Analysis of Trace Organic Pollutants in Coastal Marine Environment and a Feasibility Study Utilizing GC/MS Chromatographic Fingerprinting Techniques for Pollution Source Identification

随着社会经济的快速发展和海洋开发活动的不断增加，近岸海域的环境污染问题也越来越严重。本文针对近岸海域的污染现状，以气相色谱-质谱(GasChromatography-MassSpectrometry,GC-MS)技术为主要手段，建立了几类重要有机污染物的分析方法，发展了海洋污染物监测的新技术，并对近岸海域污染现状进行了调查；发展了海水中有机物的GC-MS指纹图谱技术，结合化学计量学模型，对所监测海域的污染来源进行判别，并计算各污染源对污染海域的贡献率；将示踪技术应用于海洋溢油的鉴别，拓展了溢油判别的思路，增强了判别方法的可靠性。具体的内容及其研究结果如下： 第一章对本工作的研究背景、意义与主...With the rapid development of economy and the accelerating effort in the exploitation of marine resources, the pollution of the coastal environment is becoming increasingly serious. In this study, we have developed several methods for the analysis of several classes of common marine contaminants including lignin, chloroacetanilide herbicides and organochlorine pesticides. Utilizing these methods, ...学位：理学博士院系专业：化学化工学院化学系_分析化学学号：B20032501

Transfer of amino acids in the food chain of key species anchovy(Engraulis japonicus) of the Yellow Sea and East China Sea food web

采用活体饵料对黄东海生态系统食物网关键种食物链的中下营养层次"浮游植物—中华哲水蚤(Calanus sinicus)—鯷鱼(Engraulis japonicus)"进行了室内模拟实验研究,以了解氨基酸在该食物链中的传递过程。通过76 d的培养实验,对采集样品做了14种氨基酸含量的定量分析。结果表明,在3个营养层次中中华哲水蚤起着十分关键的承上启下作用,它不仅将小球藻的植物性蛋白转化为动物性蛋白,大幅度地提高了赖氨酸的含量,而且将氨基酸总含量从小球藻的6.10%提高到24.16%。作为该食物网主要经济鱼类重要饵料的鯷鱼则进一步将氨基酸含量提高到27.06%。中华哲水蚤的氨基酸相对组成与小球藻有明显的相关性(r=0.606,p<0.05),其中7种必需氨基酸的相关性相对较弱,而非必需氨基酸的相关性明显较强。鯷鱼的食性由合成饵料转变为活体中华哲水蚤时,其氨基酸量也随饵料的改变而有所变化,从与合成饵料相关转为与中华哲水蚤有更紧密的相关。鯷鱼排泄粪便中的氨基酸含量主要由新陈代谢的生理过程所决定。Live baits Calanus sinicus were used to make an indoor experimental study on the intermediate and lower levels "phytoplankton-Calanus sinicus-anchovy(Engraulis japonicus)" in key species food chain of the Yellow Sea and East China Sea food web so as to know the transfer process of amino acids in the food chain.After making a cultural experiment for 76 days,the quantitative analysis of contents of 14 amino acids in the collected samples was made.It is shown from the analysis results that the copepod Calanus sinicus forms an intermediate key link,that is,the copepod not only transforms the vegetable protein of chlorella into animal protein of copepod and greatly raises the lysine content,but also raises the total amino acid content from 6.10% of chlorella to 24.16% of copepod.As an important bait of commercial fish in this food web,anchovy(Engraulis japonicus) further raises the total amino acid content of copepod to 27.06% of anchovy.There is a significant correlation between relative amino acid compositions of Calanus sinicus and chlorella(r=0.606,p<0.05),among them,the correlation between the percent contents of 7 essential amino acids of Calanus sinicus and chlorella was relatively poor,and that between the percent contents of 7 non-essential amino acids is relatively strong.The percent contents of amino acid of anchovy Engraulis japonicus changed with the change in baits when food of anchovy changed from synthetic bait to live Calanus sinicus.The amino acid contents of anchovy egesta are dependent mainly on metabolic process of anchovy.国家自然科学基金资助项目(40276046);; 国家重点基础研究发展规划资助项目(G19990437)~

