电感耦合等离子体原子发射光谱法测定金属饰品中铅、镉、铬、汞、锑、砷、硒、钡、镍溶出量

金属饰品样品用硝酸(20+80)溶液浸泡过夜,采用电感耦合等离子体原子发射光谱法测定金属饰品中铅、镉、铬、汞、锑、砷、硒、钡和镍的溶出量。选择波长为216.9,228.8,267.7,194.2,206.8,189.0,196.0,455.4,216.6nm的9条谱线依次作为测定铅、镉、铬、汞、锑、砷、硒、钡和镍的分析线。铅、镉、铬、锑、砷、硒、钡和镍的质量浓度与其发射强度在10.0mg·L-1以内、汞在2.0mg·L-1以内呈线性关系,检出限(3s)在0.002～0.05mg·L-1之间。方法用于金属饰品的分析,回收率在95.4%～103.0%之间,测定值的相对标准偏差(n=11)在0.68%～2.0%之间。     

电感耦合等离子体原子发射光谱法同时测定仿真饰品中砷、钡、镉、钴、铬、汞、镍、铅、锑和硒迁移量

仿真饰品样品用模拟人体环境的酸性汗液萃取60min后,采用电感耦合等离子体原子发射光谱法测定其中砷、钡、镉、钴、铬、汞、镍、铅、锑和硒的迁移量。试验选择波长为193.759,233.527,214.438,228.616,267.716,194.227,232.003,220.353,206.833,196.090nm的10条谱线依次作为测定砷、钡、镉、钴、铬、汞、镍、铅、锑和硒的分析线。方法的检出限(3sb/k)在0.002～0.06mg.L-1之间,测定下限(15sb/k)在0.01～0.3mg.L-1之间。方法用于仿真饰品的分析,回收率在88.0%～100%之间,测定值的相对标准偏差(n=7)在3.1%～9.8%之间。     

端视ICP-AES法同时测定玩具涂料中可溶性铅、镉、汞、砷、铬、锑、硒和钡

采用端视电感耦合等离子体原子发射光谱(ICP-AES)法同时测定玩具涂料中可溶性铅、镉、汞、砷、铬、锑、硒和钡.对仪器的工作参数和被测元素的分析谱线进行了优化和选择.铅、镉、汞、砷、铬、锑、硒和钡的检出限分别为0.006、0.0009、0.012、0.023、0.000 8、0.013、0.030和0.0006 mg/L.定量下限分别为0.99、0.15、2.0、3.8、0.14、2.2、5.0和0.10 mg/kg.相对标准偏差为0.76%～2.72%(n=8),加标回收率为96.0%～104.0%.该法适用于玩具涂料中铅、镉、汞、砷、铬、锑、硒和钡的快速测定.     

氢化物发生-原子荧光光谱法测定海洋沉积物中砷、锑、铋、汞、硒

提出了用盐酸-硝酸-水(3+1+4)混合酸消解样品,氢化物发生-原子荧光光谱法测定海洋沉积物样品中砷、锑、铋、汞、硒的方法。考察了原子荧光光谱仪的最佳工作条件。在最佳条件下砷、锑、铋、硒的检出限(3s/k)分别为0.018,0.004,0.001,0.003μg.g-1,汞的检出限(3s/k)为0.604ng.g-1。应用于3种海洋沉积物标准物质的测定,测定值与标准值吻合。     

水浴消解-氢化物发生原子荧光光谱法同时测定水中痕量汞和硒北大核心CSCD

汞和硒作为重金属污染中毒性较强的元素,一直是水质监测的重要指标。为保障后续饮用水安全,前端水源地中汞和硒的含量测定尤为重要。原子荧光光谱法具有检出限低、设备成本低、可实现半自动化操作等优点,被广泛用于水中汞和硒含量的测定^([1]),相关标准方法有HJ 694-2014《水质 汞、砷、硒、铋和锑的测定 原子荧光法》。     

氢化物发生-原子荧光光谱法同时测定食品添加剂碳酸钙中的砷和汞

应用氢化物发生-原子荧光光谱法同时测定食品添加剂碳酸钙中的砷和汞,并对样品中的主要成份及共存元素可能对检验结果的影响和实验条件进行了研究.结果表明,加入硫脲-抗坏血酸溶液后,碳酸钙中主要成份钙及可能存在的共存元素铁、铅、镉、铜、锑、硒、锡、铬、锌等不干扰砷和汞的测定.方法检出限为砷0.0124 μg/L,汞0.0009μg/L,回收率为砷101.8%～102.2%,汞102.5%～106.0%.精密度为砷0.37%,汞0.95%.建立的氢化物发生-原子荧光光谱法同时测定食品添加剂碳酸钙中砷和汞的分析方法能满足日常检验的要求.     

