固相萃取法分离富集污水样品中痕量壬基酚

本文结合气相色谱质谱选择离子(GCMS∑SIM)定量分析壬基酚含量,对固相萃取技术提取富集污水和再生水样品中痕量壬基酚的操作条件和参数进行了研究。研究结果表明,OasisRHLB固相萃取柱对壬基酚具有优良吸附保留性能,多级混合洗脱方式的洗脱效率达97.01%;测定结果准确度和精密度满足要求。     

高效液相色谱法检测土壤中的壬基酚

建立一种土壤中壬基酚的提取和含量测定方法。土壤样品经二氯甲烷索氏提取、旋转蒸发仪浓缩蒸干后,用色谱流动相溶解。以色谱甲醇与高纯水（体积比为85：15）为流动相,经C18色谱柱分离,在检测波长277nm进行紫外光检测。土壤样品中4-壬基酚的捡出限为20ng／g,4-壬基酚混合标准检测相对标准偏差范围在2．39％-4．56％之间。加入标准溶液后,土壤中壬基酚的加标回收率为98．73％～101．78％,标准偏差小于2．97％。该方法简便快速,灵敏可靠,适用于土壤样品中环境类激素4-壬基酚的含量检测。     

固相萃取-超高效液相色谱串联质谱法测定城市污水中5种β-受体阻断剂

β-受体阻断剂是一类常用的心血管疾病治疗药物. 建立了城市污水中索他洛尔、普萘洛尔、卡维地洛、奈比洛尔和纳多洛尔5种β-受体阻断剂的超高效液相色谱-串联质谱联用检测方法. 水样经MCX固相萃取小柱富集、净化,采用0.1%甲酸水溶液与乙腈为流动相进行梯度洗脱,经BEH C18色谱柱分离,通过多反应监测模式进行测定. 该方法对5种β-受体阻断剂的线性范围为0.1～100.0 μg/L,相关系数(R2)均大于0.99. 污水中索他洛尔、普萘洛尔、卡维地洛、奈比洛尔和纳多洛尔的定量限为0.2～2.0 ng/L,加标回收率为54.1%～113.4%,相对标准偏差小于22%,可用于城市污水中相关物质的分析测定.      

水中壬基酚的去除研究进展

壬基酚是环境内分泌干扰物质中具有代表性的物质,非离子表面活性剂壬基酚聚氧乙烯醚在环境中的降解产物,对生物体造成很大危害。目前检测水样中壬基酚的主要方法是采用GC—MS和HPLC,预处理主要采用固相萃取和液一液萃取。研究表明自来水厂的常规处理工艺对于水中壬基酚的去除有限;近年来倍受关注的深度处理工艺如活性炭吸附等物理方法...     

北京市再生水与地表水中的内分泌干扰物分析

文章以北京己投入运行的再生水厂及北京地区典型地表水为研究对象,利用液相色谱-质谱分析相结合的方法对环境内分泌干扰物壬基酚、双酚A和雌醇类物质进行调查,结果显示,再生水中所含内分泌干扰物与地表水没有明显差异。壬基酚在再生水和地表水中都有检出,其浓度在30~300 ng/L之间,而双酚A除方庄和吴家村再生水厂外,其余各水样均有检出,其浓度在0~30 ng/L之间。各水样中均有雌醇类物质检出,但含量极低。再生水处理工艺对内分泌干扰物浓度水平影响很大。     

