SPME-G C法测试TCE、PCE条件的正交优化试验研究

运用正交设计方法对SPME-GC法测试三氯乙烯、四氯乙烯的固相微萃取条件进行优化。首先选择样品量、NaCl用量、萃取温度、萃取时间、解析温度等因素,设计5因素3水平正交试验方案。分析数据得到优化条件为NaCl用量30 g/L,萃取温度25℃,解析温度210℃,同时得出样品量与萃取时间是对试验结果具有显著意义的影响因素,采用二次回归正交组合设计试验对其进一步优化,并对结果进行回归分析,得到最优条件为样品量为5.5 mL,萃取时间为20.13 min。     

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。     

水体新型污染物现场快速富集方法的研究

该文采用新型胶束-乳液聚合法制备了两亲多孔吸附材料作为固相萃取吸附剂,并且为其配套研制了一种可用于现场大体积富集水质中痕量污染物的全自动固相萃取采样装置(LVED)。使用新研制的装置建立了LVED-HPLC-MS/MS方法快速测定环境水样中40种痕量新型污染物的方法,实验优化了大体积固相萃取条件并进行方法学验证,证明该方法具有良好的线性关系(r~2≥0.992),以及较低的检出限(0.002～0.10 ng/L)。将此方法用于实际环境水样中新型污染物的现场富集与检测,不同污染物的加标回收率分别为78.0%～107%,部分污染物实际检测浓度在0.05～90.5 ng/L。该方法是一种简便、快速、高效的现场大体积萃取环境水样中痕量新型污染物的新方法,具有应用和推广前景。     

新型循环冷凝固相微萃取方法的研究

首次提出一种新型循环冷凝萃取(CC-SPME)方法,并以乙硫醚为研究对象进行了分析检测。实验优选条件得出CC-SPME法的萃取时间,溶液加热温度和解吸时间分别为25min,75℃,4min。该方法的重现性,检测限以及回收率分别为7.54%,0.010mg/L,97%。实验表明,此方法的线性很好,而且与传统的浸入萃取法和顶空萃取法相比,具有更高的灵敏度。故而CC-SPME法是一种简单且灵敏的分析检测方法,值得做进一步探讨。     

地表水中阿特拉津检测方法的研究

利用固相萃取的方法对水样中的阿特拉津进行富集、洗脱和浓缩,得到了良好的分离效果、较宽的线性关系和较高的灵敏度,建立了水体中阿特拉津的高效液相色谱检测法。能达到地表水环境质量标准GB3838-2002中的要求。确定了固相萃取方法的相关条件,并在0.4 mg/L的阿特拉津标准样品下对色谱条件进行了优化,得出流动相配比在80～20,柱流速在0.45 mL/min,DAD检测波长为262 nm时,检测最佳。应用此检测条件得出标准曲线为y=0.229 6x+0.007 6,R2=0.999 3。用该方法实现了对地表水中阿特拉津的检测。     

HF-LLLME-CE法测定偶氮染料氧化降解生成的有机酸

采用纤维膜三相液相微萃取(HF-LLLME)和毛细管电泳技术,对偶氮染料氧化降解过程中可能产生的小分子羧酸甲酸、乙酸、草酸、乳酸、丁二酸、柠檬酸、苹果酸进行了测定。以pH值为7.2的230 mmol/L磷酸二氢钠、115 mmol/L四硼酸钠和0.5 mmol/L十六烷基三甲基溴化铵(CTAB)溶液为缓冲液,分离电压-12 kV,检测波长200 nm的条件下,10 min内达到基线分离。三相液相微萃取以磷酸三丁酯(TBP)为有机相,供体相pH为2.5,接收相pH为12.0,萃取时间为45 min,将萃取接收相直接进行毛细管电泳(CE)测定,富集倍数在7~67之间。样品相中7种有机酸的质量浓度在5 mg/L~1 000 mg/L的范围内与电泳峰面积呈良好线性(r2>0.999 1),方法的检出限为0.09 mg/L~0.54 mg/L。运用该法对TiO2光催化降解偶氮染料过程中产生的有机酸进行测定,检测到的4种羧酸的投加回收率在93%~110%之间。     