巯基棉富集分离-氢化物原子吸收法分别测定水中痕量锑(Ⅲ)和锑(Ⅴ)

水中痕量锑可以三、五价两种氧化物存在,同铬、砷、硒等变价元素一样,锑在环境中的迁移、转化规律及生物毒性效应随其赋存价态而异。近年来,用溶剂萃取、泡沫吸附、氢化物发生等方法分离测定水中微量锑(Ⅲ)和总锑已有报导。我们在用巯基棉富集多种微量元素、分离有机汞与无机汞、砷(Ⅲ)与砷(Ⅴ)的基础上,利用它对锑(Ⅲ)与锑(Ⅴ)吸附性能的明显差异,建立了巯基棉分离、富集-氢     

石墨消解-原子荧光光谱法测定土壤中汞、砷、硒和锑的含量北大核心CSCD

取土壤样品0.25 g,以10 mL体积比3∶1∶4的盐酸-硝酸-水混合液为消解液,于120℃石墨消解3 h,每30 min摇晃1次,冷却后,用水定容至25 mL。以2 g·L^(-1)氢氧化钾-0.2 g·L^(-1)硼氢化钾混合液为汞的还原剂,5 g·L^(-1)氢氧化钾-20 g·L^(-1)硼氢化钾混合液为硒、砷、锑的还原剂,以5%(体积分数)盐酸溶液为载流,采用原子荧光光谱法测定其中汞、砷、硒和锑的含量。结果表明,汞、砷、硒和锑的质量浓度在一定范围内与对应的原子荧光强度呈线性关系,检出限(3.143s)分别为0.0005,0.008,0.002,0.007 mg·kg^(-1),低于HJ 680-2013中的检出限。分析不同类型的土壤标准样品,测定值均在认定值的不确定度范围内,测定值的相对标准偏差(n=6)均小于15%。按标准加入法进行回收试验,回收率为94.0%~103%。     

标准加入ICP-AES法测定食品包装袋中8种微量元素

建立了ICP-AES同时测定食品包装袋中锑、砷、钡、镉、铬、铅、汞、硒的方法.运用正交试验得出了仪器的最佳工作条件.各元素分析结果的回收率为88.0%～101.0%,测定结果的相对标准偏差为1.54%～4.65%(n=6).     

玩具、铅笔中可溶性砷、锑、硒的形态分析

对玩具、铅笔中可溶性砷、锑、硒的形态分析方法进行了研究,对原子荧光光谱法测定不同价态砷、锑、硒的方法进行了优化,建立了砷、锑、硒的原子荧光光谱形态分析方法。该方法样品加标回收率为82.0%~110.0%,测定结果的相对标准偏差为1.35%~2.22%(n=10)。     

ICP—OES测定饰品中砷、镉、汞、铅总量的不确定度评定

在用ICP-OES检测重金属含量过程中,含量在仪器检出限以上的得出正值结果,在仪器检出限以下的往往会产生一些负值观测结果,对饰品中铅、镉、汞、砷总量测定过程产生的正值、负值观测结果（As：-9mg／kg;Cd：46mg／kg;Hg：-4mg／kg;Pb：81mg／kg）进行了不确定度评定,最后结合样品检出限给出报告为As：小于37mg／kg;Hg：小于48mg／kg;Cd：（46±4）mg／kg（k=2）;Pb：（81±8）mg／kg（k=2）。     

Interferences of hydride forming elements and of mercury in the determination of antimony, arsenic, selenium and tin by hydride-generation AAS

Summary By means of the radiotracer technique supplemented by conventional absorption measurements, the interferences of As, Bi, Hg, Pb, Sb, Se, Sn and Te in amounts between 10 g and 1 mg with the determination of As, Sb, Se and Sn by hydride generation AAS using heated quartz tube were investigated during the hydride-generation and the atomization stages. Amounts up to 100 g of Hg and Pb do not cause any detectable interference. The interference of Bi and Te is dominant in the hydride-generation stage and that of As, Se, Sb and Sn in the atomization stage. Tin is retained to a considerable extent in the quartz tube and the resulting memory effect makes the determination of As, Sb, and Se impossible. In the absence of interfering elements, the efficiency of the formation of hydrides of As, Sb, Se and Sn was close to 100%. However, a reduction of Sb(V) to Sb(III) prior to the hydride-generation is necessary for which an improved procedure was developed.