海洋生物组织中酚类内分泌干扰物分析方法的建立与应用

应用高效液相色谱-串联质谱(LC-MS/MS)建立了同时测定生物体中壬基酚、辛基酚、双酚A、对特辛基苯酚、2,4-二氯酚和对叔丁基苯酚6种酚类内分泌干扰物的分析方法。以CH2Cl2作为萃取剂,采用加速溶剂萃取和氨基固相萃取柱对样品进行提取和净化。LC-MS/MS分析选用Waters Symmetry-C18色谱柱,以CH3OH和0.2%NH3·H2O溶液为流动相,进行梯度洗脱,在电喷雾电离负离子模式下,采用选择性反应监测模式进行检测。实验结果表明,6种酚类内分泌干扰物的回收率在67.0%~89.0%,相对标准偏差在4.3%~8.5%,方法检出限为(1.0~1.2)×10-9。5种生物样品检测结果表明:6种酚类内分泌干扰物在各种生物体中检出率较高,含量在ND(未检出)~384×10-9。方法验证和实际样品分析表明该方法具有灵敏度高,准确度和精密度好的优点,适用于海洋生物组织中酚类内分泌干扰物的分析。     

污水处理流程中几种典型酚类化合物的分布

研究了辛基酚、壬基酚和双酚A等典型酚类雌激素在污水处理流程中的分布.采集于天津某污水处理厂的7个污水样品中的辛基酚、壬基酚和双酚A用二氯甲烷液液萃取,经三氟乙酸酐衍生后进行GC MS SIM定量检测.结果表明,污水样品中辛基酚、壬基酚和双酚A的浓度分别在44 3～110 7,260 5～1657 5和28 6～506 0ng·L-1之间.在污水处理流程中,污染物主要产生于厌氧消化处理过程中,以壬基酚为主要产物.     

固相萃取-气相色谱法快速分析水中硝基苯类化合物

建立了固相萃取-气相色谱定量分析水中硝基苯类化合物的分析方法,详尽地叙述了水样预处理过程.对固相萃取,水样预处理和色谱分离条件做了试验并予以优化.采用ODS-C18固相萃取柱将样品浓缩富集后,以DB-17色谱柱(30 m×0.32 mm×0.25 μm)为分离柱,以ECD和FID检测.方法检出限在0.12～90 μg/...     

气相色谱-质谱法分析饮用水源水中甲基汞

采用自动固相萃取-气质联用法分析饮用水源中的甲基汞,通过巯基棉小柱萃取大体积(5L)水样后,选择离子扫描方式(SIM)进行定量。实验对比国家标准方法具有更好的线性关系,实际操作简单快捷,灵敏度高。3个浓度水平进行加标回收实验,回收率分别大于71.0%、74.4%、76.0%。对10μg/L浓度重复进样6次,相对标准偏差(RSD)为4.8%。该方法检出限可达到3×10-4μg/L,满足饮用水源水中甲基汞标准限值要求。     

固相微萃取-气质联用法测定水中痕量土臭素和二甲基异崁醇

采用固相微萃-气相色谱/质谱法(SPME-GC/MS)对GSM和2-MIB进行富集检测。实验对萃取富集和仪器条件进行了优化,得出最佳实验条件：NaCl投加量30%,萃取温度65℃,萃取时间40 min,解吸3 min,不分流进样,SIM模式采集数据。实验还对萃取头的使用次数和维护进行了探讨。利用已经建立的SPME-GC/MS法对佛山市28家水厂的出厂水和原水、佛山典型景观千灯湖和亚艺公园湖水进行普查。该法具有操作简单快速、能实现自动化连续检测、准确、灵敏度高等特点,适用于饮用水中嗅味物质定性和定量。     

Determination of alcohol compounds using corona discharge ion mobility spectrometry

Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions （H2O）nH^＋ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions （H2O）nH^＋. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.     

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.     

壬基酚初级生物降解产物的辨认

为分析污水生物处理过程中壬基酚的去除机制,采用混合基质加标对照培养活性污泥、单一基质培养优势菌群2种生物降解实验,结合气相色谱-质谱谱图解析,从分子水平分析了壬基酚初级代谢产物和代谢途径.研究结果表明,活性污泥降解壬基酚的初级代谢产物主要为C4-C6烷基取代苯酚,烷基链的结构差异与其母体壬基的异构方式有关,烷基上的支链主要为甲基;优势降解菌群代谢壬基酚的初级产物除烷基苯酚外,还有苯乙酸等.污水生物处理过程中壬基酚可能的初级生物代谢途径是壬基上的长支链断裂为短的甲基链,生成一系列带有不同分支结构的短链烷基酚类代谢产物,进一步的代谢产物有苯乙酸.根据烷基酚类物质的内分泌干扰特性,短链烷基酚仍然具有雌激素活性,因此在壬基酚污染防治过程中应给与足够的重视.     

