天津野生鲫鱼体内壬基酚聚氧乙烯醚和壬基酚监测

采用GCB固相萃取作为净化方法 ,利用LC ESI MS技术测定鱼体内不同聚合度壬基酚聚氧乙烯醚 (NPnEO ,n≥ 3) ;用GC MS技术测定NP和NPnEO(n <3) .此方法与传统的氧化铝法相比较 ,GCB固相萃取作为净化方法的回收率较高 ,不同聚合度的NPnEO回收率为 70 4 %— 12 0 % ;方法检测限为 1ng g.用此方法调查了北京排污河中鲫鱼体内的NPnEO的残留情况 ,在所捕获的 12条鲫鱼中均检出了不同浓度的NPnEO和NP .NPnEO在北京排污河天津段鱼体内的残留浓度为 4 0— 6 80ng g ,NP的浓度在 30— 15 10ng g ,和水体中浓度之间的比值分别为 898和 94倍 .     

壬基酚和短链壬基酚聚氧乙烯醚在土壤中的降解研究

研究了壬基酚(NP)类内分泌干扰物在土壤体系和添加污水处理厂剩余污泥的土壤体系中的降解行为.结果表明,NP、壬基酚单氧乙烯醚(NPEO1)、壬基酚二氧乙烯醚(NPEO2)在土壤中的降解遵循一级动力学方程,其降解速率随温度升高而升高.30℃时,初始浓度分别为100、50和100 mg·kg-1的NP、NPEO1和NPEO2可在45 d内完全降解.相同条件下,土壤中NP的降解速率大于NPEO1和NPEO2.体系中添加污泥促进了NPEO1和NPEO2的降解,同时抑制了NP的降解.     

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.     

壬基酚聚氧乙烯醚对成年雄性斑马鱼HPG轴相关基因表达的影响

本研究以模式动物斑马鱼（Danio rerio）为受试生物,采用半静态水体暴露的方式研究了不同浓度壬基酚聚氧乙烯醚（NPEO）对斑马鱼雄性成鱼下丘脑-垂体-性腺轴（HPG轴）的影响.结果显示,考察浓度范围内的NPEO暴露可以显著上调斑马鱼脑中GnRH2、GnRHR1、GnRHR2、GnRHR4、FSHβ和LHβ基因,以及性腺中LHR基因的相对表达量.GnRHR和LHR基因表达量对较低浓度NPEO暴露较为敏感,其中GnRHR4和LHR基因表达量在低至0.001mg/L的NPEO暴露下即出现显著上调.0.1和10mg/L NPEO暴露可以显著抑制斑马鱼精巢中CYP17基因的表达量,而10mg/L NPEO暴露则可以显著诱导CYP19a基因的表达量.GnRH相关调控基因表达量的上调,表明NPEO暴露可以诱导下丘脑分泌GnRH,进而刺激垂体分泌GtH.NPEO暴露诱导CYP19a基因的表达,促进了内源雌激素的合成.同时,NPEO通过抑制CYP17表达,可能抑制睾酮（T）的合成,干扰斑马鱼精巢中原有的性激素平衡.斑马鱼精巢内雌激素水平升高负反馈给垂体,刺激垂体分泌促性腺激素.由此表明,考察浓度范围内（0.001~10mg/L）的NPEO的暴露可以影响雄性斑马鱼成鱼HPG轴的反馈调节.     

壬基酚聚氧乙烯醚在MBR 与CASR 中的行为

对比研究了壬基酚聚氧乙烯醚(NPnEO, n 为1~4)在膜-生物反应器(MBR)和传统活性污泥反应器(CASR)中的去除效果和迁移行为.结果表明,在相同NPnEO 污泥负荷的条件下,采用不主动排泥的运行模式,2 种反应器均能有效去除NPnEO,去除率分别为99.2%和97.1%,MBR 的去除效果更稳定.前21d 中,2 种反应器中混合液NPnEO 浓度均呈现先增大后减小的趋势,但MBR 出水NPnEO 浓度小于其混合液浓度,而CASR 出水浓度则高于其混合液浓度;21d 后,2 种反应器混合液与出水浓度均趋于一致.活性污泥对NPnEO 具有吸附作用,但对去除NPnEO 的贡献很小;推测生物降解是去除NPnEO 的主导作用.     

壬基酚聚氧乙烯醚在碱性印染废水中的降解

通过静态和动态连续降解实验,揭示了壬基酚聚氧乙烯醚(NPEO,Nonylphenol ethoxylates,浓度6.25~12.5 mg·L-1)在碱性牛仔布印染废水中的去除规律.批式活性污泥实验表明,厌氧环境下,随着p H值的增加,壬基酚(NP,Nonylphenol)产生受到抑制,短链NPEO(环氧乙烯加成数1~3,NP(1~3)EO)总浓度水平虽然只有500~900μg·L-1,却呈现增加趋势;好氧环境下,尽管NPEO总量降解率超过85%,但产生的各种短链NP(1~3)EO和短链壬基酚聚氧乙烯醚酸酯(NPEC,Nonylphenol polyethoxycarboxylate)浓度区间为10~110μg·L-1,碱性环境下两类物质总量最低,不足100μg·L-1.耦合厌氧水解和好氧曝气的连续实验表明,增设填料的厌氧折板水解池出水中短链NP(1~3)EO的总浓度增至4000~5000μg·L-1,这与厌氧环境下一部分NPEO附着在废水杂质和厌氧污泥上,在污泥龄较长的附着型污泥作用下,生成了大量的NP(1~3)EO有关;好氧段出水中NP(1~3)EO浓度降至230~610μg·L-1,短链NPEC(NP(1~3)EC)总量上升到800~1000μg·L-1,NP(1~3)EC由NP(1~3)EO转化来的可能最大.印染出水中NP及NP(1~3)EO受厌氧段出水中NP及NP(1~3)EO浓度影响明显.     

