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.     

工艺过程源和溶剂使用源挥发性有机物排放成分谱研究进展

工艺过程源和溶剂使用源是我国大气挥发性有机物(VOCs)最主要的工业来源,近年来源成分谱的研究逐步受到重视.本文总结梳理了2000年以来国内外有关工艺过程源和溶剂使用源排放VOCs特征的相关研究,对比分析了不同研究结果的差异,结合不同研究的对象和方法,探讨了影响溶剂使用和工艺过程源排放成分谱研究的主要影响因素.结果表明,工艺过程源下分的32个三级子类(参照国家《大气挥发性有机物源排放清单编制技术指南》源分类方法)中,有相关研究报道的包括八类;溶剂使用源下分的10个三级子类中,有相关研究报道的包括四类.总体而言,细化的行业研究种类比较少,不同行业排放VOCs组成差异大,可比性较差.污染源采集测试方法对同一行业源排放成分谱研究结果有较大影响.此外,成分谱中VOCs物质名录的不统一也不利于不同研究结果的比较;含氧VOCs是上述两类污染源排放的重要组分,需要纳入测量范围.未来,有必要建立开放交互式的工艺过程源和溶剂使用源排放VOCs成分谱库平台,鼓励并形成不同研究结果的共享及录入机制;并建立相关研究成果数据入库规范,包括研究的对象、方法、地区、时段以及样本量等详细信息,以便开展不同VOCs源成分谱不确定性评判.     

环境友好农业生产的生态补偿机制探索与实践

围绕中德技术合作＂中国华北地区集约化农业的环境战略＂项目实施过程中,为鼓励农民采用节水、节肥、节药环境友好方式生产安全优质设施蔬菜,减轻农业面源污染,保护农业生态资源与环境而开展的生态补偿的实践进行论述,结合项目的实践从补偿原则、补偿对象、补偿标准、补偿形式、补偿环节、补偿监管等方面进行了探讨。笔者认为,建立健全农业生态环境补偿制度符合世界贸易组织农业协议绿箱政策,有利于推动环境友好技术的应用。环境友好农业生产的生态补偿应以项目（政府）补贴为主导,以农民自愿为前提,以骨干农户、农民专业合作社为主要补偿对象,以技物结合为主要补偿形式,以兼顾生态、经济和社会效益为目标。     

加速溶剂萃取/气相色谱质谱法测定鱼类样品中的多环麝香

建立了鱼类样品中5种多环麝香的分析方法.采用加速溶剂萃取(ASE)提取,经凝胶渗透色谱(GPC)以及中性氧化铝层析柱净化后,浓缩并定容洗脱液,用GC-SIM-MS进行检测.本方法对替代物标样荧蒽-d10.的回收率为92.7%-112.9%.以六氯苯(13C)为内标,5种合成麝香的线性范围为1.0-1000.0 ng·g...     

A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils

An optimized procedure based on gas chromatography-mass spectrometry (GC-MS) combined with accelerated solvent extraction (ASE) is developed for the analysis of six phthalic acid esters (PAEs), which are priority soil pollutants nominated by United States Environmental Protection Agency (USEPA). Quantification of PAEs in soil employs ultrasonic extraction (UE) (USEPA 3550) and ASE (USEPA 3545), followed by clean up procedures involving three different chromatography columns and two combined elution methods. GC-MS conditions under selected ion monitoring (SIM) mode are described and quality assurance and quality control (QA/QC) criteria with high accuracy and sensitivity for target analytes were achieved. Method reliability is assured with the use of an isotopically labeled PAE, di-n-butyl phthalate-d4 (DnBP-D4), as a surrogate, and benzyl benzoate (BB) as an internal standard, and with the analysis of certified reference materials (CRM). QA/QC for the developed procedure was tested in four PAE-spiked soils and one PAE-contaminated soil. The four spiked soils were originated from typical Chinese agricultural fields and the contaminated soil was obtained from an electronic waste dismantling area. Instrument detection limits (IDLs) for the six PAEs ranged 0.10–0.31 μg·L^-1 and method detection limits (MDLs) of the four spiked soils varied from a range of 20–70 μg·kg^-1 to a range of 90– 290 μg·kg^-1. Linearity of response between 20 μg·L^-1 and 2 mg·L^-1 was also established and the correlation coefficients (R) were all>0.998. Spiked soil matrix showed relative recovery rates between 75 and 120% for the six target compounds and about 93% for the surrogate substance. The developed procedure is anticipated to be highly applicable for field surveys of soil PAE pollution in China.     