Kinetics of Vesicle Formation and Breakdown

利用停流装置研究了十二烷基硫酸钠(SDS)和十二烷基三甲基溴化铵(DTAB)复配形成囊泡的过程和囊泡破坏过程的动力学性质,并结合动态光散射技术和电子透射显微镜探索囊泡形成和囊泡破坏过程的机理.动态光散射和电子透射显微镜的研究结果表明囊泡的形成过程主要包括四个阶段:混合胶团→柔性的长棒状聚集体→"非平衡囊泡"→平衡囊泡,而与其对应的粒度分散度则呈现"单分散性→多分散性"的周期性变化规律.此外,动力学结果表明囊泡形成过程很长,但其活化能不大,这意味着囊泡形成过程的控制步骤可能不是活化能控制.而相对于囊泡的形成,囊泡的破坏过程是十分迅速的.A combination of stopped-flow,transmission electron microscopy and dynamic light-scattering techniques has been used to study the kinetics of vesicle formation and breakdown as well as the mechanism of vesicle formation and breakdown in DTAB/SDS aqueous solutions.The results show that the process of vesicle formation can be modeled as a sequence of distinct processes:mixed micelles→flexible stick-shaped aggregates→non-equilibrium vesicles→equilibrium vesicle system,and the evolution of particle dispersion degree appears to be a periodical change of "monodispersity→polydispersity".In addition,the kinetic analysis shows that the process of vesicle formation lasts for a long time.However,the activation energy of vesicle formation is not too high,which implies that the control procedure of the process is independent of activation energy.In contrast to the process of vesicle formation,vesicle breakup to mixed micelles appears to be a rapid process.厦门大学科技创新重点项目(No.XMKJCX20052001)资助项目

Determination of Organophosphorus Pesticides in Seawater by GC-FPD Using Two Columns

本文提出了一种GC-FPD测定海水中28种有机磷农药残留的新方法。采用双柱法,即选用DB-1701柱进行定性、定量分析,用HP-5柱验证。既发挥了FPD检测器灵敏、定量准确的优点,又利用了双柱法的定性功能。方法对各目标物均有良好的线性关系,回收率和RSD分别在70.2%~103.2%、8.7%~17.5%之间,适合于海洋水体中痕量有机磷农药的分析。A GC method has been developed to determine 28 kinds of OPPs in seawater simultaneously by GC-FPD.The columns were DB-1701 and HP5.The column DB-1701 used for analysis and the column HP-5 used for validate.The linear dynamic ranges were well.the recovery was from70.2 %～103.2 %,the RSD was from 8.7 %～17.5 %.The method was used for the determination of trace OPPs in sea water.国家863项目(项目编号:2003AA635180

The Determination of Polycyclic Aromatic Hydrocarbons in Sediments with ASE/GC-MS

建立了用加速溶剂萃取技术提取含硫沉积物中痕量多环芳烃的可靠方法,优化了不同萃取剂,不同提取程序等萃取条件,研究了沉积物中的硫化物对色谱分离的影响。15种多环芳烃的检出限为0.09~1.34ng/g,相对标准偏差(RSD,n=6)为12.5%~23.9%,15种多环芳烃的低浓度加标回收在74%~138%之间。高浓度加标回收率除吲哚芘为62%外,其余都在80%~122%之间。基本上达到了痕量分析的要求。用该方法分析山东半岛近岸海域沉积物中多环芳烃的含量,测得15种PAHs的总量为273~579 ng/g。与其它地区沉积物中多环芳烃含量相比,属轻/中度污染。An accelerated solvent extraction method for the extraction of polycyclic aromatic hydrocarbons(PAHs) in sediments was developed.The extraction conditions such as extraction solvent and program were optimized.The effects of sulfide on chromatographic separation were studied.The detection limits for the fifteen PAHs were 0.09-1.34 ng/g,and the relative standard deviations(RSDs) ranged from 12.5% to 23.9%.The recoveries of high level concentration ranged from 62% to 122% and those of low level concentration ranged from 74%-138%.The contents of PAHs in sediment samples collected in the coastal regions off the Shandong peninsula,China were analyzed by this method.The PAHs in these samples ranged from 273 ng/g to 579 ng/g.Overall,the PAHs levels were comparable to those reported in the literature for sediment samples collected from similar environments around the world.国家高技术研究发展计划(863)基金项目(2003AA635180);; 青岛科技将才计划基金项目(04-3-J.J-11