浅析重金属在氧化沟式污水处理工艺中的迁移转化

目前重金属污染事故已经成为我国重点关注的民生污染问题,被国家列为优先解决的环境污染问题,针对重金属污染的整治力度势必也是前所未有的。本文就常用的氧化沟式污水处理工艺分析重金属在其中的迁移转化现象,为该工艺处理含有重金属污染的污水提出一些指导意见。     

环境中氮化物迁移转化过程研究进展

本文对近年来国内外有关氮化物迁移转化过程研究取得的新成果作了较为全面的叙述，包括氮化物在不同的生态系统中的硝化和反硝化的规律，转化的动力学以及数学以得的研究成果。     

影响有机污染物在土壤中的迁移,转化行为的因素

本文介绍了有机污染物在土壤中的吸附与解吸附，渗 滤，挥发和降解等行为过程。探讨了吸附与解吸附机理，土壤有机质含量和类型，水分含量及温度对此过程的影响。依据某些典型的化合物行为模型，论述了影响土壤中有机污染物渗滤的因素。有机污染物需要先从土壤深层迁移至地表，然后挥发至大气，在土壤中迁移的速率较慢，控制着整个挥发过程，可用Ｆｉｃｋ第二定律来描述。     

重庆流域嘉陵江和长江水环境中壬基酚污染状况调查

利用固相萃取（SPE）－气相色谱－质谱法（GC－MS）对嘉陵江和长江重庆段河流和以这两条河流为水源的5个自来水厂水样中壬基粉（NP）进行了检测,河流水样中4月份NP的浓度范围为0.02-1.12μg/L，7月份为1．55－6.85μg/L，自来水厂的水样中，4月份NP浓度范围为＜0．01－0．06μg/L,7月份为.10-2.73μg/L，方法的自来水加标回收率大于90％，环境水样中的加标回收率大于80％，检测限为0.01μg/L.     

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.     

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.     

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.     

珠三角城市污泥中壬基酚及重金属特征分析

对珠三角地区典型城市的13家污水处理厂剩余污泥中壬基酚(Nonylphenol,NP)、部分重金属及养分含量进行了检测和分析.结果表明,珠三角地区典型城市13家污水处理厂污泥中NP范围在0.45~65.17 mg·kg~(-1)(以干重计,下同)之间,平均值为10.87 mg·kg~(-1),工业废水是影响污水处理厂污泥中NP含量的一个重要因素,该地区污泥中NP含量相比于世界其他地区较低,但其中有2家污水处理厂污泥中NP含量超过或接近2000年欧盟污泥指令文件对污泥中NP、NP1EO、NP2EO(NPE)总量限制值(50 mg·kg~(-1)).13家污水处理厂污泥样中Cu、Pb、Cd及Zn含量的几何平均值分别为435.43、78.88、2.72、1088.01 mg·kg~(-1),与《城镇污水处理厂污染物排放标准》(GB18918—2002)中施用土壤(p H6.5)限值进行比较,仍有部分污水处理厂污泥中Cu、Cd、Zn含量超标.13家污水处理厂污泥样中有机质、总氮、总磷及总钾的算术平均值分别为294.40、12.92、39.63、9.12 g·kg~(-1),与过去的研究相比,污泥中有机质与养分含量总体呈上升趋势.相关性分析的结果表明,13家污水处理厂污泥样中NP含量与污泥中总Cu的含量具有显著的正相关关系.     

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]     

Comparative toxicity study of a novel non-ionic surfactant, vanillin ethoxylates, and nonylphenol ethoxylates in Chinese hamster ovary cells in vitro

Surfactants such as alkylphenol polyethoxylates (APEOs) and nonylphenol ethoxylates (NPEOs) are commonly used worldwide, but the majority of these compounds, together with their metabolites, have been reported to induce severe biological toxicity. Here, we evaluated for the first time the cytotoxicity, genotoxicity and mitochondrial damage in Chinese hamster ovary (CHO-K1) cells caused by a novel non-ionic surfactant, vanillin ethoxylates (VAEOs), an alternative to APEOs. In parallel, the same in vitro bioassays were conducted on NPEOs along with their metabolic byproducts 4-nonylphenol (4-NP) and vanillin. The results showed that the cytotoxic potency order was NPEOs?>?4-NP?>?VAEOs > vanillin using CCK-8 assays. Also, 4-NP showed potential direct DNA damage in SOS/umu tests, whereas NPEOs, VAEOs and vanillin showed no positive result with and without S9 addition. In addition, none of the test compounds showed obvious genotoxic effects with low olive tail moment value using comet assays. However, all test compounds were shown to cause mitochondrial impairment by increasing mitochondrial mass and decreasing mitochondrial membrane potential in a concentration-dependent manner. And further analysis of reactive oxygen species (ROS) and mitochondrial superoxide (MNSOD) measurement showed that mitochondrial impairment was induced by oxidative stress with intracellular ROS and MNSOD overproduction. It's worth noting that VAEOs and vanillin cause relative lower cytotoxic, genotoxic and mitochondrial damage effects than NPEOs and 4-NP, indicating that VAEOs have the potential to substitute NPEOs as suitable surfactants. Take together, this study elucidates the toxicity profiles of VAEOs and NPEOs relatively comprehensively, and further toxicity analyses are suggested in the population, community and ecosystem.     

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.