环境浓度下壬基酚对秀丽隐杆线虫时间依赖性的毒性兴奋效应

为研究暴露时间对壬基酚生态毒理学效应的影响,选取秀丽隐杆线虫(Caenorhabditis elegans)作为受试生物,采用急性(24 h和72 h)、慢性(10 d) 3个不同时间点,进行壬基酚环境浓度下(0、0.0001、0.001、0.01、0.1、0.2 mg·L~(-1))的暴露实验,以秀丽隐杆线虫的生理指标(体长、运动行为)、生化指标(氧化应激、细胞凋亡、脂褐素)为终点进行评估。结果表明:急性暴露24 h后,活性氧自由基(ROS)在0.01 mg·L~(-1)时即出现了明显的下降,其他生理生化指标无统计学意义上的明显变化。72 h暴露条件下,体长随壬基酚浓度的增加呈现倒U型趋势,在0.0001 mg·L-1时表现出最大刺激效应,比对照组高出26.4%(P0.01);头部摆动频率和身体弯曲频率在2个较高浓度(0.1和0.2 mg·L~(-1))时表现出明显的刺激效应;细胞凋亡水平在0.0001 mg·L~(-1)时显著性下降,呈现负剂量-效应关系(P0.05),在0.2 mg·L~(-1)时表现出最大刺激效应,比对照组降低了45.5%; ROS及脂褐素在壬基酚暴露浓度范围内呈正相关性增加。慢性暴露条件下,脂褐素在0.001 mg·L~(-1)时表现出最大效应,和对照组相比下降了65.4%,并且随着壬基酚浓度的增加呈现U型趋势;其他生理生化指标随着壬基酚浓度的增加表现出明显的负面效应。研究揭示了环境浓度水平的壬基酚对秀丽隐杆线虫的生态毒理效应是时间依赖性的,急性暴露以引起刺激作用为主,表现为毒性兴奋效应,而长期暴露后壬基酚对生理生化指标的负面效应更为明显。上述结果为进行壬基酚的毒性评价及更好地理解其毒性作用机理提供基础数据。     

TiO2悬浮体系光催化降解壬基酚的研究

研究了以悬浮态TiO2为催化剂,在H2O2存在的条件下,壬基酚的光催化降解反应.分别研究了pH值、TiO2和H2O2的加入量、壬基酚的初始质量浓度以及光照时间对降解反应的影响.结果表明:在pH=5,30 mg/L的H2O2中,初始质量浓度为20 mg/L壬基酚的溶液光照180min后,降解率达54.42%.     

壬基酚对中国林蛙精巢中StAR表达的影响

为研究水体壬基酚(Nonylphenol,NP)污染对两栖动物精巢中类固醇生成急性调节蛋白(StAR)的影响,将雄性成体中国林蛙(Rana chensinensis)分别暴露于c(NP)为10-7,10-6和10-5 mol/L的水体中10,20和30 d.取其精巢组织,在成功扩增获得273 bp的StAR cDNA片段后合成探针,用原位杂交方法检测StAR mRNA在精巢的表达,用免疫组织化学方法检测StAR蛋白的表达.结果在对照组和各NP处理组中均检测到StAR mRNA和蛋白的阳性表达,阳性反应主要在精巢的Leydig细胞.StAR表达相对值的检测结果表明,c(NP)为10-5 mol/L 的水体对StAR表达有抑制趋势,c(NP)为10-7和10-6 mol/L 的水体可上调StAR的表达,表明NP对StAR表达由抑制转向诱导的临界浓度在c(NP)为10-6 mol/L与10-5 mol/L 之间.在c(NP)为10-7和10-6 mol/L 处理组,StAR表达值随c(NP)的增高而增加.在c(NP)为10-6 mol/L 处理组,暴露30 d后StAR表达相对值最大,呈现NP对StAR表达具有累积效应.c(NP)为10-7 mol/L对StAR表达不随时间延长显示累积效应.提示一定剂量范围的NP可通过调控StAR的表达干扰动物类固醇激素的合成.      

太原小店污灌区土壤壬基酚的分布特征

本研究以内分泌干扰物壬基酚(NP)为例,研究了太原小店污灌区土壤NP的污染浓度水平及空间分布特征.结果表明,NP在研究区污灌土壤中普遍存在,含量高低顺序为:污灌区>过渡区>清灌区;总体上离灌渠越远,土壤中NP含量越低;NP含量与土壤有机质(TOC)呈正相关,与土壤pH值呈负相关;在垂直钻孔沉积物中,随土壤深度增加,NP含量逐渐减小,但在一定深度会出现NP的富集层,富集层深度受土壤理化性质的影响,间接反映了该区域的污灌历史及NP的下渗迁移能力.     

