研究对象,使其暴露于不同含量DEP的模拟污染土壤,以蚯蚓体内的抗氧化酶活性、ROS含量、GST活性、MDA含量和DNA损伤程度为评估参数,研究含DEP污染土壤对蚯蚓的毒性作用并分析其机制.结果表明,在DEP胁迫作用下,蚯蚓体内的抗氧化酶和谷胱甘肽-S-转移酶(GST)活性、活性氧自由基(ROS)均发生变化并导致基因损伤产生.在28d的实验周期内0.1~50 mg·kg-1DEP的胁迫下,ROS含量水平呈现增加状态,存在"剂量-效应"关系,并且过量的ROS引起脂质过氧化反应造成机体内MDA含量增加.在ROS和MDA共同作用下,蚯蚓体腔内的DNA受到损伤并且损伤程度与DEP含量存在"剂量-效应"关系.从实验结果可以看出,DEP可以对蚯蚓机体和DNA造成一定程度的损伤,表现出较强的生态毒理效应.     

Pollution of NPEOs in four municipal sewage treatment plants in the north of China

The concentration and distribution of nonylphenol polyethoxylates (NPEOs represents the mixture, and NPnEO represents the monomer) and its metabolites in the influent and effluent of four municipal sewage treatment plants (STPs) in the north of China were measured. Moreover, the concentration and distribution of the above chemicals in the sludge of two STPs were also determined, and the transfer and fate of NPEOs in the sewage treatment process were discussed primarily by analyzing the distribution of the products in the effluent and the sludge. The results showed that NPEOs and its metabolites existed in all the samples of the influent, effluent, and sludge. NPEOs were degraded in the sewage treatment process with the removal efficiency in the range of 23.38%–77.11%, or an average of 52.86%. However, the large analogs of NPnEO were only degraded to small ones, whose degradation rate was rather slow, and consequently the degradation was not complete. Hence, the concentrations of some small metabolites, such as nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) were elevated in the effluent. These small metabolites are more toxic than the large NPnEO analogs, and some of them were reported to exhibit environmental endocrine disrupting activity. From this point of view, the process of sewage treatment does not reduce but elevate the risk of NPEOs, which becomes the main source of these small NPnEO in the environment. The sludge exhibited good adsorption ability for NPEOs, especially for the small analogs, which led to the high level of NPEOs in the sludge. Hence, reasonable disposal of the surplus sludge to avoid re-pollution is very important. Translated from Research of Environmental Sciences, 2006, 19(3): 61–66 [译自: 环境科学研究]     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

生物毒性测试微孔板MTOXPlate的分析性能研究

采用以11种微生物为指示生物的毒性测试微孔板MTOXPlate,以污染物对微生物细胞的脱氢酶活性抑制为测试终点,对重金属Hg2+、Cd2+、Cr6+、Pb2+,酚类化合物2,4-二氯酚(2,4-DCP)、邻氯苯酚(2-CP)、对氯苯酚(4-CP)、邻硝基酚(2-NP)、对硝基酚(4-NP)及地表水、生活污水、印染废水的生物毒性进行分析.结果表明,MTOXPlate生物毒性测试微孔板具有良好的毒性分析性能,Hg2+、Cd2+、Cr6+和Pb2+的EC50值分别为0.617、21.05、35.21和11.22 mg·L-1,2,4-DCP、2-CP、4-CP、2-NP和4-NP的EC50值分别为27.26、64.29、44.19、85.89和33.84 mg·L-1.MTOXPlate分析得到地表水原水的抑制率均小于20%,生活污水的EC50值为62.19%,印染废水的EC50值为16.42%,表明生物毒性测试微孔板MTOXPlate能真实地反映地表水、生活污水和印染废水的毒性情况.     

The short-chain perfluorinated compounds PFBS, PFHxS, PFBA and PFHxA, disrupt human mesenchymal stem cell self-renewal and adipogenic differentiation

Per- and polyfluorinated alkyl substances (PFASs) are commonly used in industrial processes and daily life products. Because they are persistent, they accumulate in the environment, wildlife and humans. Although many studies have focused on two of the most representative PFASs, PFOS and PFOA, the potential toxicity of short-chain PFASs has not yet been given sufficient attention. We used a battery of assays to evaluate the toxicity of several four-carbon and six-carbon perfluorinated sulfonates and carboxyl acids (PFBS, PFHxS, PFBA and PFHxA), with a human mesenchymal stem cell (hMSC) system. Our results demonstrate significant cyto- and potential developmental toxicity for all the compounds analyzed, with shared but also distinct mechanisms of toxicity. Moreover, the effects of PFBS and PFHxS were stronger than those of PFBA and PFHxA, but occurred at higher doses compared to PFOS or PFOA.     

农田土壤中辛基酚聚氧乙烯醚降解菌的分离

研究针对采自上海孙桥农业园区8个不同来源的农田表层土壤样品(旱田、水田、大棚中的不同作物土壤),以辛基酚聚氧乙烯醚(OPEOn)为唯一碳源培养,在好氧条件下,观察其生物降解情况,并初步分离得到了六株OPEOn降解菌株(1个真菌,5个细菌),它们能够不同程度地降解OPEOn,利用气相色谱仪(GC)对降解产物进行了表征和鉴别,分别从3个土壤样品中分离得到的菌株对OPEOn降解得最为彻底,为后续研究工作的深入奠定了生物学基础。     

