土壤中邻苯二甲酸酯的高效液相色谱检测方法

为了更加高效、快捷、经济地检测土壤中的邻苯二甲酸酯(PAEs),本文构建并优化了超声萃取-高效液相色谱(UE-HPLC)检测方法.选取美国环保署优先控制的邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二正丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二正辛酯为实验对象,通过对6种PAEs的最大紫外吸收波长值进行测定、优化高效液相色谱运行条件,进而构建了土壤中6种PAEs的HPLC检测方法,具体参数如下:检测时间为30min;进样量为20μL;分离系统以乙腈-UP水为流动相、初始流速为1.0mL/min,采用梯度洗脱的方式分离PAEs,柱温为40℃;检测系统采用紫外检测器检测、开启波长切换模式,波长分别为205和290nm.采用线性回归方程及相关系数、加标回收率、相对标准偏差和检出限对方法进行评价.结果表明,该方法具有较宽的线性范围,最大质量浓度范围在0.1～100mg/L,相关系数均在0.999以上.1和5mg/kg的6种PAEs加标回收率范围分别为73.03%～91.89%和72.59%～90.70%,相对标准偏差范围分别为1.78%～12.46%和0.30%...     

高效液相色谱-串联质谱法测定水中邻苯二甲酸酯

建立了水中7种邻苯二甲酸酯(PAEs)的液相色谱-串联质谱分析方法.样品经过甲醇饱和正己烷超声波萃取后,采用液质联用法测定邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二戊酯(DPP)、邻苯二甲酸二己酯(DHXP)、邻苯二甲酸二壬酯(DNP...     

GC-MS法测定水中邻苯二甲酸酯

采用气相色谱-质谱（GC-MS）联用测定水中邻苯二甲酸酯（包括邻苯二甲酸二甲酯,邻苯二甲酸二乙酯,邻苯二甲酸二正丁酯,邻苯二甲酸丁基苄基酯,邻苯二甲酸二（2-乙基己基）酯,邻苯二甲酸二正辛酯）,优化了试验条件。GC-MS选择SIM扫描方式,外标法定量,定性定量准确,线性响应良好,干扰小。邻苯二甲酸酯的方法检出限为0.002 mg/L-0.03 mg/L,平均加标回收率在94.2%-110%之间,RSD在0.4%-6.3%之间。     

固相萃取-气相色谱质谱法测定水样中5种邻苯二甲酸酯研究

建立了采用固相萃取技术结合气相色谱质谱法对5种邻苯二甲酸酯(PAEs) 进行富集、检测的方法,并成功应用于实际水样分析.实验中采用加标回收率来评价萃取效率,考察并优化了影响萃取效率的主要因素,包括固相萃取小柱的种类、洗脱剂类型、洗脱次数和用量、样品环境影响等.结果表明:在最佳萃取条件下,该法对5种PAEs(邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯和邻苯二甲酸(2-乙基己基)酯)具有较高的萃取效率;在浓度范围为0.50~10.0 mg/L时,线性相关系数为0.992 6~0.999 8;检出限为0.05~0.37μg/L,定量限为0.20~1.48μg/L,空白水样加标回收率范围为95%~115%,相对标准偏差为2.4%~11.1%.该方法操作简单、稳定性好、回收率高,可以用于测定实际水样中的PAEs类增塑剂.     

化妆品中邻苯二甲酸酯类环境激素检测方法研究

建立了用高效液相色谱法测定化妆品中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)3种邻苯二甲酸酯类环境激素的方法。样品用甲醇超声提取、高速离心、0.45μm有机相滤膜过滤。色谱条件选择流动相组成为甲醇-水(85∶15,v/v),紫外检测器波长为224nm。回收率在98.1%～99.8%之间,相对标准偏差RSD在0.78%～1.5%之间,最低检出限在0.48～0.91μg/L之间,相关系数均>0.998。该方法简便易行,可作为化妆品中邻苯二甲酸酯类的测定。     