固相微萃取-气相色谱-质谱联用测定海水和沉积物间隙水中的痕量多环芳烃

建立了固相微萃取(SPME)与气相色谱-质谱(GC-MS)联用同时测定海水中16种多环芳烃的分析方法,研究了萃取时间、盐度条件的影响．同时用SPME的方法研究了海水中的溶解有机物(DOM)对多环芳烃萃取的影响．计算出不同DOM浓度下多环芳烃KDOM与KOW的关系: CDOM=5 mg／L时,logKDOM=0．7944KOW+0．773(R2=0．91)．CDOM=10 mg／L时,logKDOM= 0．7905KOW+0．668(R2=0．97);CDOM=30 mg／L时,logKDOM=0．714KOW+1．0407(R2=0．91)．该法对16种多环芳烃的检出限为0．1-3．5 ng／L,相对标准偏差(RSD,n=5)为4％-23％．用该法分析海洋环境中的痕量多环芳烃,16种多环芳烃的平均回收率为88.2±20．4％,方法快速、灵敏、简单,适用于快速分析海水和沉积物间隙水样中的痕量多环芳烃．国家高技术研究发展计划(863)(批准号:2003AA635180);; 青岛科技将才计划(批准号:04-3-JJ-1)资助项

Simultaneous Determination of Multi-class Antibiotics Residues in Dried Aquatic Products by Liquid Chromatography-Tandem Mass(LC-MS/MS)Spectrometry

运用液质联用技术建立了水产干制品中40种抗生素的同时测定方法。含0.1%甲酸乙腈进行提取,考察了不同萃取溶剂及nA2EdTA添加量对目标抗生素回收率影响。目标抗生素在0.1~100μg/kg范围内线性良好;以基底匹配工作曲线进行定量,在高加标浓度下虾仁、鳗鱼干、红娘鱼干的加标回收率和rSd(n=4)分别为40.5%~138.6%和0.4%~19.4%、41.3%~134.5%和1.3%~11.6%、及40.3%~136.7%和0.1%~14.7%,方法检测限在0.1~0.5μg/kg。方法快速、简便,已成功应用于厦门周边常见水产干制品的检测。A method for simultaneous determination of 40 antibiotics in dried aquatic products was established using liquid chromatography tandem mass spectrometry(LC-MS/MS).Effects of experimental conditions,such as extraction solvents and Na2 EDTA adding on extraction efficiency were investigated.Under the optimized conditions,recoveries of 40 target drugs calculated by matrix match calibration curve at 20 μg/kg spiking level and RSD(n=4)were 40.5%~138.6% and 0.4%~19.4% for dried shrimp,41.3%~134.5% and 1.3%~11.6% for dried ell and 40.3%~136.7% and 0.1%~14.7% for dried gurnard,respectively.Most of method detection limits of target antibiotics ranged from 0.1 to 0.5 μg/kg.The method was sensitive,accurate,fast and successfully applied in the analysis of residual antibiotics in typical aquatic products in Xiamen

Progress in Analysis of Traditional Chinese Medicines for Organochlorine Pesticide Residues by Gas Chromatography

综述了中草药及其制剂中有机氯类农药残留的气相色谱分析技术,包括样品前处理方法,气相色谱分离分析及确证鉴定技术,对近几年来该领域研究进展进行了总结和讨论。This paper was mainly concerned on the application progress of gas chromatography(GC)in the analysis of Traditional Chinese Medicines(TCMs)for organochlorine pesticide residues(OCPs),such as DDTs and HCHs.The related procedures or techniques for extraction,clean_up,preconcentration,GC separation and identification/confirmation were reviewed respectively.Some typical analytical protoˉcols for several herbal materials(such as Radix Ginseng,Salvia miltiorrhiza Bge.,Herba Asari and etc.)or patent medicines were outlined in table.国家自然科学基金2003重点项目(20235020);; 亿利集团公司甘草GAP项

