Development and Application of the Online Photochemical Vapor Generation Technique Coupled with ICPMS

光化学蒸气发生技术（PCVG）应用于痕量元素分析方面具有诸多优势：由于它是一种气体进样技术，其样品传输效率几乎接近100%；实现了分析物与样品基体的分离，从而减少基体对检测过程的干扰；挥发性产物经气液分离后被引入检测器，避免了液体进样时原子化器/离子源温度降低，进而影响方法性能的情况；添加的小分子有机试剂还原性较弱，过程中产生的氢气量较少，有利于后续检测仪器的稳定；试剂最终光解为H2O、CO2等小分子，对环境十分友好。正因为这些优点，PCVG受到越来越多分析工作者的关注，并开展了大量的元素分析、形态分析、机理研究、相关硬件研发等方面的研究工作。可见，PCVG技术在痕量元素分析方面有很好的应用前...As one of the most promising CVG techniques, photochemical vapor generation (PCVG) has numerous advantages on the application of trace element analysis. Because it is a gas sampling technique, its analyte transport efficiency is very high and nearly 100%; it separates the analyte from the matrices and decreases the matrix effect on detection; volatile products are separated from the liquid phase b...学位：理学博士院系专业：海洋与地球学院_海洋化学学号：2242011015361

Study and Application of Photochemical Vapor Generation-ICPMS method for noble metal elements

光化学蒸气发生技术（PCVG）是一种实现了分析物与样品基体分离的气体进样技术，应用于痕量元素分析方面具有诸多优势。本研究利用特制的光化学蒸气发生装置首次得到了Ir和Ru的稳定可靠的PCVG信号。将光化学蒸气发生装置，与流动注射体系以及ICPMS检测技术联用，通过优化小分子有机酸的种类及浓度、照射时间、载气流量等条件，建立了FI-PCVG-ICPMS分析水样中Au、Ag、Pt、Rh、Pd、Ir、Ru等贵金属元素的方法。方法精密度除了Ru为9.2%（0.1µg/L，n=5）外，其他元素均小于4.6%（Ag，0.2µg/L，n=5）。检测限（LOQ，10σ，n=10）为5pg...Photochemical vapor generation (PCVG), as a gas sampling technique that makes analytes separate from matrix, has numerous advantages on the application of trace element analysis. In this study, stable and reliable PCVG signals of Iridium and ruthenium were firstly abtained using a special PCVG device. The PCVG device was coupled with a flow injection system and ICPMS technique. The main factors of...学位：博士后院系专业：化学化工学院_分析化学学号：201517005

Accurate Measurement of Trace Level of As, Sb, Bi, Ge, Sn, and Hg in Coastal and Estuarine Seawater and Its Application

研究论文内容分为4章：第1章介绍了砷（As）、锑（Sb）、铋（Bi）、锗（Ge）、锡（Sn）和汞（Hg）六种元素的环境地球化学特征，总结了常用的分析测定方法，对As、Sb、Bi、Ge、Sn和Hg等六种元素的研究进展进行了概述。 第2章建立了化学蒸汽发生（CVG）与电感耦合等离子体质谱（ICP-MS）联用同时测定As、Sb、Bi、Ge、Sn和Hg的方法。将CVG与灵敏度高的检测器ICPMS联用，克服了海水盐度高、待测元素浓度低等特点对分析方法的限制，建立了同时测定近岸及河口海水中痕量As、Sb、Bi、Ge、Sn和Hg等元素的方法。研究了CVG过程中KBH4、盐酸和硫脲浓度，以及样品流速、载气流...The thesis contains four chapters. The first part is a summary of the background information on As, Sb, Bi, Ge, Sn and Hg research, including the environmental characteristics and analysis method. The second and third parts of this work are to design a rapid and accurate procedure to measure trace level of As, Sb, Bi, Ge, Sn, and Hg in coastal and estuarine seawater and to apply it in Jiulongjiang...学位：理学硕士院系专业：海洋与环境学院海洋学系_海洋化学学号：2242008115146

