微波消解-微波等离子体炬原子发射光谱法测定无铅汽油中痕量铅的研究

四乙基铅作为一种良好的抗爆添加剂,曾广泛用于汽油生产中,但由于四乙基铅有很强的毒性,目前国际上已停止生产和使用车用含铅汽油,因此在生产车用无铅汽油时严格控制和准确测定铅的含量十分必要.迄今,测定汽油中铅含量的常用方法是铬酸盐容量法^[1]、一氯化碘法^[2]、X射线光谱法^[3]、分光光度法^[4,5]、原子吸收光谱法^[6]和等离子体光谱法^[7].这些方法或操作烦琐,测定时间较长^[4],或灵敏度低^[1～3],或测定误差较大,且在测试中需使用毒性较大的四乙基铅^[5],或所需的氯化甲基三辛基铵不易购买^[6],或处理过程繁琐,且仪器设备昂贵^[7].因此,建立一种简便、快速、灵敏、准确和无毒副作用的测定无铅汽油中痕量铅的方法已显得十分迫切.近年来发展的微波等离子体炬原子发射光谱法^[8]已有商品化仪器问世^[9].本文利用微波等离子体炬原子发射光谱仪研究了无铅汽油中痕量铅的测定方法,并提出用微波消解法预处理无铅汽油样品,将微波消解技术与微波等离子体炬原子发射光谱法相结合,建立了简便、快速、灵敏、准确和无污染的测定无铅汽油中痕量铅的新方法.     

水溶液中丙酮的敏化室温磷光测定

测定水溶液中微量丙酮,常用吸光光度法^[1～3]和色谱法^[4,5]等,这些方法固然灵敏度较高,但样品的预处理比较复杂,分析速度慢,线性范围窄.本文以丁二酮为能量受体,建立了水溶液中微量丙酮的敏化室温磷光测定法.方法简便快速,重现性好,灵敏度亦高.     

茜素红S螯合树脂分离富集测定地质样品中的痕量金、铂和钯

用螯合树脂对金属进行分离富集及测定,前人已做了许多有意义的研究^[1～4].曾用含键合S双硫腙(P-D)和脱氢双硫腙(P-DT)功能团的离子交换树脂和螯合树脂分离金和铂族金属^[5],用双硫腙负载树脂分离富集Cu(Ⅱ)^[6]。     

缝管增强火焰原子吸收分析灵敏度的研究—铅的测定

近年来,人们为了提高火焰原子吸收光谱分析的灵敏度,采用了一些新技术.Watling首先提出使用开缝石英管提高火焰原子吸收法测定某些元素的分析灵敏度和准确度。之后,缝式石英管火焰原子吸收技术在实际工作中得到了应用和发展.最近,刘永铭等考察了管性能的影响,指出该技术的可行性。一般认为缝管火焰原子吸收法提     

静电纺丝法制备NiO纳米纤维及其表征

纳米级NiO因具有优良的催化和热敏等性能而被广泛用于催化剂^[1]、电池电极^[2,3]、光电转化材料^[4～6]、电化学电容器^[7～8]等诸多方面.迄今,已成功地制备出N iO的纳米颗粒^[9]、纳米线^[10]及纳米薄膜^[11],但是对于具有准一维结构的NiO纳米纤维的制备及性能研究尚未见报道.     

碳苷研究(Ⅵ)——1-芳基-D-吡喃葡萄糖碳苷的快原子轰击质谱

快原子轰击质谱(FAB-MS)是近几年发展起来的一种质谱新技术^[1],特别适于极性大、不易挥发和对热不稳定的化合物,已用于多肽^[2]、核酸^[3]及苷^[4]的结构测定。     

植物生物分子的电分析化学研究Ⅷ.秋水仙碱的微分脉冲极谱行为及分析应用

秋水仙碱是近年来新发现的有前途的抗癌植物有效成分。秋水仙碱的测定方法,如容量滴定法^[1]、电位滴定法^[2]、紫外分光光度法^[3]、荧光分析法^[4]和高效液相色谱法^[5]等,手续均不太简便。电化学分析研究秋水仙碱主要有阳极伏安法^[6]和交流极谱法^[7],前者因使用固态电极,重现性较差。后者用非水溶剂作介质,灵敏度不高。     

用乙基紫作铼的分光光度测定

用甲基紫^[1-5]及其他碱性染料^[6-8]作试剂萃取及光度测定铼已有记录.此类方法选择性较硫氰酸盐法为高.Оболончик曾指出,如增加染料分子量能提高测定灵敏度.与甲基紫比较,乙基紫(C.I.42600)分子量较高,可能利于萃取.实验证实,用此试剂光度测定铼可获较高灵敏度^[1].本文报告用苯萃取高铼酸乙基紫的各种条件,提出有钼等其他元素共存时分光光度测定痕量铼的方法.     