Determination of Andrographolide and Dehydroandrographolide in Andrographis paniculata Nees Materials and Related Patent Medicines by Reversed-Phase High Performance Liquid Chromatography

发展了穿心莲药材及其中成药中两种主要成分穿心莲内酯和脱水穿心莲内酯的反相高效液相色谱测定方法。采用甲醇振荡提取法进行样品前处理 ,在以乙腈 水为流动相作梯度洗脱、ODS柱、检测波长为 2 2 5nm的条件下 ,穿心莲内酯和脱水穿心莲内酯在 1 5min内可达到基线分离。两种内酯在 1 0mg/L～ 1 0 0mg/L时其浓度与峰面积成良好的线性关系 ,加标回收率为 96 %～ 1 0 4 %。该法适用于穿心莲药材及其制剂的质量分析检验A simple and accurate method for the determination of andrographolide and dehydroandrographolide in andrographis paniculata Nees materials and patent medicines with high performance liquid chromatography (HPLC) has been developed. The two components were extracted from powdered samples by shaking with methanol. The resultant extracts were separated within 15 min on a BECKMAN C 18 column (4 6 mm i d ×250 mm, 5 μm) and with a gradient elution of acetonitrile water at a flow rate of 0 5 mL/min . The detection wavelength was 225 nm and the injection volume was 20 μL. In gradient elution program the volume fraction of acetonitrile in mobile phase was as follows: 0 min-1 min, 40%; 1 min-5 min, 40%-50%; 5 min-15 min, 50%-70%. Both andrographolide and dehydroandrographolide have good linearity in the range of 10 mg/L to 100 mg/L with the correlation coefficients of 0 997?6 and 0 998?6 respectively. This method has been successfully applied for the analysis of andrographis paniculata Nees materials and related patent medicines.科技部中药现代化重中之重项目( 99 92 9 0 213);; 福建省科技部中药质量控制重点项目 (2 0 0 0F0 0 1)

Application of oil spill identification by GCMS——A case study

通过对中国近海海域一个具体海面溢油事例的研究,提出了通过气相色谱及气质联用技术进行海面溢油鉴别的方法。采用GC-FID对油样中的正构烷烃的主要组分进行定性分析,利用GC-MS对油中难降解的生物标记化合物:霍烷及其他五环三萜类化合物、规则甾烷及重排甾烷类化合物、三芳甾类化合物、多环芳烃进行分析,计算相应的比值并采用"t-分布"方法进行溢油样品和可疑溢油源样的相关分析。结果如下:(1)从GC-FID色谱图可以看出,YY2679与KY0631、KY0632的色谱图极其相似,与其余四个可疑油源的色谱图差异较大。六个可疑油源的R值在0.04~1.95之间,只有KY0631和KY0632的R值小于0.1,KY0633~KY0636与YY2679的差异不是由风化引起的,可以排除,由此可以推断出YY2679溢油样品可能来源于KY0631或KY0632两个可疑溢油源。(2)采用21个生物标志物指标进行相关性判别,KY0631可疑溢油源在比值点的区间范围为95%和98%时,有多个点x或y误差棒均未跨过直线y=x。KY0632可疑溢油源在比值点的区间范围为95%时,各点的x或y误差棒均跨过直线y=x,由此推断YY2679溢油样品和可疑油源KY0632是同一油源。On the basis of a case study,a method to identify the spilled oil at sea was introduced.N-alkane distribution patterns of unknown oil were recognized by gas chromatography-mass spectrometry determined the distribution of a suit of petroleum biomarkers hopanes,triterpanes,regular steranes diasteranes,triaromatic steroids and polycyclic aromatic hydrocarbons.The calculated diagnostic ratios for selected biomarker in the source of the spilled oil were done.The correlation studies compared the spill sample and suspected source were made.The results showed three samples nearly identical GC chromatographic profiles,n-alkane distribution patterns,as well as nearly identical diagnostic ratios.This implies that they were most likely from the same source.In 95%confidence limit,all diagnostic ratios of sample KY0632 is exactly the same as for YY2679,so conclusion that the sample of KY2679 and YY0632 are come from the same source