用GC-ECD测定水中痕量溴酸根的方法

研究了用GC-ECD测定水中痕量溴酸盐浓度的方法,优化了用工程丙酮作溴酸根衍生化试剂的反应条件.在最佳衍生反应条件下、溴酸根浓度为3.8～92 μg·L-1范围内,溴酸根浓度和相应溴代衍生物的峰面积有良好的线性关系(R2=0.9954).本方法的检出限为0.75 μg·L-1,测定系列浓度溴酸根水溶液的相对偏差(RSD)均小于5%,样品加标平均回收率为105.1%～107.6%.在正常臭氧氧化时间内测定臭氧氧化后的过滤水中的溴酸根浓度时,只要臭氧投量与TOC比值大于0.8 mg·mg-1,溴酸根的测定就不受本底天然有机物的影响.     

氮磷浓度对东海原甲藻优势种群吸附BDE28和BDE47的影响

以东海原甲藻为优势种群的浮游微藻作为研究对象,在不同氮浓度(0、128、512μmol·L-1)和磷浓度(0、8、32μmol·L-1)下培养,研究了氮、磷浓度对东海原甲藻优势种群生化组成和吸附2,4,4’-三溴联苯醚(BDE28)和2,2’,4,4’-四溴联苯醚(BDE47)的影响,分析了东海原甲藻优势种群对BDE28和BDE47的吸附量与生化组成的相关性.结果表明,氮浓度为0μmol·L-1时,单位细胞对BDE28和BDE47的吸附量分别为2.2 ng·(106cells)-1和2.9 ng·(106cells)-1,是氮为128μmol·L-1和512μmol·L-1浓度的1.3～1.9倍.不同氮浓度之间单位体积藻液吸附量和对BDE28和BDE47的吸附百分数均没有显著差异,单位体积藻液吸附量范围为0.160～0.184 ng·mL-1,吸附百分数为80.2%～92.1%.磷浓度为0μmol·L-1时,单位细胞BDE28和BDE47的吸附量分别为7.6 ng·(106cells)-1和8.4 ng·(106cells)-1,是磷为8μmol·L-1、32μmol·L-1浓度时的5.4～6倍,单位体积藻液吸附量和吸附百分数在不同磷浓度间未出现显著差异,单位体积藻液的吸附量为0.167～0.194 ng·mL-1,吸附百分数为80.2%～93.2%.相关性分析表明,氮浓度与单位细胞BDE28和BDE47的吸附量呈负相关,磷浓度与单位体积吸附量和吸附百分数呈正相关;同时,吸附量与总脂呈正相关关系.氮、磷浓度导致东海原甲藻优势种群细胞的生化组成发生变化,进一步引起对BDE28和BDE47吸附的变化.     

溴酸根在颗粒活性炭上的还原

小试研究了溶液中溴酸根在颗粒活性炭上还原与溴离子生成的过程,考察pH、离子强度、温度和初始浓度对该过程的影响.结果表明,活性炭对溴酸根的去除性能与表面碱性官能团有一定相关性.其它阴离子对吸附/还原过程有阻碍作用,实验中影响顺序为ＮＯ^-₃>SO^２－₄ > Cl^-.溴酸根的吸附与溴离子的生成可分别用拟二级速率方程和粒子内扩散模型进行模拟,绝大部分相关系数在0.97以上.低pH和低离子强度有利于溴酸根的吸附与还原.15～42℃范围内吸附与还原速率随温度提高先降低后升高.实验中活性炭对溴酸根的最大吸附容量可达到769.23 μmol/g（98.4 mg/g）,但反应较慢且易受干扰.推测活性炭表面微孔部分对溴酸根的吸附也受到溴离子释放的阻碍.     

UV/氯联合处理含溴溶液中溴酸根的生成

研究了UV和氯联合作用下溴酸根离子(BrO^-₃)在低浓度含溴溶液中的生成,旨在探讨pH、次氯酸钠(NaOCl)浓度、溶解氧(DO)、光强和温度等因素对其生成的影响.研究表明,暗反应条件下H₂O-NaOCl-Br^-体系较稳定,而UV照射可使游离氯浓度持续降低,同时伴有部分Br^-（6 .6%～32%）被氧化成BrO^-₃离子;pH、温度和光强恒定时余氯的分解可用拟一级反应速率方程拟合;实验条件下（I为610～1 896 μW/cm²,T为12 .2～36 .1℃）,拟一级反应速率常数分别与体系温度和光强值有线性关系;BrO^-₃的生成大致可以分为快速、慢速和平缓3个阶段;在慢速生成阶段,BrO^-₃的生成量与余氯的分解量有良好的线性关系（绝大部分相关系数在0 .96以上）;实验范围内（pH为4 .41～11 .07,DO为1 .5～9 　mg/L,Cl₂为1 .23～4 .50 　mg/L）,低pH、低DO和高初始NaOCl（以氯计）浓度有利于溴酸根的生成,提高温度与光强均不同程度提高溴酸根生成速度,但同时因加速余氯的分解而减少了溴酸根的总生成时间.     