Composition analysis of colored dissolved organic matter in Taihu Lake based on three dimension excitation-emission fluorescence matrix and PARAFAC model, and the potential application in water quality monitoring

Taihu Lake is one of the five biggest lakes in China. Surface water samples from 26 sampling sites of Taihu Lake were collected. Furthermore wet chemical analysis （CODCr and BOD5） and measurement of three dimensional excitation-emission matrix （3DEEM） spectra in the laboratory have been conducted. Using parallel factor analysis （PARAFAC） model, three components of colored dissolved organic matter （CDOM） have been identified successfully, based on the analysis of 3DEEM data. The characteristics of the three components also have been described by comparing them to some components of CDOM, identified in earlier researches. Meanwhile, spatial variations of concentration for the three components in Taihu Lake have been analyzed, and the result indicates that the concentration of component 1 depends more on the situation of wastewater pollution and can be used as the indicator of wastewater pollution. The relationship between the concentrations of the three components and results of the wet chemical analysis show that none of the three components can be used as indicators of gross organic matter in water. However, the concentrations of all the three components have obvious linear relationships with the BOD5 value, especially for component 1 （r = 0.72878）. Finally, the potential applications of the composition analysis based on 3DEEM and PARAFAC model in water quality monitoring have been illuminated.     

Composition analysis of colored dissolved organic matter in Taihu Lake based on three dimension excitation-emission fuorescence matrix and PARAFAC model, and the potential application in water quality monitoring

Taihu Lake is one of the five biggest lakes in China. Surface water samples from 26 sampling sites of Taihu Lake were collected. Furthermore wet chemical analysis (CODCr and BOD5) and measurement of three dimensional excitation-emission matrix (3DEEM) spectra in the laboratory have been conducted. Using parallel factor analysis (PARAFAC) model, three components of colored dissolved organic matter (CDOM) have been identified successfully, based on the analysis of 3DEEM data. The characteristics of the three components also have been described by comparing them to some components of CDOM, identified in earlier researches. Meanwhile, spatial variations of concentration for the three components in Taihu Lake have been analyzed, and the result indicates that the concentration of component 1 depends more on the situation of wastewater pollution and can be used as the indicator of wastewater pollution. The relationship between the concentrations of the three components and results of the wet chemical analysis show that none of the three components can be used as indicators of gross organic matter in water. However, the concentrations of all the three components have obvious linear relationships with the BOD5 value, especially for component 1 (r=0.72878). Finally, the potential applications of the composition analysis based on 3DEEM and PARAFAC model in water quality monitoring have been illuminated.     

复合菌群生物强化削减NPEO内分泌干扰毒性的试验研究

印染废水中的壬基酚聚氧乙烯醚(nonylphnol polyethylene ether, NPEO)在生化处理过程中会产生雌激素活性更强的壬基酚(NP)等中间产物,导致处理后印染废水内分泌干扰毒性升高.为探索以NPEO和NP为降解靶点进行菌群生物强化脱毒的可行性,分别以NPEO和NP驯化富集印染活性污泥,并将得到的降解菌群以单独和组合投加方式进行生物强化试验,考察强化控毒效果.结果表明：(1)NPEO降解菌群(NPEB)和NP降解菌群(NPB)中的优势菌均为Proteobacteria,二者对10 mg/L NPEO和NP的48 h去除率均高于98%.(2)单独或组合投加5 mg/L的NPEB和NPB至混合液悬浮固体浓度(MLSS)为500 mg/L的活性污泥体系,均能显著提升活性污泥对不同浓度(10和1 mg/L) NPEO的降解性能,大幅缩短NPEO降解过程中雌激素活性的变化周期,并使体系的雌激素活性维持在较低水平.(3)当降解体系中加入1 000 mg/L葡萄糖作为额外碳源时,NPB的强化性能被完全抑制,而NPEB在降解性能受抑的情况下仍能增强活性污泥的NPEO降解速率并缩短控...     