Determination of 24 Trace Level of Rare Earth and Metal Elements in Coastal and Estuarine Seawater by Polymer Complexation-Ultrafiltration Technique and Inductively Coupled Plasma Mass Spectrometry

建立了聚丙烯酸螯合-超滤(PCP-uf)分离富集、电感耦合等离子体质谱(ICP-MS)测定海水中痕量稀土及金属元素的方法。PH值高于7.5时,海水中的稀土离子、Cu2+、Pb2+、Cd2+、CO2+、nI2+等与聚丙烯酸(PAA)形成稳定的高分子螯合物,经超滤截留、硝酸解离后,实现了稀土及金属元素从海水中的分离、富集;采用ICP-MS的全定量数据采集模式、内标校正的标准校正曲线法对待测元素进行定量分析。在优化实验条件下,方法的相对标准偏差(rSd)为1.7%~7.3%,加标回收率为73%~96%;方法的定量下限(lOQS,10σ)为0.23~13.9 ng/l,方法空白为0.09~8.38 ng/l。建立的方法可用于近岸及河口海水中痕量稀土及金属元素的同时测定。A method of polyacrylic acid-complexation and ultrafiltration for matrix modification and inductively coupled plasma mass spectrometry(ICP-MS)was developed for the determination of 24 trace level of rare earth elements(REEs) and metal elements in coastal and estuarine seawater.REEs ions,Cu2+,Pb2+,Cd2+,Co2+,Ni2+ could reacted with polyacrylic acid(PAA) to form stable complexes when the pH value was above 7.5,which could be separated and enriched absolutely after trapped and eluted from the ultrafilter.Full quantitative data collection mode and internal standard calibration curve were used for the ICP-MS determination.Under the optimized conditions,the relative standard deviations(RSDs) were in the range of 1.7%-7.3%,and the spiked recoveries were between 73% and 96%.The limits of quantitation(LOQs,10σ) ranged from 0.23 ng/L to 13.9 ng/L.The method blank ranged from 0.09 ng/L to 8.38 ng/L.The developed method could be applied in the simultaneous determination of REEs and metal elements in coastal and estuarine seawater.厦门大学近海海洋环境科学国家重点实验室自主创新项目(MELRI0703

Simultaneous Determination of Ultra-trace Level of As,Sb,Bi,Ge,Sn and Hg in Coastal and Estuarine Seawater by Chemical Vapor Generation and Inductively Coupled Plasma Mass Spectrometry

建立了化学蒸汽发生(CVg)电感耦合等离子体质谱(ICP MS)同时测定近岸及河口海水中超痕量AS、Sb、bI、gE、Sn和Hg元素的方法。研究了CVg过程中kbH4、盐酸和硫脲的浓度以及样品流速、载气流速、海水样品盐度等对方法分析性能的影响。结果表明,在0.70%盐酸、0.10 g/l硫脲、11.0 g/l硼氢化钾、载气0.40 l/MIn条件下,6种待测元素的信噪比最高。优化实验条件下,AS、Sb、bI、gE、Sn和Hg的质量浓度在0.1~5.0μg/l内呈良好线性,相关系数不低于0.996 6;方法对0.1μg/l加标样品的相对标准偏差(rSd,n=5)为3.9%~8.9%,实际海水样品的加标回收率为89%~112%;方法的流程空白为0.012~0.036μg/l,定量下限(lOQS,10σ)在0.006 7~0.026μg/l之间,可满足近岸及河口海水样品中超痕量元素测定的需要。A chemical vapor generation(CVG) and inductively coupled plasma mass spectrometric(ICP MS) method was proposed for the simultaneous determination of ultra-trace level of As,Sb,Bi,Ge,Sn,and Hg in coastal and estuarine seawater.Effects of operating parameters,including concentrations of KBH4,HCl and thiourea,pump flow rate and carrier gas flow rate on analytical performance were studied.The results showed that good signal to noise(S/N) ratios for all the analysed elements were obtained when 0.70% HCl,0.10 g/L thiourea,11.0 g/L KBH4,and 0.40 L/min carrier gas were used in the CVG procedure.The relative standard deviations(RSDs,n=5) for 0.10 μg/L spiked sample were in the range of 3.9%-8.9%.The spiked recoveries for the seawater samples were between 89% and 112%.The method blanks were in the range of 0.012-0.036 μg/L.The limits of quantitation(LOQs,10σ) for the developed method were obtained between 0.006 7 μg/L and 0.026 μg/L.The method could be applied in the simultaneous determination of As,Sb,Bi,Ge,Sn and Hg in coastal and estuarine seawater.近海海洋环境科学国家重点实验室自主创新项目(MELRI0703