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Störungen von Hydridbildnern und von Quecksilber bei der Bestimmung von Antimon, Arsen, Selen und Zinn durch die Hydrid-AAS

Zusammenfassung Mittels der Radiotracertechnik und Atomabsorptionsspektrometrie wurde der Störeinfluß unterschiedlicher Mengen (10–1000 g) von As, Bi, Hg, Pb, Sb, Se, Sn und Te auf die Bestimmung von As, Sb, Se und Sn mit der Hydrid-AAS untersucht. Durch diese Verfahrenskombination war es möglich, das Ausmaß der Störungen durch diese Elemente sowohl im Hydrierungs- als auch im Atomisierungsschritt zu bestimmen sowie zum großen Teil auch die Gründe für ihr Auftreten aufzuklären. Keine nachweisbare Störung verursachen Hg und Pb bis zu jeweils 100 g. Die Störung durch Bi und Te tritt hauptsächlich im Hydrierungsgefäß auf, hingegen die durch As, Sb, Se und Sn im wesentlichen in der Quarzabsorptionszelle. Bei Zinn wurde ein starker Memoryeffekt festgestellt, der aus der Ablagerung dieses Elements in der Quarzküvette resultiert und der die Bestimmung von As, Sb und Se völlig unmöglich macht. Ohne diese Störelemente liegen die Hydrierungsausbeuten für As, Sb, Se und Sn bei nahezu 100%. Bei Antimon ist allerdings eine vorherige Reduktion von Sb(V) zu Sb(III) notwendig, für die ein verbessertes Verfahren vorgeschlagen wurde. Denn durch die Radiotracertechnik konnte nachgewiesen werden, daß die während der Alterung von Sb(V)-Lösungen durch Kondensationsprozesse entstehenden Polysäuren nicht mehr hydriert werden können.

     

Determination of As,Cd, Cr,Cu, Hg,Sb and Se concentrations by radiochemical neutron activation analysis in different Brazilian regional diets

The present paper describes radiochemical separation procedures developed for the determination of seven elements: As, Cd, Cr, Cu, Hg, Sb and Se in different Brazilian regional diets. In the case of the elements As, Hg, Sb and Se, the procedure was based on retention in inorganic exchanger TDO (tin dioxide) and determination of Hg by extraction with Ni(DDC)₂. For determination of Cd, Cr, Cu and Se the procedure chosen was based on retention in inorganic exchanger HMD (hydrated managese dioxide) and extraction of Cu and Cd as diethyldithiocarbamate compounds. The accuracy and precision of the methods studied were tested by means of analyses of different reference materials. Due to the lack of data on trace element levels in Brazilian foodstuffs and diets, these methods were applied to determination of these elements in different Brazilian regional diets. These diets were supplied by the Food and Experimental Nutrition Department of the Faculty of Pharmaceutical Science, University of São Paulo. The daily dietary intake values for these diets are presented for As, Cd, Cr, Cu, Hg, Sb and Se.     

Determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal slurries by CVG-ETV-ICP-MS using external or isotopic dilution calibration

A method for the multi-elemental determination of As, Ge, Hg, Pb, Sb, Se and Sn in coal reference materials by slurry sampling chemical vapor generation (CVG) using external calibration and isotopic dilution (ID) calibration and detection by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) is proposed. As, Ge, Sb, Se and Sn were determined using the external calibration, while, Hg, Pb, Se and Sn were determined by isotopic dilution. About 50–250 mg of sample was mixed with an acid solution, containing aqua regia and HCl, in an ultrasonic bath. For the isotopic dilution calibration, the enriched isotopes ²⁰¹Hg, ²⁰⁶Pb, ⁷⁷Se and ¹¹⁹Sn were added to the slurry in an adequate amount in order to produce an altered isotopic ratio close to 1. The vapor produced by the reaction of the sample slurry with the reducing agent was transported to the vaporizer and trapped in a Ir-treated graphite tube at 200 °C, before vaporization at 2100 °C and transportation of the vapor to the plasma. The accuracy of the method was assured by the analysis of four certified reference coal samples, using external calibration with aqueous solutions, prepared in the same medium and subjected to the same CVG and trapping procedure as the slurries and also by isotopic dilution calibration. The obtained concentrations were in agreement with the certified values, using the t-Student test for a confidence level of 95%. The detection limits (3 s; n = 5) of isotopic dilution, in ng g^− 1, were: 0.4 for Hg, 900 for Pb, 0.3 for Se and 0.2 for Sn. For external calibration, the detection limits, in ng g^− 1, were: 1.6 for As, 0.1 for Ge, 0.3 for Sb, 0.9 for Se and 7.5 for Sn. The relative standard deviations generally were lower than 14%, adequate for slurry analysis.     