水和废水中五日生化需氧量测定全程质量控制

质量控制是环境监测赖以生存和发展的基础,加强全程质量控制才能确保监测数据的准确性和可靠性。结合环境监测工作实际,应用最新修订国标方法-稀释与接种法(HJ505-2009)对水和废水中五日生化需氧量测定进行了全程质量控制技术探讨。概述了方法原理,简介了方法所需仪器与试剂,深入探讨了运用该方法进行水和废水中五日生化需氧量测定全程质量控制技术问题。指出在最新修订国标方法基础上,正确进行水样干扰消除和预处理操作,准确确定水样稀释倍数,严格控制测定和培养温度,优先选取电化学探头法测定溶解氧浓度,准确进行测定结果数据处理,切实规范监测数据结果填报,能够在确保水样五日生化需氧量测定精密度和准确度的同时简化大批量成分复杂水样测定过程。     

Rapid detection of multiple class pharmaceuticals in both municipal wastewater and sludge with ultra high performance liquid chromatography tandem mass spectrometry

This work described the development, optimization and validation of an analytical method for rapid detection of multiple-class pharmaceuticals in both municipal wastewater and sludge samples based on ultrasonic solvent extraction, solid-phase extraction, and ultra high performance liquid chromatography-tandem mass spectrometry quantification. The results indicated that the developed method could effectively extract all the target pharmaceuticals （25） in a single process and analyze them within 24 min. The recoveries of the target pharmaceuticals were in the range of 69%-131% for wastewater and 54%-130% for sludge at different spiked concentration levels. The method quantification limits in wastewater and sludge ranged from 0.02 to 0.73 ng/L and from 0.02 to 1.00μg/kg, respectively. Subsequently, this method was validated and applied for residual pharma- ceutical analysis in a wastewater treatment plant located in Beijing, China. All the target pharmaceuticals were detected in the influent samples with concentrations varying from 0.09 ng/L （tiamulin） to 15.24 μg/L （caffeine）; meanwhile, up to 23 pharmaceuticals were detected in sludge samples with concentrations varying from 60 ng/kg （sulfamethizole） to 8.55 mg/kg （ofloxacin）. The developed method demonstrated its selectivity, sensitivity, and reliability for detecting multiple-class pharmaceuticals in complex matrices such as municipal wastewater and sludge.     

深圳居民膳食壬基酚和辛基酚暴露的风险评估

为了解深圳市居民壬基酚和辛基酚的膳食暴露水平并预测其风险,利用深圳总膳食研究采集的膳食调查数据及代表性膳食样品进行暴露评估:采用分层整群随机抽样方法,抽取深圳城市区和农村区的244户居民、853人进行家庭膳食调查,利用3d 24h回顾法和称重记账法采集食物消费量数据;同时,采用高效液相色谱-质谱分析手段检测膳食样品中的壬基酚和辛基酚含量;并用风险指数评估人群暴露风险.结果表明,深圳城市区、农村区、深圳市居民的壬基酚膳食暴露水平分别为89.7,128.9,116.2ng/(kg×bw);辛基酚的暴露水平分别为42.7,35.3,39.3ng/(kg×bw).深圳城市区、农村区、深圳市居民壬基酚膳食暴露的风险指数分别为0.02、0.03、0.02,辛基酚的风险指数均为0.0004.深圳市居民壬基酚的膳食暴露水平高于辛基酚,但两者的风险指数均远低于1,暴露风险在可接受范围之内.