北京地区地表水中OCPs和PCBs的污染分析

在夏、冬两季对北京地区密云,潮白河,玉渊潭和通惠河等地表水中17种有机氯农药（OCPs）和84种多氯联苯（PCBs）的含量进行了分析及来源解析.实验结果表明,OCPs总量在7.86～53.1ng/L之间,平均值为（16.9±14.6）ng/L.PCBs总量在2.99～32.7ng/L之间,平均浓度为（10.9±10.4）ng/L.HCHs,硫丹,DDTs和HCB是主要的OCPs污染物,其含量分别为（13.9±11.5）ng/L,（2.20±2.01）ng/L,（0.63±1.51）ng/L和（0.12±0.14）ng/L.α-HCH/γ-HCH平均比值为1.53,小于工业HCH中比值4～7,表明北京地区地表水中存在林丹的使用.而DDT/（DDD+DDE）比值<1.22,表明北京地区并无新的DDTs污染源输入环境.PCBs以低氯代联苯为主,其中二氯,三氯,四氯和五氯联苯总和占∑₈₄PCBs总量的79.2%.北京地区地表水中不同氯取代数PCBs组成与我国历史PCB产品组成相符,均以低氯代联苯为主,表明北京地区地表水中PCBs污染来源为历史使用.相比于国内其他区域水质而言,北京地区地表水OCPs和PCBs污染水平较低.     

铜镍电镀退镀废液资源化处理工艺

针对硝酸型铜镍退镀废液,确定了蒸馏法回收硝酸、溶剂萃取法分离提取铜、沉淀分离法回收镍的工艺路线.探讨了采用P507煤油体系萃取分离硝酸介质中的铜和镍及用硫酸反萃铜的条件及影响规律,确定了最佳工艺参数.结果表明,硝酸回收率可达97.8%;当最佳萃取工艺条件为:料液浓度Cu 15～20mg/mL,Ni 5～10 mg/mL,料液pH为1～2,萃取剂体积分数35%,皂化度60%,相比为1∶1,振荡时间2min,温度20℃～25℃,铜的一级萃取率达90%以上,铜镍分离系数为75,经过三级逆流萃取废液中的铜镍已达到完全分离;以NaOH作沉淀剂,溶液的pH为10～11,镍的回收率可达99.9%.经上述处理后,使排放液达到国家工业废水排放标准要求.     

含钴镍废水的萃取处理研究

采用Ｎ２３５作萃取剂，在合适的酸度和氯离子浓度条件下，对含钴镍废水进行溶剂萃取处理，重点研究了酸度、氯离子浓度、萃取级数及反萃条件对钴镍分离效率的影响，试验结果表明，可以有效地回收利用废水中的钴和镍。     

[Bmim]PF_6溶剂浮选UV-Vis检测水中四环素类抗生素

建立了一种分离/富集的新体系——离子液体气浮溶剂浮选,该体系集离子液体萃取和气浮溶剂浮选优势于一体,以离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim]PF)6和乙酸乙酯(EA)混合溶剂为浮选溶剂,以稀土金属离子La(Ⅲ)或Ce(Ⅲ)为捕集剂,分离/富集了水中的四环素类抗生素,并用紫外-可见分光光度法测定其总含量,线性范围分别为0.0～34μg/L、0～23.0μg/L,表观摩尔吸光系数分别为ε390=1.92×105L/(mol·cm),ε380=1.15×105L/(mol·cm)。实测了鱼塘水样,加标回收率为84.06%～106.15%,RSD3.31%。研究结果表明:该方法灵敏度高、选择性好、富集倍数大、污染小,适用于环境水样中痕量四环素类抗生素的分离分析。     

［omim］［PF6］萃淋树脂的制备及对萘吸附机制的研究

将离子液体[omim][PF6]以液膜的形式固定在大孔吸附树脂上,制备萃淋树脂,研究其对水相中萘的吸附及影响因素.结果表明,离子液体[omim][PF6]萃取萘的过程,萘主要分配在[omim]+的疏水饱和碳链上;树脂和离子液体质量比为10∶1和20∶1的萃淋树脂,[omim][PF6]在水相中的溶解明显小于2∶1和5∶1的萃淋树脂;不同质量比萃淋树脂对萘的饱和吸附量大小为10∶1萃淋树脂>20∶1萃淋树脂>树脂,对吸附等温线的拟合结果表明,树脂对萘的吸附更符合Freundlich吸附等温式,而萃淋树脂对萘的吸附则更符合Langmuir吸附等温式.不同温度萃淋树脂对萘的饱和吸附量大小为:20℃>15℃>25℃,随着pH的升高饱和吸附量下降,随着无机盐浓度的提高饱和吸附量均有提高;正交实验确定的最佳条件为:温度=30℃、pH=3、NaCl浓度=2 000 mg.L-1,其中pH值是最主要的影响因素.