微波消解-ICP-OES法测定汽车涂料中8种重金属

建立微波消解-电感耦合等离子体发射光谱(ICP-OES)测定汽车涂料中Pb,Cr,Se,Ba,Sb,As,Cd,Hg含量的方法。以HNO_3-H_2O_2(体积比为4∶1)混合酸消解样品,各元素分析谱线:Pb 220.353 nm,Cr 267.716 nm,Se196.090 nm,Ba 233.527 nm,Sb 217.581 nm,As 189.042 nm,Cd 228.802 nm,Hg 184.950 nm。8种元素测定结果的相对标准偏差为2.02%~12.94%(n=6);对白色、蓝色、红色汽车漆样品进行加标回收试验,Pb,Cr,Se,Ba,As,Cd,Hg,的加标回收率为81.26%~99.79%,Sb的回收率为62.43%~87.61%。该方法快速、简便,精密度、准确度较高,可用于汽车涂料中重金属含量的监控。     

Determination of hydride forming elements (As,Sb, Se,Sn) and Hg in environmental reference materials as acid slurries by on-line hydride generation inductively coupled plasma mass spectrometry

A method for the determination of As, Hg, Sb, Se and Sn in environmental and in geological reference materials, as acidified slurries, by flow injection (FI) coupled to a hydride generation system (HG) and detection by inductively coupled plasma mass spectrometry (ICP-MS) is proposed. The HG unit has a gas liquid separator and a drying unit for the generated vapor. The slurries were prepared by two procedures. Approximately 50 mg of the reference material, ground to a particle size ≤50 μm, was mixed with acid solutions in an ultrasonic bath. In Procedure A, the medium was a hydrochloric acid solution while in Procedure B, the medium was aqua regia plus a hydrochloric acid solution. The conditions for the slurry formation and the instrumental parameters were optimized. Harsh conditions were used in the slurry preparation in order to reduce the hydride forming analytes to their lower oxidation states, As (III), Se(IV), Sb(III) and Sn(II), before reacting with sodium tetrahydroborate. To test the accuracy, 10 certified reference materials were analyzed (four sediments, three coals, one coal fly ash and two sewage sludges), with the analyte concentrations mostly in the μg g⁻¹ level. Good agreements with the certified values were obtained for Hg, Sb and Sn in the sediments using Procedure A and calibration against aqueous standard solutions. Using Procedure B, good results were obtained for Hg, Se and Sn in the sediment samples, for Se in the coal and coal fly ash samples and for Hg in the sewage sludge samples, also using external calibration with aqueous standard solutions. For As in sediments, coals and coal fly ash, Procedure B and the analyte addition calibration was required, indicating matrix effects. The relative standard deviations were lower than 5%, demonstrating a good precision for slurry analysis. The limits of quantification (10 times the standard deviation; n=10), in the samples, in ng g⁻¹, were: 20 for As, 60 for Hg, 80 for Sb, 200 for Se and 90 for Sn. The method requires small amounts of reagents and reduces contamination and losses.     

Flow injection electrochemical hydride generation inductively coupled plasma time-of-flight mass spectrometry for the simultaneous determination of hydride forming elements and its application to the analysis of fresh water samples