搅拌棒吸附萃取-气相色谱-质谱联用测定海水中邻苯二甲酸酯

为了测定海水中痕量邻苯二甲酸酯,构建并优化了搅拌棒吸附萃取-气相色谱-质谱联用方法.选取邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯这6种邻苯二甲酸酯作为研究对象,优化了萃取时间和解析时间等5种因素,通过回收率和相对标准偏差等对SBSE-GC-MS方法进行验证.结果表明,最佳萃取时间为2 h,最佳甲醇添加量为10%,最佳氯化钠添加量为5%,最佳解析时间为50 min,最佳解析溶剂为甲醇∶乙腈=4∶1(体积比).6种邻苯二甲酸酯的峰面积和质量浓度线性对应关系良好,相关性系数均大于0.997,检出限在0.25~174.42 ng·L-1之间,不同质量浓度的回收率均在56.97%~124.22%之间,相对标准偏差在0.41%~14.39%之间.在建立方法的基础上,测定了胶州湾主要河流入海口的样品,结果表明所有采样点均检出邻苯二甲酸酯,邻苯二甲酸二乙酯检出率为100%,质量浓度较大的污染物为邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯.     

胶束电动毛细管色谱测定塑料工业废水中邻苯二甲酸丁苄酯

运用胶束电动毛细管色谱法同时分离测定了水中 5种邻苯二甲酸酯的标准混合物,建立了对实际工业废水样中邻苯二甲酸丁苄酯的定量测定方法。结果表明,30min内 5种邻苯二甲酸酯得到了较好的分离。以峰面积定量,在4～ 5 0mg L的浓度范围内,邻苯二甲酸丁苄酯的标准曲线具有良好的线性相关性,相关系数较好。相对标准偏差<2 6 %,工业废水加标测定,邻苯二甲酸丁苄酯的回收率在 10 4 %～ 10 9%之间     

我国城市污泥中邻苯二甲酸酯的研究

应用GC/MS对我国内地和香港共11个城市污泥中的6种U.S. EPA优控的邻苯二甲酸酯化合物(PAEs)进行了研究.各城市污泥中邻苯二甲酸酯化合物的总含量(∑PAEs)在10.465～114.166mg/kg之间,多数在20mg/kg左右.分子量较低的邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸正二丁酯(DnBP)和邻苯二甲酸丁基苄基酯(BBP)在所有的城市污泥中均检测到,但多数含量较低(小于1.0mg/kg).邻苯二甲酸正二辛酯(DnOP)在少数城市污泥中未检测到,但在其他城市污泥中的含量都较高.邻苯二甲酸(2-乙基己基)酯(DEHP)仅在个别城市污泥中检测到,且含量较低.各城市污泥中的邻苯二甲酸酯都是以个别化合物为主,显示出不同的分布特征.污泥中邻苯二甲酸酯化合物的种类和含量与污水来源、污水处理方式、污泥类型、化合物的结构和理化性质等因素有关.     

固相微萃取-液相色谱法测定水中二苯并噻吩

分别采用高效液相色谱与固相微萃取-高效液相色谱法建立了水中微量二苯并噻吩的分析方法,结果表明固相微萃取对二苯并噻吩具有非常明显的富集作用。实验得到固相微萃取技术最佳检测条件为:吸附时间20min,解析时间3min,色谱流动相甲醇/水=90/10,方法的变异系数为2.85%,加标回收率102.4%,检测限0.03μg/mL。     

泉州湾邻苯二甲酸酯的地球化学特征

于2013年10月和2014年3月采集泉州湾表层海水、沉积物和生物体样品,采用气相色谱-质谱(GC-MS)联用技术对16种邻苯二甲酸酯(PAEs)进行定性、定量分析,研究泉州湾海水、沉积物及生物体中16种邻苯二甲酸酯(phthalate esters,PAEs)的含量分布、化学组成及环境意义。结果表明,研究的16种邻苯二甲酸酯类化合物中,表层海水、悬浮颗粒物(SPM)、表层沉积物以及牡蛎样品中均检出邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯(DiBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)和邻苯二甲酸二环己酯(DCHP);泉州湾表层海水中邻苯二甲酸酯溶解态总含量(PAEs)在1059.78~5893.17 ng/L之间,平均值为2996.82 ng/L,悬浮颗粒态总含量在11.09~270.39 g/g之间,平均值为110.47 g/g,表层沉积物中PAEs在206.6~464.2 g/kg之间,平均值为348.2 g/kg,生物体牡蛎中PAEs在179.29~254.24 g/kg之间,平均值为216.77 g/kg;DiBP、DBP和DEHP为PAEs的主要成分。与其他地区比较,泉州湾海洋环境中PAEs总体污染水平处于中等偏低水平。     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.