沉积物中雌激素及壬基酚、辛基酚、双酚A的测定

近些年来雌激素及烷基酚类化合物由于其对水生生物的内分泌干扰作用越来越受到广泛关注.沉积物作为环境中有机污染物的重要储存库,研究目标物在其中的浓度分布对于探明此类物质在环境中的迁移转化具有重要意义.但沉积物中基质组成复杂而雌激素又痕量存在,这增加了前处理的难度.本研究从雌激素及烷基酚类化合物的理化性质入手,采用碱液提取、液液萃取和LC-MS/MS分析测定沉积物样品中的雌激素及壬基酚、辛基酚、双酚A.结果表明,经过优化的方法对7种目标物的回收率介于61.9%～93.7%之间.该方法能有效去除沉积物中那些不溶于强碱和既溶于酸又溶于碱的有机污染物,同时操作简单、成本低,但回收率高、检出限低,可广泛适用于河流沉积物样品及土壤样品的前处理.     

单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

金属离子对δ-MnO2 去除对叔辛基酚抑制作用的研究

研究了pH 4.0的水溶液中各种金属离子对合成的δ-MnO2去除对叔辛基酚(4-t-OP)的影响.实验表明反应150 min时,δ-MnO2对4-t-OP的去除率达到100%,但当反应体系中含有金属离子时,去除效果受到抑制.抑制效果随金属离子浓度的增加而增大,并随金属离子的不同表现出较大的差异.在pH 4.0条件下,Pb2+和Mn2+的抑制效果最强,其次为过渡金属离子,再次是碱土金属离子,而碱金属离子基本上不产生抑制作用.还比较了δ-MnO2对多种金属离子的吸附能力,其对Pb2+的吸附作用最强,在其余的金属离子中,对过渡金属离子的吸附量稍大于碱土金属离子.结果表明,金属离子所产生抑制作用的源于其占据了δ-MnO2表面反应位点并与4-t-OP形成竞争,而抑制作用大小的差异主要来源于δ-MnO2与金属离子间吸附作用强弱的差别,MnO2表面结构的变化,以及溶液中自由态金属离子的分布比例及其离子半径的不同.     

UV和H2 O2联合消毒灭活饮用水中大肠杆菌研究

以大肠杆菌为研究对象,对单独紫外线(UV)、H2O2及两者不同组合方式的灭活效果进行了分析.结果表明,单独H2O2对大肠杆菌基本无灭活效果,加入浓度为20 mg·L-1的H2O2接触时间为30 min时,灭活率仅为0.02个对数级;单独UV工艺可在一定程度上灭活大肠杆菌,紫外线剂量为10 mJ·cm-2时,灭活率可达到4.51个对数级.紫外线和H2O2联合消毒在一定程度上提高了消毒效果,且不同的组合方式对灭活效果有很大的影响.先UV后H2O2消毒效果优于先H2O2后UV,当紫外线剂量为5 mJ·cm-2时,加入H2O2分别反应2.5、5、10、20 min后,两者的灭活率分别较单独UV消毒增加0.09、0.35、0.38、0.68和0.01、0.07、0.14、0.53个对数级.而UV与H2O2同时消毒效果优于UV与H2O2顺序消毒,当紫外线剂量为5 mJ·cm-2时,加入H2O2反应20 min后,灭活率较UV-H2O2和H2O2-UV工艺分别增加了0.43和0.58个对数级.随着紫外线强度的增加,大肠杆菌的灭活效果不断提高.     

Electrochemical treatment of olive mill wastewater: Treatment extent and effluent phenolic compounds monitoring using some uncommon analytical tools

Problems related with industrials effluents can be divided in two parts: (1) their toxicity associated to their chemical content which should be removed before discharging the wastewater into the receptor media; (2) and the second part is linked to the difficulties of pollution characterisation and monitoring caused by the complexity of these matrixes. This investigation deals with these two aspects, an electrochemical treatment method of an olive mill wastewater (OMW) under platinized expanded titanium electrodes using a modified Grignard reactor for toxicity removal as well as the exploration of the use of some specific analytical tools to monitor effluent phenolic compounds elimination. The results showed that electrochemical oxidation is able to remove/mitigate the OMW pollution. Indeed, 87% of OMW color was removed and all aromatic compounds were disappeared from the solution by anodic oxidation. Moreover, 55% of the chemical oxygen demand (COD) and the total organic carbon (TOC) were reduced. On the other hand, UV- Visible spectrophotometry, Gaz chromatography/mass spectrometry, cyclic voltammetry and 13 C Nuclear Magnetic Resonance (NMR) showed that the used treatment seems efficaciously to eliminate phenolic compounds from OMW. It was concluded that electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of all phenolic compounds present in OMW. Among the monitoring analytical tools applied, cyclic voltammetry and 13 C NMR are among the techniques that are introduced for the first time to control the advancement of the OMW treatment and gave a close insight on polyphenols disappearance.     

