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.     

壬基酚在活性污泥系统中的去除研究进展

壬基酚是一种持久性有毒的内分泌干扰物,它会对生物系统产生有害影响。本文介绍了壬基酚的来源、物化性质、化学结构、城市污水处理厂和实验系统中的迁移转化及去除,以及壬基酚在活性污泥分离的菌种中的降解。最后分析了目前研究中存在的问题并提出了相应的解决方法。     

Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

大孔吸附树脂对烷基酚聚氧乙烯醚的吸附行为

烷基酚聚氧乙烯醚(APEOn)是一类重要的非离子表面活性剂,由于其生物代谢产物被证实具有较大的毒性,因此引起人们广泛关注.本文使用两种不同的大孔吸附树脂XAD-4、NDA-804对APEOn类物质NP10进行吸附,该技术可为使用大孔吸附树脂去除此类污染物提供理论依据.研究结果表明:XAD-4、NDA-804对NP10都有较好的吸附效果,温度对吸附有较大的影响,升高温度吸附量增大.NDA-804对NP10的吸附效果要好于XAD-4,这与它的化学特性以及孔结构有关.NP1O在两种树脂上的吸附都能用Langmuir吸附等温线方程很好的拟合,表明属于单层分子吸附.吸附热力学参数计算结果表明,XAD-4、NDA-804对NP10的吸附过程是吸热和自发的.吸附动力学拟合结果表明,NP10在XAD-4、NDA-804上的吸附都符合假二级反应动力学.     

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.     

壬基酚与壬基酚聚氧乙烯醚对多刺裸腹溞的复合毒性效应

为了探讨壬基酚聚氧乙烯醚（NP10EO）与其降解产物壬基酚（NP）对多刺裸腹溞的复合毒性效应,在实验室条件下研究了NP和NP10EO单一暴露对多刺裸腹溞的急性毒性和亚慢性毒性,以及两者混合暴露对多刺裸腹溞的联合毒性效应。结果表明：NP和NP10EO两种物质单一暴露对多刺裸腹溞的24 h LC50分别为0.154和3.37 mg.L-1,48 h LC50分别为0.065和2.11 mg.L-1。联合毒性实验中,定义0.5×LC50（NP）＋0.5×LC50（NP10EO）为一个毒性单位（1TU）。NP和NP10EO混合暴露后对多刺裸腹溞的24 h和48 h的LC50分别是0.646TU和0.291TU,联合毒性强度明显高于两种物质单一暴露时的毒性强度。在持续混合暴露条件下,多刺裸腹溞的首次生殖时间延迟、母体体长和初生幼体体长严重缩短、首次生殖数量大幅减少。说明NP和NP10EO对多刺裸腹溞的复合毒性表现出明显的协同效应。     

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。     

Occurrence of endocrine disruptor compounds in the estuary of the Iberian Douro River and nearby Porto Coast (NW Portugal)

Previous studies in the Douro River estuary, based on occasional sampling, showed the presence of several estrogenic disrupting chemicals (EDCs). In sequence, we hypothesized that such type of pollution was more likely an enduring issue than an occasional phenomenon, and that it may even affect recreational beaches in each side of the estuarine mouth. Thus to conclude about the continuous influx of EDCs, water samples were taken twice a day, once per a week, from March to May of 2009, at four sites within the estuary and at two sites in the coastline. After solid-phase extraction, the extracts were prepared for GC-MS analysis of 11 reference EDCs. These embraced natural and pharmaceutical estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A). Data showed the ubiquitous presence of potentially hazardous amounts of natural estrogens (particularly of estradiol, ca 5.5?ng?L^?1) and persistent organic pollutants such as nonylphenol mono (up to 550?ng?L^?1) and diethoxylate (up to 2000?ng?L^?1). It was concluded that the targeted area is continuously polluted by the assayed EDCs, and as a consequence, conditions exist for endocrine disturbance in the biota by chronic exposure to EDCs.     

Effects of nonylphenol on the brain cytochrome P450 gene expression in F1 generation rats

In order to explore the effects of nonylphenol (NP) on brain cytochrome P450 gene expression in F1 generation rats microarray analysis techniques were used. mRNA were extracted from the brain of 2-day-old F1 generation rats whose F0 male generation were treated with NP, then reversely transcribed to cDNA and labeled with cy5 and cy3 for fluorescence. Subsequently, the cDNA probes were hybridized to the mouse 40S cDNA microarray; and fluorescent signals produced by cy5 and cy3 were scanned and analyzed. Sixteen identified genes were found to be expressed differently from control, including three cytochrome P450 genes, in which two were up-regulated and one down-regulated. Data suggest that NP affects the expression of some cytochrome P450 genes in rat brain when administered perinatally.     

烷基酚和烷基酚聚氧乙烯醚的环境行为

烷基酚聚氧乙烯醚(APEOs)是一种广泛使用的表面活性剂,在污水处理厂和环境中降解为持久性更强,毒性更大的烷基酚(A^)--辛基酚(OP)及壬基酚(NP),以及短链的NPEO1、NPEO2和NPEO3.这些代谢物中的有些有类环境激素性质,目前环境中存在的浓度已经达到扰乱野生生物和人类内分泌功能的剂量.本文对APEOs和APs在环境各介质中的行为进行综述,列出了该类物质在大气、室内空气、地表水和水底沉积物中、污水处理厂的出水、剩余污泥中,以及土壤等环境各相中的浓度阈分布,同时也分析了其在环境中的迁移转化和归趋,旨在为今后的研究提供有效的依据.