A flow injection (FI) method was developed using electrochemical hydride generation (EcHG) as a sample introduction system, coupled to an inductively coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) for rapid and simultaneous determination of six elements forming hydrides (As, Bi, Ge, Hg, Sb and Se). A novel low volume electrolysis cell, especially suited for FI experiments was designed and the conditions for simultaneous electrochemical hydride generation (EcHG; electrolyte concentrations and flow rates, electrolysis voltage and current) as well as the ICP-TOFMS operational parameters (carrier gas flow rate, modulation pulse width (MPW)) for the simultaneous determination of 12 isotopes were optimized. The compromise operation parameters of the electrolysis were found to be 1.4 and 3 ml min⁻¹ for the anolyte and catholyte flow rates, respectively, using 2 M sulphuric acid. An optimum electrolysis current of 0.7 A (16 V) and an argon carrier gas flow rate of 0.91 l min⁻¹ were chosen. A modulation pulse width of 5 μs, which influences the sensitivity through the amount of ions being collected by the MS per single analytical cycle, provided optimum results for the detection of transient signals. The achieved detection limits were compared with those obtained by using FI in combination with conventional nebulization (FI-ICP-TOFMS); values for chemical hydride generation (FI-CHG-ICP-TOFMS) were taken from the literature. By using a 200 μl sample loop absolute detection limits (3σ) in the range of 10-160 pg for As, Bi, Ge, Hg, Sb and 1.1 ng for Se and a precision of 4-8% for seven replicate injections of 20-100 ng ml⁻¹ multielemental sample solutions were achieved. The analysis of a standard reference material (SRM) 1643d (NIST, “Trace Elements in Water”) showed good agreement with the certified values for As and Sb. Se showed a drastic difference, which is probably due to the presence of hydride-inactive Se species in the sample. Recoveries better than 93% for Ge and Hg and 83.9% for Se were achieved on a spiked SRM sample. The developed method was successfully applied to the simultaneous multielemental determination of hydride forming elements in spring water samples originating from two different regions in Hungary.     

Simultaneous determination of hydride forming elements (As, Sb, Se, Sn) and Hg in sonicate slurries of biological and environmental reference materials by hydride generation microwave induced plasma optical emission spectrometry (SS-HG-MIP-OES)

A slurry sampling hydride generation (SS-HG) method for the simultaneous determination of hydride forming elements (As, Sb, Se, Sn) and Hg, without total sample digestion, has been developed using batch mode generation system coupled with microwave induced plasma optical emission spectrometry (MIP-OES) from certified biological and environmental reference materials. Slurry concentration up to 3.6% m/v (particles < 80 μm) prepared in 10% HCl containing 100 μl of decanol, by the application of ultrasonic agitation, was used with calibration by the standard addition technique. Harsh conditions were used in the slurry preparation in order to reduce the hydride forming elements to their lower oxidation states, As(III), Sb(III), Se(IV) and Sn(II) and Hg, being reduced to mercury vapor, before reacting with sodium tetrahydroborate. An ultrasonic probe was used to homogenize the slurry in the quartz cup just before its introduction into the reaction vessel. For 10 ml of slurry sample, detection limits (LOD, 3σ_blank, peak area) of 0.06, 0.08, 0.15, 0.12 and 0.10 μg g^− 1 were obtained for As, Sb, Se, Sn and Hg, respectively. The method offers relatively good precision (RSD ranged from 9 to 12%) for slurry analysis. To test the accuracy, three certified reference materials were analyzed with the analyte concentrations mostly in the μg g^− 1 level. Measured concentrations are in satisfactory agreement with certified values for the biological reference materials: NRCC LUTS-1 (lobster hepatopancreas), NRCC DOLT-2 (Dogfish Liver) and environmental reference material: NRCC PACS-1 (Marine Sediment), all adequate for slurry sampling. The method requires small amounts of reagents and reduces contamination and losses.     

Electrolytic hydride generation atomic absorption spectrometry for the determination of antimony, arsenic, selenium, and tin--mechanistic aspects and figures of merit

This article deals with the electrocatalytic and electrochemical mechanisms of hydride formation and their dependence on hydrogen overvoltage. A three-electrode-arrangement was used to determine the hydrogen overvoltage of different cathode materials (Pt, Au, Ag, glassy carbon, Cd, Pb, amalgamated Ag). The applicability of these cathode materials was tested for hydride formation using As(III), As(V), Sb(III), Sb(V), Se(IV), and Sn(IV). Glassy carbon is the most suitable cathode material for hydride generation with As(III), Sb(III), Se(IV), and Sn(IV). Hg-Ag is well suited for the production of stibine and arsine. As(III), As(V), Sb(III), and Sb(V) were all converted into their hydrides with efficiencies > 90%. A detection limit in the range of 0.11-0.13 microg L(-1) for As and Sb (sample volume 200 microL) was obtained for cathode materials with a high hydrogen overvoltage. The precision of replicate measurements was better than 5% calculated as variation coefficient. The accuracy of the presented method was verified by analysis of certified reference materials and tissues of cancer patients. The recovery rates for As and Se were calculated to be 93-108%.