超高效液相色谱串联质谱测定地表水中5种磺胺类药物残留研究

建立了一种快速、灵敏、同时定性和定量的固相萃取(SPE)和超高效液相色谱串联质谱法(UPLC-MS/MS)来测定地表水中5种常用磺胺类药物(SAs)残留。100 m L水样经0.45μm滤膜过滤后,利用HLB固相萃取柱来浓缩富集。色谱分离柱选用BEH C18(1.7μm,50×2.1 mm)色谱柱,流动相选用甲酸水溶液/乙腈,0.30m L/min梯度洗脱。在电喷雾-多反应监测正离子模式下,进行定量定性分析。线性范围在0.2~20 ng/m L之间,r2≥0.997。以标准加入法计算回收率和相对标准偏差,在2~10 ng/L添加浓度范围内,平均回收率在75.2%~84.6%之间,相对标准偏差在4.1%~8.6%之间,最低检测限和定量限分别为0.03 ng/L和0.05 ng/L。综合讨论了HLB萃取柱对水和废水中磺胺类药物的浓缩富集作用,探讨了几种影响浓缩富集效果的条件,优化了提取和净化方法。最后应用该方法检测哈尔滨周边地点地表水中5种磺胺类药物的残留情况。     

分散液液微萃取气相色谱质谱联用法测定海水中三氯苯

本文建立了分散液液微萃取结合气相色谱质谱联用法测定海水中三氯苯(TCBs)的方法。考察了萃取剂和分散剂的种类、体积、超声萃取时间、萃取温度等对模拟海水加标样品的萃取效率的影响,得到最佳萃取实验条件为:以丙酮为分散剂、氯苯为萃取剂,超声萃取时间为10 min,萃取温度为25℃。样品的加标回收率为97.8%~102.5%,相对标准偏差为2.8%~6.6%。1,3,5-,1,2,4-和1,2,3-TCB的方法检出限分别为1.5 g/L,0.5 g/L和2.0 g/L。该方法与顶空、液液萃取和固相萃取法相比具有检出限低、富集因子高、重现性好、操作简便、干扰小等优点。采用本方法对5个实际海水样品中的TCBs进行了定量检测,结果表明其中两种样品含有2~3种待测物,浓度范围为1.9~6.7 g/L。     

污灌区地下水中有机污染物的分离鉴定与致突变活性研究

应用XAD系列大孔网状树脂萃取富集法,结合GC、GC/MS/DS1的分离鉴定技术,研究了北京东郊污灌区深层(90m)和浅层(18m)地下水中的有机污染物。采用LSC-GC/MS/DS装置测定了地下水中的挥发性有机物,并对水样进行了Ames试验以检验水样的致突变活性。结果从深井水样中检出32种非挥发性有机物,未检出挥发性有机物,致突变试验阴性。浅井水样中同时检出非挥发性和挥发性有机物。两种菌株在所有试验条件下均呈现阳性致突变反应。     

高温水萃取在食品安全快速检测中的应用研究

采用高温水萃取方法对食品中农药残留、甲醛、亚硝酸盐、抗生素等成分进行快速萃取,结合分光光度法、液相色谱等分析方法进行了上述成分的快速检测研究。结果表明,蔬菜中甲胺磷的萃取条件为pH=8.0的磷酸缓冲溶液、萃取温度120℃、萃取时间2～3min;腐竹中甲醛的萃取条件为0.1mLH3PO4溶液/10mL、萃取温度120℃、萃取时间5min;肉制品中亚硝酸盐的萃取条件为5mL硼砂饱和溶液/10mL、萃取温度120℃、萃取时间5min;饲料中四环素的萃取条件为pH=2.0的盐酸溶液、萃取温度100℃、萃取时间4min。与现有的蒸馏、振荡萃取、超声萃取等预处理方法比较,高温水萃取法具有萃取效率高、精密度好、快速、简便和不使用有机溶剂的优点,可以满足实际样品快速检测的需要。     

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.