对-氯甲基苯乙烯共聚物引发合成接枝共聚物

接枝共聚物含有性质差别很大的主链和支链,具有许多特殊的性质,因而一直是人们感兴趣的研究课题之一^[1～5].原子转移自由基聚合(ATRP)^[6,7]的问世,为接枝共聚物的合成提供了一条新的途径.本文用对-氯甲基苯乙烯和其它乙烯基单体自由基共聚.     

PAP-H2O2-HRP伏安酶联免疫分析新体系测定人血清总甲状腺素

目前临床检测中测定总甲状腺素(T₄)的常用方法有间接血凝试验、琼脂双扩散及ELISA等方法^[1].其中ELISA法是目前较为流行的检测方法,但灵敏度不高.伏安酶联免疫分析法具有广阔的应用前景^[2,3].     

Application of the slotted quartz tube in flow-injection flame atomic-absorption spectrometry

The slotted quartz has been applied to flow-injection flame atomic-absorption spectrometry (FI-FAAS) showing several important advantages. The tube life was improved by a factor of 5-6 compared to conventional continuous aspiration. Flow impact systems were found not to be necessary in the applications so that larger enhancement factors may be achieved without sacrifice in precision. For 1.0 mg/l. copper, 1.0 mg/l. lead, 0.1 mg/l. cadmium and 1.0 mg/l. gold sensitivity enhancement factors of 3.1, 5.5, 5.3 and 4.0 were obtained with precisions of 1.3%, 1.1%, 1.6% and 1.7% RSD (n = 11) respectively. Application of the slotted quartz tube FI-FAAS method to the determination of heavy metals in urine has shown improved tolerance to interfering matrices. Recoveries obtained by spiking undiluted urine samples with 0.1 mg/l. copper and lead, and 0.01 mg/l. cadmium were in the range 100-102%.     

Direct determination of cadmium at parts-per-billion level in waters by derivative atomic absorption spectrometry using atom trapping technique

A method has been described for the direct determinations of trace cadmium using derivative atom trapping flame atomic absorption spectrometry with an improved water-cooled stainless steel trapping equipment. The characteristic concentration (gave a derivative absorbance of 0.0044) and detection limit (3sigma) of cadmium were 0.028 and 0.02 ng ml(-1) when collecting for a 1 min, respectively, which were 992 and 145-fold better than those of the conventional flame atomic absorption spectrometry. The detection limit and sensitivity of the proposed method for a 2 min collection time were 1 and 2 orders of magnitude higher than those of conventional flame atomic absorption spectrometry. The present method was applied to the determinations of cadmium in water samples with a recovery range of 91 approximately 111% and a relative standard deviation of 4.7 approximately 5.6%.     

On-line hyphenation of hydride generation with in situ trapping flame atomic absorption spectrometry for arsenic and selenium determination.

The analytical performances of coupled hydride generation, integrated atom trap (HG-IAT) atomizer flame atomic absorption spectrometry (FAAS) systems were evaluated for determination of As and Se in biological and environmental reference materials. Arsenic and Se hydrides are atomized in air-acetylene flame-heated IAT. A new design of HG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangements (a water-cooled single silica tube, double-slotted quartz tube or an "integrated trap") was investigated. A dramatic improvement in detection limit was achieved compared with that obtained using anyone of the above atom trapping techniques separately. The concentration detection limits were 4 and 3 ng ml(-1) for As and Se, respectively. For a 2 min in situ preconcentration time, sensitivity enhancement, compared to FAAS, were 875 and 833 folds for As and Se, respectively, using hydride generation, atom trapping technique. The sensitivity can be further improved by increasing the collection time. The relative standard deviations (RSDs) are of the order of 5 - 9% for this hyphenated technique. The designs studied include slotted tube, water-cooled single silica tube and integrated atom trap. The accuracy was assessed by analyses of NRCC DOLT-2 (Dogfish Liver) and NIST SRM 1648 (Urban Particulate Matter) reference materials. The measured As and Se contents in two reference materials were in satisfactory agreement with the certified values.     

Online preconcentration for the determination of lead, cadmium and copper by slotted tube atom trap (STAT)-flame atomic absorption spectrometry

An online sensitivity enhancement by using atom trapping in flame atomic absorption spectrophotometry was examined for increasing the residence time of the analyte atoms in the light path. For this purpose, various parameters of quartz tubes of the slotted tube atom trap were tested. The studied parameters include the internal diameter, the length of the upper slot and the wall thickness of quartz tube. The best sensitivities as high as 7-fold, 13-fold and 3-fold enhancement were achieved by the tubes having an internal diameter of 6 mm, an upper slot length of 1.0 cm and the wall thickness of 1.5 mm for lead, cadmium and copper, respectively. The limits of quantitation were found to be 30 ng mL(-1) for Pb and 3 ng mL(-1) for Cd and 30 ng mL(-1) for Cu by the optimized method. The achieved technique was applied to determine the concentrations of Pb, Cd and Cu in different plant leaves taken around cement and textile industries.     