A New Method for the Measurement of Complexation Stability Constant and Average Coordination Number of Metallic Element with Polymer

建立了基于化学平衡理论模型以及凝胶过滤色谱(gfC)-电感耦合等离子体质谱(ICPMS)联用技术的高分子聚合物-金属配合物稳定常数、平均配位数测定新方法。以聚乙烯亚胺(PEI)和Cu2+为例,对形成的PEI-Cu配合物稳定常数、平均配位数进行测定,以0.02 MOl·l-1 HAC-nAAC为流动相,凝胶色谱柱分离大分子PEI-Cu配合物以及Cu的小分子配合物、游离态离子,最后用ICPMS测定不同形态金属元素的浓度;利用建立的化学平衡理论模型,计算PEI与金属离子形成配合物的稳定常数、平均配位数,测得25℃,PH4.1~5.3时,PEI-Cu配合物稳定常数为109.6~1010.7,平均配位数为1.0~1.3。建立的在线分离、测定方法具有快速、准确的特点,为高分子聚合物-金属配合物的研究提供新的技术手段。A new method using gel filtration chromatography(GFC) and inductively coupled plasma mass spectrometry(ICPMS) was developed for the measurement of complexation stability constant and average coordination number of the complex of metallic ion with polymer.As an example,the binding of PEI with Cu2+was shown and investigated.The macromolecular PEI-Cu complex and micromolecular species of Cu (Ⅱ) were firstly separated by a low efficiency GFC column with a mobile phase of 0.02 mol·L-1HAc-NaAc buffer,and then directly introduced into ICPMS for elemental analysis.The results of complexation stability constant and average coordination number characterized by putting the concentration of different species of metallic element into the equations of the novel chemical equilibrium model which was developed in this study.The results shown that the complexation stability constants(KPEI-Cu) were between 109.6and 1010.7and the average coordination numbers(n) were in the range of 1.0~1.3 when pH was changed from 4.1 to 5.3 at 25 ℃.This online,rapid and accurate method of GFC-ICPMS is a novel technique for the research of polymer-metallic complex.厦门大学近海海洋环境科学国家重点实验室自主创新项目(MELRI0703)资助项

第十八届美国理论与应用力学大会总结

1会议概况2018年6月5—9日,第18届美国理论与应用力学大会(18th U.S. National Congress of Theoretical and Applied Mechanics, USNCTAM2018)在美国芝加哥召开.本次大会由美国力学国家委员会和中国力学学会联合主办,旨在探讨和交流近四年世界范围内在理论和应用力学领域的基础研究、创新技术的最新进展,吸引了来自世界各地的近千名专家学

Determination of Trace Metal Elements in Coastal and Estuarine Seawater by Polymer-Complexation-Ultrafiltration Technique and Inductively Coupled Plasma Mass Spectrometry