基于枯草芽孢杆菌微生物传感器的毒性分析

采用枯草芽孢杆菌(Bacillus subtilis)为指示生物的微生物传感器毒性分析系统,对重金属(Hg2+、Cu2+、Zn2+、Cr6+、Cd2+、Pb2+和Co2+)、有机污染物[邻氯苯酚(2-CP)、2,4-二氯酚(2,4-DCP)、邻硝基酚(2-NP)、对硝基酚(4-NP)、四环素和十二烷基苯磺酸钠]及石油废水等的生物急性毒性进行分析.结果表明,对数生长后期和稳定期的Bacillussubtilis微生物传感器具有良好的毒性分析性能,Cd2+、Zn2+、Cr6+、Cu2+、Hg2+、Pb2+对Bacillus subtilis的EC50分别为47.3,10.9,14.0,2.6,0.8,100.1mg/L,Co2+的EC30为56.6mg/L,2-CP、2,4-DCP、2-NP、4-NP、四环素和十二烷基苯磺酸钠的EC50分别为559.6,450.8,588.5,487.0,121.3,558.9mg/L,该微生物传感器能真实反映石油废水的毒性情况.     

Molecular toxicity and defense mechanisms induced by silver nanoparticles in Drosophila melanogaster

The widely use of silver nanoparticles (AgNPs) as antimicrobial agents gives rise to potential environmental risks. AgNPs exposure have been reported to cause toxicity in animals. Nevertheless, the known mechanisms of AgNPs toxicity are still limited. In this study, we systematically investigated the toxicity of AgNPs exposure using Drosophila melanogaster. We show here that AgNPs significantly decreased Drosophila fecundity, the third-instar larvae weight and rates of pupation and eclosion in a dose-dependent manner. AgNPs reduced fat body cell viability in MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays. AgNPs caused DNA damage in hemocytes and S2 cells. Interestingly, the mRNA levels of the entire metallothionein gene family were increased under AgNPs exposure as determined by RNA-seq analysis and validated by qRT-PCR, indicating that Drosophila responded to the metal toxicity of AgNPs by producing metallothioneins for detoxification. These findings provide a better understanding of the mechanisms of AgNPs toxicity and may provide clues to effect on other organisms, including humans.     

Seasonal variations in the concentration and removal of nonylphenol ethoxylates from the wastewater of a sewage treatment plant

In this study, we investigated the occurrence and fate of nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) in a full scale sewage treatment plant, which applied an Anaerobic/Oxic process. Concentrations of NP, NP1EO and NP2EO in the wastewater were measured during the period spanning a whole year. The results showed remarkable seasonal variation in the concentrations of the compounds. The NPnEO compounds were most abundant in winter, with the total concentrations of influent NP, NP1EO and NP2EO ranging from 3900 to 7000 ng/L, 4000 to 4800 ng/L and 5200 to 7200 ng/L, respectively. Regarding the total removal efficiencies of the three types of short-chain NPnEO compounds, different trends were exhibited according to different seasons. The average removal efficiency of NP for the different seasons ranked as follows: winter > summer > autumn > spring; NP2EO concentrations decreased as follows: summer > autumn > winter > spring, while NP1EO concentrations reduced according to: spring > summer > autumn > winter. We also investigated the contribution ratio of individual treatment units in the A/O process, with the findings suggesting that the anaerobic treatment unit plays an important role in the elimination of short-chain NPnEOs from the wastewater.     

全氟辛酸对酿酒酵母细胞毒性作用

全氟辛酸(PFOA)广泛应用于工业生产中,具有高度的生物毒性及生物蓄积性,然而PFOA对环境微生物的毒性影响仍有待深入开展.通过流式细胞术测定了酵母菌在不同浓度PFOA胁迫下细胞膜通透性、ROS、线粒体跨膜电位的变化,并且测定了MDA含量和Na+K+-ATPase、Ca2+Mg2+-ATPase活性变化.结果显示PFOA可使PI染色细胞比例增高,酿酒酵母细胞膜通透性增大、ROS和MDA含量升高、线粒体跨膜电位降低,且ROS含量、MDA含量与线粒体跨膜电位降幅均与PFOA胁迫浓度和时间呈正相关.Na+K+-ATPase、Ca2+Mg2+-ATPase活性先上升后降低,表明酿酒酵母在PFOA胁迫下,其生理活性受到抑制甚至发生细胞凋亡.证明PFOA对酿酒酵母具有生物毒性,100 mg·L-1PFOA对酿酒酵母具有即时毒性.该结果可为PFOA的影响评价提供更多依据.     

PM2.5暴露对小鼠肝脏能量代谢的影响

通过细颗粒物(particulate matter 2.5,PM_(2.5))的暴露,探讨其对小鼠肝脏能量代谢方式的影响及作用机制.采用透射电镜(TEM)观察肝脏组织中线粒体超微结构的改变,并检测了三磷酸腺苷(ATP)、丙酮酸和乳酸含量的变化,同时用实时荧光定量-聚合酶链式反应(RT-PCR)检测糖酵解相关基因果糖-2,6-二磷酸酶(PFKFB3)和乳酸脱氢酶(LDHB)及三羧酸循环(TCA)相关基因丙酮酸脱氢酶(PDHA1)、柠檬酸合成酶(CS)和延胡索酸酶(FH)的表达情况.此外,还对活性氧(ROS)的水平进行检测.结果表明,PM_(2.5)暴露对小鼠肝脏组织中的线粒体造成损伤,导致ATP的下降,丙酮酸和乳酸的积累.此外,PDHA1、CS和FH的表达明显降低,PFKFB3和LDHB的表达显著升高,这些结果共同表明PM_(2.5)改变了小鼠肝脏的能量代谢方式.同时ROS水平明显升高,表明PM_(2.5)暴露可能是通过ROS抑制三羧酸循环,增强糖酵解方式来为机体提供能量,从而对肝脏的能量代谢产生影响.