Development of Isotope Dilution Surface Ionization Mass Spectromety and its Use as the Absolute Analytical Method for Heavy Metals in Standard Reference Materials

用<^(107)Ag>、<^(116)Cd>、<^(65)Cu>、<^(61)Ni>、<^(206)Pb>、<^(203)Tl>和<^(68)Zn>加峰后，在低温高压下分解成<HNO_3>、HC <10_4>和HF的混合物。将分解后的样品加热干燥，得到的残渣溶解在稀释的<HNO_3>溶液中。从溶液的等分物中提取重金属作为二硫代盐进入氯仿中，并将其应用于配备有Re单灯丝表面电离装置的日立RMU-6质谱仪。随着电离温度的升高，可以通过测量<^(205)Tl> / <^(203)Tl>、<^(109)Ag> / <^(107)Ag>、<^(63)Cu> / <^(65)Cu>、<^(114)Cd> / <^(116)Cd>、<^(208)Pb> / <^(206)Pb>、<^(58)Ni> / <^(61)Ni>和<^(66)Zn> / <^(68)Zn>来依次测定它们在样品中的浓度。本方法可以测量上述元素的微小量，即<10^(-9)> - <10^(-11)> g，精度为1%。样品都是在超洁净通风室和100级加压室的长凳上制备的，后者由不锈钢双层墙壁和甲氧基树脂覆盖的地板构成。试剂和水均采用亚沸点蒸馏法纯化。质谱计可以探测到元素发射的质谱中小于10^(-19)> A的发射极电流，并以0.1%的变异系数精度测量同位素比值。这些刺钉是从田纳西州的橡树岭国家实验室进口的。将每个穗溶解在稀释的<HNO_3>溶液中，并储存在密封的聚四氟乙烯或石英瓶中。每个峰的同位素丰度和摩尔浓度都与标准物质进行了标准化。工作复合钉钉溶液是在使用前通过混合原液制备的。该方法已成功应用于岩石、植物、动物、极地冰和海洋水等环境样品以及工业材料。少

After spiking with <^(107)Ag> , <^(116)Cd> , <^(65)Cu> , <^(61)Ni> , <^(206)Pb> , <^(203)Tl> and <^(68)Zn> , the spiked sample was decomposed in a mixture of <HNO_3> ,HC <10_4> and HF at low temperature under pressure. The decomposed sample was heated to dryness and the residue obtained was dissolved in a dilute <HNO_3> solution. The heavy metals were extracted from an aliquot of the solution as their dithizonates into chloroform and applid to the mass spectrometer(Hitachi RMU-6) equipped with a surface ionization device incorporating a Re single filament.Their concentrations in the sample could be successively determined by measuring <^(205)Tl> / <^(203)Tl> , <^(109)Ag> / <^(107)Ag> , <^(63)Cu> / <^(65)Cu> , <^(114)Cd> / <^(116)Cd> , <^(208)Pb> / <^(206)Pb> , <^(58)Ni> / <^(61)Ni> and <^(66)Zn> / <^(68)Zn> with raising ionization temperature. The present method could measure minute amounts, i.e., <10^(-9)> - <10^(-11)> g of the above elements with an accuracy of 1%.Samples were all pr … More epared in a ultra clean draft chamber and on benches set in a class 100 pressurized room,the latter being constructed of stainless steel double walls and having a methoxy-resin covered floor. Reagents and water were all purified by sub-boiling distillation method.The mass spectrometer could detect an emitter current of <10^(-19)> A for the mass spectrum emitted by an element and measure the isotopic ratio with an accuracy of 0.1% in the coefficient of variations.The spikes were imported from the Oak Ridge National Laboratory, Tenn., U.S.A., and each spike was dissolved in a dilute <HNO_3> solution and stored in a tightly stoppered teflon or quartz bottle. The isotopic abundance and molar concentration of every spike were standardized to the reference materials. The working composite spike solution was prepared by mixing the stock solutions just prior to the use.The method has been applied with a good success to the environmental samples such as rocks,plants,animals,Polar ice and oceanic waters as well as industrial materials. Less