泥龄对A~2O工艺去除多环麝香的影响

研究了A2O工艺不同污泥龄(Sludge retention time,SRT)条件下中佳乐麝香(Galaxolide,HHCB)与吐纳麝香(Tonalide,AHTN)的去除和迁移的变化情况。采用固相萃取与气相质谱联用的方法对各池中水相与泥相中HHCB和AHTN的浓度进行分析。结果发现:A2O工艺对HHCB的去除效果好于AHTN。高SRT条件(15,20 d)下HHCB、AHTN的总去除率明显小于低SRT条件(5,10 d)下的总去除率。     

Adsorption of 2-mercaptobenzothiazole from aqueous solution by organo-bentonite

The adsorption behavior of 2-mercaptobenzothiazole onto organo-bentonite was investigated.Natural bentonite from Gaozhou in Guangdong Province,China was collected.Organo-bentonite was prepared by intercalation of cetyltrimethyl ammonium bromide into the natural bentonite.The physicochemical properties of the prepared organo-bentonite were characterized by X-ray diffraction,N2 adsorption-desorption isotherm and Fourier transform infrared spectroscopy.The results showed that montmorillonite is the main component of the natural bentonite.The basal spacing of the natural bentonite is 1.47 nm,which increased to 1.98 nm on intercalation with cetyltrimethyl ammonium bromide.Moreover,both the surface area and pore volume increased with intercalation.Clear CH2 stretching(3000-2800 cm-1) and scissoring(1480-1450 cm-1) modes of the intercalated surfactants were observed for organobentonite.Compared with the pseudo first-order kinetic model,the pseudo second-order kinetic model is more suitable to describe the adsorption kinetics of 2-mercaptobenzothiazole onto organo-bentonite.The adsorption capacity of 2-mercaptobenzothiazole onto organo-bentonite increased with increasing initial concentration of 2-mercaptobenzothiazole,but decreased with increasing adsorbent dosage.The adsorption isotherm of 2-mercaptobenzothiazole onto organo-bentonite fits well with the Langmuir model.The maximum adsorption capacity of organo-bentonite for 2-mercaptobenzothiazole was 33.61 mg/g,indicating that organo-bentonite is a promising adsorbent for 2-mercaptobenzothiazole.     

Effects of physical and chemical characteristics of surface sediments in the formation of shallow lake algae-induced black bloom

Surface sediments are closely related to lake black blooms. The dissolved oxygen （DO） distribution and its penetration depth in surface sediments as well as the migration and transformation of redox sensitive elements such as Fe and S at the sediment-water interface are important factors that could influence the formation of the black bloom. In this study, dredged and undredged sediment cores with different surface properties were used to simulate black blooms in the laboratory. The Micro Profiling System was employed to explore features of the DO and ∑H2S distribution at the sediment-water interface. Physical and chemical characteristics in sediments and pore waters were also analyzed. The results showed that sediment dredging effectively suppressed the black blooms. In the undredged treatment, DO penetration depth was only 50 μm. Fe^2＋ concentrations, ∑H2S concentrations, and ∑H2S production rates were remarkably higher in surface sediments and pore waters compared to control and dredged treatments. Furthermore, depletion of DO and accumulation of Fe^2＋ and ∑H2S in surface sediments and pore waters provided favorable redox environments and necessary material sources for the blooms. The study results proved that physical and chemical characteristics in surface sediments are important factors in the formation of the black bloom, and could provide scientific guidance for emergency treatment and long-term pre-control of black blooms.     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

贯彻落实“大气十条”的环境监测技术需求

2013年9月,国务院发布《大气污染防治行动计划》（以下简称《大气十条》）,捆响了向PM2.5污染宣战的“发令枪”,掀起了以防治大气污染为目标的全社会行动。《大气十条》提出,经过五年努力,使全国空气质量总体改善,重污染天气较大幅度减少;京津冀、长三角、珠三角等区域空气质量明显好转。《大气十条》把解决人民群众最关心、最直接、最现实的PM2.5污染问题作为根本出发点和落脚点,切实维护人民群众身体健康和环境权益。