四川妇女血清中多溴联苯醚的浓度水平与组成特征

用气相色谱-质谱的选择离子法测定四川省妇女血清中多溴联苯醚的质量浓度,并对其组成特征及主要来源进行了研究.在被测的11种多溴联苯醚当中,BDE-209是主要成分,质量浓度从0.12～2.38μg.L-1,中值为0.63μg.L-1,占多溴联苯醚总量的质量分数为63.57%～90.34%,其次是BDE-66、-99和-100,其它多溴联苯醚几乎没有检出,表明污染主要来自十溴联苯醚,其次是四溴和五溴联苯醚.实验结果与其它国家的数据相比,表明多溴联苯醚对普通妇女的污染在四川还处于一个较低的水平.     

同步衍生超声乳化微萃取气相色谱法测定环境水样中的苯胺类化合物

本研究建立了一种针对环境水样中苯胺类化合物检测的新方法——同步衍生超声乳化微萃取气相色谱法(SDUSAEME-GC-FID).通过氯甲酸丁酯(作为衍生剂/萃取相)的用量、超声时间、样品溶液p H值、离子强度和离心条件等因素对衍生/萃取效果影响的实验研究,确定了最优条件的关键性控制参数.结果表明,在选定条件下分析测定环境水样中5种苯胺类化合物,在6~60 000μg·L-1浓度范围内线性良好,相关系数R2为0.999 7~0.999 9,检测限LOD(3倍信噪比)为1.1~4.1μg·L-1,相对标准偏差RSD(n=6)为2.4%~5.7%,富集系数EF为317~846,测定7种实际环境水样的相对回收率RR为86.8%~105.5%.本方法具有操作简便、灵敏度高、经济环保的特点,可以作为检测环境水样中苯胺类化合物的一种首选方法.     

单克隆抗体间接竞争ELISA测定水体中氟虫腈

制备了氟虫腈单克隆抗体 ,在此基础上建立了水体中氟虫腈测定的间接竞争性酶联免疫吸附测定 (ELISA)法 .在优化条件下 ,氟虫腈测定的线性浓度范围为 1 0 -1 μg·L-1 ～ 1 0 3μg·L-1 ,最低检出浓度 (I1 0 )为 0 0 8μg·L-1 ,检测灵敏度 (I50 )为6 6 8μg·L-1 ;常见的几种与氟虫腈结构类似的农药的交叉反应率均低于 1 % ,不干扰氟虫腈的检测 ;2 0 %丙酮、5 %甲醇、2 %二甲基甲酰胺、2 %乙腈和 2 %乙酸乙酯基本不影响免疫测定 .利用建立的间接竞争性ELISA方法检测不同水样中氟虫腈 ,结果表明不同水样均可直接进行测定 ,方法的精密度和准确度均符合残留测定的要求     

关于气相色谱法测定水中丙烯酰胺的研究

研究并建立了毛细柱气相色谱-微池电子捕获检测器测定水中丙烯酰胺的方法。水样中丙烯酰胺经溴化衍生后,用乙酸乙酯萃取,经气相色谱法分析,取l00ml水样时方法检出限为0．017μg／L。丙烯酰胺在0．50～12．50μg／L范围内线性良好,在低、中、高3个添加水平,平均加标回收率为99．3％～114％,相对标准偏差为0．4％-3．5％。本方法准确度高、精密度好,适用于水中丙烯酰胺测定。     

某市岩溶地下水四氯化碳污染特征研究

赋存于寒武系和奥陶系灰岩中的岩溶水是某市的主要供水水源,每天供水量约为35×104t.2000年11月地下水监测资料表明,南郊水源地的岩溶水已受到了四氯化碳污染.污染源为一农药厂,该厂位于七里沟水源地补给区的山坡上,生产农药时用四氯化碳做溶剂.该厂生产废水中四氯化碳的浓度从281 0μg·L-1到2584 3μg·L-1.到2001年5月,水源地中53口水井中发现了四氯化碳,污染面积达17 5km2,井水中四氯化碳浓度最高达3909 2μg·L-1.根据四氯化碳浓度,污染区可以被划分为3个亚区:污染源附近亚区(初始最大浓度为3909 2μg·L-1,2003年4月最大浓度1891 5μg·L-1),集中抽水排泄区污染亚区(初始最高浓度195 5μg·L-1,2003年4月最大浓度504 5μg·L-1)和中间污染相对较轻的过渡区(一般20～200μg·L-1).过去3a间64口水井水质资料监测表明,岩溶含水层中四氯化碳含量受降雨、承压水位和含水层深度等多种因素的综合控制.由于四氯化碳为一种微溶于水的比水重的非水相有机物(DNAPL),它主要沿含水层底部运移,因此比较浅的水井(深度<150m)中四氯化碳含量比较低,而在深度较大的水井(深度>150m)中则浓度较高.     

含溴水源水臭氧处理时溴酸盐的产生与控制

针对南方某含溴水库水(溴离子浓度15～38μg·L-1),利用连续运行实验装置研究了臭氧氧化时溴酸盐的产生条件,同时初步考察了后续生物活性炭(BAC)对溴酸盐的去除效果.研究结果表明,单独采用预臭氧方式时,在臭氧消耗量控制为2.0mg·L-1以内的条件下,溴酸离子浓度低于6 μg·L-1;而采用预臭氧与后臭氧联合处理时,在总臭氧消耗量为2.0mg·L-1的条件下,出现了溴酸离子超标(10μg·L-1)情况.长期运行结果表明,尽管新炭对溴酸离子没有去除效果,但系统连续运行3个月后,BAC上的微生物对溴酸盐具有一定的去除能力.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

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.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

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.