建立了高分子聚合物螯合-超滤(PCP-uf)分离富集、电感耦合等离子体质谱(ICP-MS)测定海水中痕量金属元素的方法。海水中的Cu2+,Pb2+,Cd2+,CO2+,nI2+等金属离子与聚乙烯亚胺(PEI)形成高分子螯合物,经超滤截留、酸解离后,实现金属离子从海水中定量分离、富集。ICP-MS采用全定量数据采集模式、内标校正的标准校正曲线法进行定量分析。在最佳条件下,方法的相对标准偏差(rSd)在3.4%(Cd)~9.3%(Pb)之间(0.20μg/l,n=5),标准加入回收率为78.7%(Ag)~95.2%(Cu);检出限(dl,10&)为1.2 ng/l(Cd)~9.8 ng/l(Cu),空白为1.1 ng/l(Cd,Ag)~9.1 ng/l(Cu)。本方法可应用于近岸及河口海水样品中痕量金属元素的同时测定。A method using polymer-complexation and ultrafiltration for matrix modification and inductively coupled plasma mass spectrometry(ICP-MS) for determination of trace level of metal elements(Cu2 +,Pb2 +, Cd2 +,Ni2 + and Ag +) in coastal and estuarine seawater has been developed.Full quantitative data collection mode and internal standard calibration curve were used for ICP-MS measurement.Under optimized conditions, the relative standard deviations(RSDs) were lower than 9.3%(0.20 μg/L,n = 5),and the standard added recoveries were 78.7%-95.2%.Detection limits(10 &) were from 1.2 ng/L(Cd) to 9.8 ng/L(Cu).The method blank ranged from 1.1 ng/L(Cd,Ag) to 9.1 ng/L(Cu).The developed method has been applied to simultaneously determine the metals in coastal and estuarine seawater.厦门大学近海海洋环境科学国家重点实验室自主创新项目(No.MELRI0703)资

Simultaneous Determination of 5 Water-soluble Vitamins by HPLC with On-line Photochemical Derivatization and Fluorescence Detection

建立了高效液相色谱分离-在线光化学衍生/荧光光谱法测定水溶性维生素烟酸(nIA)、烟酰胺(nIC)、b1、b12及b2的新方法。以含有0.018 MOl/l三乙胺、0.002 MOl/l庚烷磺酸钠的0.05 MOl/l磷酸盐缓冲液(A相,PH 5.8)和甲醇(b相)为流动相(85∶15),等度洗脱分离5种水溶性维生素;将自制的程序控制时间/光强光化学反应器接在二极管阵列检测器(dAd)和荧光检测器(fld)之间,进行光化学衍生。优化了光化学衍生的条件,并用于复合维生素片中水溶性维生素的测定。在优化实验条件下,5种水溶性维生素的线性范围分别为:nIA、nIC为0.1~10.0 Mg/l,b1、b12为0.2~20.0 Mg/l,b2为0.01~1.0 Mg/l,方法的检出限(lOd,3σ)和定量下限(lOQ,10σ)分别为1.5~25.4μg/l和5.0~84.7μg/l,优于传统的高效液相色谱分离/二极管阵列检测方法。方法的相对标准偏差(n=7)不大于7.8%,样品的加标回收率为98%~103%。A high performance liquid chromatographic(HPLC) method using on-line photochemical derivatization and fluorescence detection was developed for the simultaneous determination of nicotinic acid(NIA),nicotinamide(NIC),thiamine hydrochloride(B1),riboflavin(B2) and cyanocobalamin(B12).A self-built time/energy programmed photochemical reactor(PCR) with an ultraviolet mercury lamp was installed between the diode-array detector(DAD) and fluorescence detector(FLD) to convert the non-or weakly fluorescent vitamins into fluorescence compounds.The separation of NIA,NIC,B1,B12 and B2 was achieved within 12 min using 0.05 mol/L phosphate buffer(pH 5.8)-0.018 mol/L triethylamine-0.002 mol/L sodium heptane sulfonate(A) and methanol(B) as mobile phase by isocratic elution(A∶B,85∶15).The separation and photochemical derivatization conditions were optimized.Under the optimal conditions,the calibration curves of five vitamins were linear in the range of 0.1-10.0 mg/L for NIA and NIC,0.2-20.0 mg/L for B1 and B12,0.01-1.0 mg/L for B2 with correlation coefficient(r) more than 0.996.The limits of detection(LOD,3σ) ranged from 1.5 μg/L to 25.4 μg/L and the limits of quantitation(LOQs,10σ) were 5.0-84.7 μg/L,which were better than those of the traditional HPLC/DAD method.The relative standard deviations(RSDs,n=7) were not more than 7.8% and the spiked recoveries were between 98% and 103%.The developed method was successfully applied in the determination of vitamins NIC,B1 and B2 in multivitamin tablets.UniversityresearchgrantfromAgilentTechnologiesFoundation;US