Determination of cadmium and lead in reference materials by volatile species generation with in situ trapping flame atomic absorption spectrometry

The analytical performance of coupled volatile species generation-integrated atom trap (VSG-IAT) atomizer flame atomic absorption spectrometry (FAAS) system was evaluated for determination of Cd and Pb in reference materials. Lead using formation of PbH₄ and Cd⁰ vapors are atomized in air-acetylene flame-heated IAT. A new design of VSG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangements (a water-cooled single silica tube, double-slotted quartz tube or an “integrated trap”) was investigated. A dramatic improvement in detection limit was achieved compared with that obtained using either of the above atom trapping techniques separately. The concentration detection limits, defined as 3 times the blank standard deviation (3σ), were 0.05 and 0.40 ng mL^− 1 for Cd and Pb, respectively. For a 120 s in situ pre-concentration time, sensitivity enhancement compared to flame AAS, was 500 and 575 folds for Cd and Pb, respectively, using volatile species generation-atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision, expressed as RSD, was 4.4% and 4.1% (n = 6) for Cd and Pb, respectively. The designs studied include slotted tube, single silica tube and integrated atom trap-cooled atom traps. The accuracy of method was verified using certified reference materials (PLANTS 3 and IAEA/W-4) by standard addition calibration technique. The measured Cd and Pb contents in two reference materials were in satisfactory agreement with the certified values.     

Determination of tellurium by hydride generation with in situ trapping flame atomic absorption spectrometry

The analytical performance of coupled hydride generation — integrated atom trap (HG-IAT) atomizer flame atomic absorption spectrometry (FAAS) system was evaluated for determination of Te in reference material (GBW 07302 Stream Sediment), coal fly ash and garlic. Tellurium, using formation of H₂Te vapors, is atomized in air–acetylene flame-heated IAT. A new design HG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangements (a water-cooled single silica tube, double-slotted quartz tube or an “integrated trap”) was investigated. An improvement in detection limit was achieved compared with using either of the above atom trapping techniques separately. The concentration detection limit, defined as 3 times the blank standard deviation (3σ), was 0.9 ng mL^− 1 for Te. For a 2 min in situ pre-concentration time (sample volume of 2 mL), sensitivity enhancement compared to flame AAS, was 222 fold, using the hydride generation — atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision, expressed as RSD, was 7.0% (n = 6) for Te. The designs studied include slotted tube, single silica tube and integrated atom trap-cooled atom traps. The accuracy of the method was verified using a certified reference material (GBW 07302 Stream Sediment) by aqueous standard calibration curves. The measured Te contents of the reference material was in agreement with the information value. The method was successfully applied to the determination of tellurium in coal fly ash and garlic.     

An investigation of atom collection phenomena in the atomic absorption spectrometry of copper

Analyte collection within a premixed air—acetylene flame for atomic absorption spectometric measurements is described. Copper species of the aspirated solution are collected for fixed periods of time on a water-cooled silica tube positioned within the flame, with the flame burning normally. At the end of a specified time, collection is stopped, the coolant water is quickly flushed out of the silica tube, and the copper species that evaporate into the analyzing radiation beam in the flame, and are atomized, are measured by atomic absorption at 324.8 nm. Aqueous and hydrochloric acid solutions were examined, and the effects of varying flame conditions, positions of the collector and signal measurement, etc., are discussed. A characteristic concentration of 0.0008 ppm was obtained for 0.01 ppm Cu²⁺ solution. With the same equipment in the absence of a collector tube, the value was 0.04 ppm. The presence of a 10,000-fold amount of Al³⁺ enhanced the sensitivity of the collection technique slightly.     

石英缝管火焰原子吸收法测定食醋中的痕量铅

采用石英缝管装置,辅助火焰原子吸收光谱法测定了食醋中的痕量铅。对铅的测量灵敏度较常规火焰原子吸收法提高了4倍以上。装置简单,方法简便,有效地降低了对测量灵敏度较低的组分的富集要求,提高了分析结果的可靠性。     

Determination of lead traces in water and liqueurs by derivative atom trapping flame atomic absorption spectrometry

 A new method for the direct determination of lead traces using derivative atom trapping flame atomic absorption spectrometry (DAT-FAAS) with an improved water-cooled stainless steel trapping equipment in an air-acetylene flame was investigated. The optimum conditions concerning the sensitivity were studied. For a 1 min collection, the characteristic concentration (given as derivative absorbance of 0.0044) and the detection limit (3s) were 1.4 ng/mL and 0.27 ng/mL, respectively. This is 361 and 74-fold better than those of the conventional flame atomic absorption spectrometry (FAAS) and comparable to those of graphite furnace atomic absorption spectrometry (GFAAS). The detection limit and sensitivity of DAT-FAAS for a 3 min collection time were 2 and 3 orders of magnitude higher than those of conventional FAAS. The present method was applied to the determination of lead in water and liqueur samples with a recovery range of 94–108% and a relative standard deviation of 3.5–5.6%. Received: 10 January 1996/Revised: 9 December 1996/Accepted: 20 December 1996