胺基树脂吸附去除水中的壬基酚聚氧乙烯醚

使用氯球作为前驱体与二乙烯三胺在回流条件下反应合成一种胺基树脂,对胺基树脂的特征进行了表征,并研究了胺基树脂对水中的壬基酚聚氧乙烯醚(NP₁₀EO)的吸附行为.树脂的红外、元素分析及比表面积与平均孔径分析结果表明,胺基官能团成功地嫁接到树脂表面,胺基浓度为5.6 mmol/g,且胺基树脂的比表面积较氯球有较大增加.胺基树脂对NP₁₀EO的吸附等温线表明,温度的升高有利于吸附,在35 ℃下胺基树脂对NP₁₀EO的最高平衡吸附量达58.36 mg/g.采用Langmuir方程和Freundlich方程用于吸附等温线的解释,结果表明,吸附等温线更加符合Langmuir模型,相关系数(R2)均大于0.98. NP₁₀EO在胺基树脂上的吸附符合准二级动力学方程,初始ρ(NP_10EO)越低达到吸附平衡所需时间越短,初始ρ(NP_10EO)为9.41 mg/L的溶液能在2 h内达到吸附平衡.      

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.     

Distribution patterns of octylphenol and nonylphenol in the aquatic system at Mai Po Marshes Nature Reserve, a subtropical estuarine wetland in Hong Kong

Spatial and temporal distribution of octylphenol （OP） and nonylphenol （NP） in Mai Po Marshes, a subtropical estuarine wetland in Hong Kong, were investigated. Surface water samples were collected every month from 11 sites during the period of September- December 2004. Concentrations of OP and NP ranged from 11.3 to 348 ng/L and from 29 to 2591 ng/L, respectively. The high levels of NP and OP were found in November and December than in September and October. The levels of OP and NP have no significant spatial differences except September. Total organic matter in the sediments appeared to be an important factor in controlling the fate of these compounds in the aquatic environment.     

壬基酚聚氧乙烯醚在水溶液中的光降解行为研究

采用模拟日光灯和长波紫外灯（UVA-365nm）2种光源,对水溶液中壬基酚聚氧乙烯醚（NPEOs）的光降解动力学、降解过程中NPEO同系物成分的变化、以及氧化剂过氧化氢的加入对光降解的影响进行了研究,并采用LC-MS对光降解的产物进行了分析.研究表明,实验周期内NPEOs在模拟日光和长波紫外光下均发生不同程度的光降解,降解速率常数分别为6.20×10^-3　μmol/(L·h)和1.18×10^-2　μmol/(L·h).在模拟日光下,在NPEOs降解过程中观察到短链的NPEO_1,3分布比例的增加,而在长波紫外光下的降解过程中并没有发现NPEO成分分布的变化.过氧化氢的加入对NPEOs的光降解具有明显的促进作用,特别是在模拟日光下,0.01 mmol/L和1.00 mmol/L H₂O₂的加入使NPEOs的96h降解率由20.9%分别提高至44.4%和91.5%.通过LC-MS分析,初步认为壬基酚三乙氧基乙酸的烷基氧化产物(CA_3～9PEC₃)是溶液中NPEOs光降解的主要产物,并据此推断了可能的反应历程.     

Synthesis of branched para-nonylphenol isomers: occurrence and quantification in two commercial mixtures

Eight tertiary nonanols were synthesized via Grignard reaction and coupled by Friedel–Crafts alkylation with phenol to the corresponding nonylphenols. Six branched para-nonylphenols (NP) were obtained: 4-(3′-methyl-3′-octyl)phenol (33NP), 4-(2′-methyl-2′-octyl)phenol (22NP), 4-(2′,5′-dimethyl-2′-heptyl)phenol (252NP), 4-(2′,5′,5′-trimethyl-2′-hexyl)phenol (2552NP), 4-(2′,4′-dimethyl-2′-heptyl)phenol (242NP) and 4-(4′-ethyl-2′-methyl-2′-hexyl)phenol (4E22NP). Their structures were confirmed by GC–MS and NMR spectroscopy. These six isomers as well as the earlier synthesized 4-(3′,5′-dimethyl-3′-heptyl)phenol (353NP), 4-(3′,6′-dimethyl-3′-heptyl)phenol (363NP) and 4-(2′,6′-dimethyl-2′-heptyl)phenol (262NP) were compared with commercial NP mixtures purchased from Acros and Fluka by GC–MS (equipped with a 100 m polysiloxane column). The analyses revealed that all obtained isomers are occurring in different quantities in both commercial NP mixtures.     

1株壬基酚降解菌的分离鉴定及其降解特性研究

从给水处理系统长期运行的颗粒活性炭上分离到1株可以以壬基酚(NP)为唯一碳源生长的好氧细菌F-10,利用Sherlock微生物鉴定系统(MIS)分析,初步鉴定为红球菌属中的红串红球菌.通过摇瓶实验考察了温度、pH、NP初始浓度、细菌投量、金属离子等因素对F-10降解NP性能的影响,得出最佳降解条件是温度30℃,pH值6.0,在该条件下,2%菌投量对1 mg/L NP去除率达到了62%,且降解过程满足一级动力学模型,速率常数(k)为0.086 5 d-1,半衰期(t1/2)为8.0 d;此外,菌的降解速率与NP的初始浓度关系不大,而与菌量呈正相关;增加溶液中NH4、Mn2 、Mg2 、NaCl浓度或加入葡萄糖、醋酸钠和酵母膏等底物对菌降解NP均有促进作用;而Ca2 、Cu2 、Fe2 和磷酸盐的作用则相反;同时混合菌体系的降解性能要优于纯菌.