Contents of arsenic, mercury and other trace elements in Napoleon's hair determined by INAA using the k0-method

Two samples of Napoleon's hair were received for determination of arsenic, mercury and other trace elements by INAA. Before sample irradiation, the hairs were washed following the IAEA washing procedure. Two standard reference materials of GBW09101 (human hair) and NIST/SRM1572 (citrus leaves) were analyzed along with Napoleon's hair for quality control. Standardization was conducted by applying the k ₀-method implemented in the program MULTINAA. The contents of arsenic and mercury as well as three additional elements chromium, antimony and zinc in Napoleon's hair are reported. Compared to the present normal levels, all of the determined elements in Napoleon's hair, except the mercury, are found to be irregular.     

A rapid and simple method for the determination of trace metals in hair samples by atomic absorption spectrometry

Acid digestion procedures are described for the dissolution of human head hair in routine determinations of cadmium, chromium, mercury, lead and zinc in the same sample solution by means of atomic absorption spectrometry. The techniques employed are atomization in a Massman graphite furnace or in an air—acetylene flame; the cold-vapor cell is used for mercury. The entire analytical procedure is tested with powdered homogenized head hair samples, previously analyzed by other analytical techniques. Comparison of the results demonstrates that the proposed technique is at least as precise and accurate as the other procedures used.     

化学蒸气发生-四通道原子荧光光谱法同时测定水样中的痕量砷、锑、硒和汞

应用自行设计的化学蒸气发生-四通道无色散原子荧光光谱仪,建立了同时测定水样中As、Sb、Se、Hg的新方法.在实验中优化了四元素同时化学蒸气发生条件和测定的最佳工作参数.在样品预处理阶段用HCl将Se6+还原为Se4+,然后用质量浓度5 g/L硫脲将As5+和Sb5+还原为As3+和Sb3+.在最佳条件下,方法对As、Sb、Se、Hg的检出限分别为0.05、0.03、0.05、0.01 ng/mL(3d);RSD分别为0.42%、0.74%、0.97%、1.0%(对5 ng/mL As、Sb、Se和0.5ng/mL Hg混合标准,n=7).用所建立的方法对不同类型水样中的As、Sb、Se、Hg进行了同时测定,测定结果与用标准方法测定所得结果之间无明显差异,各元素的加标回收率在93%～105%.     

微波消解-电感耦合等离子体原子发射光谱(ICP-AES)法测定含铜污泥中多种重金属

为了填补现有方法的技术空白,本方法采用微波消解和电感耦合等离子体原子发射光谱法（ ICP-AES）相结合,实现对含铜污泥中铅、锌、铬、镉、砷、镁、铝、锑量的同时测定。首先采用盐酸-硝酸-氢氟酸微波消解进行样品的前处理,消解后加入高氯酸置于电热板进行除碳并赶酸,溶样效果理想,且有效避免了高温溶样对易挥发元素砷、锑的损失,整个过程安全、高效、无损。溶样后以电感耦合等离子体发射光谱法（ ICP-AES）进行测定。对含铜污泥的分解方法进行了合理选择,并对测定时的元素分析谱线及各测定元素间干扰情况等进行了讨论。该方法的加标回收率在95.31%~107.28%%,相对标准偏差（RSD）在0.31%~2.05%之间（n=7),结果表明,该方法准确度高,操作简单快捷,可同时测定多种元素,能满足批量的测定含铜污泥中铅、锌、镍、铁、镉、铬、砷、锑含量的测定要求。     

电感耦合等离子体原子发射光谱法测定学生用品中8种可迁移元素

建立电感耦合等离子体原子发射光谱法测定学生用品中锑、砷、钡、镉、铬、铅、汞、硒8种可迁移元素。样品粉碎后过筛,以0.07 mol/L的盐酸为消解液,于(37±2)℃避光条件下连续振荡1 h,在选定的仪器工作条件下进行测定。各元素的质量浓度在0.0~6.0 mg/L范围内与光谱强度有良好的线性关系,相关系数均大于0.999,方法的检出限为0.002 7~0.075 mg/L。测定结果的相对标准偏差为0.7%~2.1%(n=6),样品的加标回收率为94.2%~102.4%。该方法操作简单、稳定性好,可用于测定学生用品中的可迁移元素。     

Literature survey of on-line elemental speciation in aqueous solutions

The literature about the on-line speciation in water has been comprehensively studied. Critical examination of this subject reveals that a great deal of work has been performed in this area for inorganic metal species and some organic compounds. The topic studied mainly includes the speciation of chromium, selenium, copper, arsenic, lead, cadmium, mercury, iron, aluminium, nickel, tin, antimony, phosphorus, nitrogen and others. The present literature survey includes also comments about the possibilities and problems of speciation as a function of analytical steps, general strategies involved and methods proposed in the literature for each element or a series of elements.     

Simultaneous determination of arsenic,mercury, antimony and selenium in biological materials with prior collection of gaseous products followed by neutron activation analysis

A method combining prior collection of gaseous products with subsequent neutron activation analysis has been developed for simultaneous determination of traces of arsenic, mercury, antimony and selenium in biological materials. The generation of hydrides of arsenic, antimony and selenium and cold vapor of mercury in the vapor generaion and collection system was investigated by the use of radiotracers of the respective elements. The result indicates that selenium and mercury can be completely evaporated from the digested sample solution in 5M HCl with the addition of 5% sodium tetrahydroborate solution, while additional reduction proces by potassium iodide and ascorbic acid is needed for complete evaporation of arsenic and antimony. The gaseous products were collected in a quartz tube for neutron irradiation. The detection limits of these elements were fount to be in the range of 10^–7 to 10^–8 g under the present experimental conditions. The reliability was checked with NBS standard reference materials.     

Heavy metal determination in aquatic species for food purposes

New analytical procedures and sample mineralizations are proposed regarding the determination of arsenic, selenium, copper, lead, cadmium, zinc and mercury in matrices involved in food chain as mussel, clams and fishes. As regard As, Se, Cu, Pb, Cd and Zn determinations, H2SO4-HNO3 acidic mixture is used for the digestion of each matrix. In the case of Hg the sample digestion is performed using a concentrated suprapure H2SO4-K2Cr2O7 mixture and the results are compared with those from other conventional methods. Differential pulse cathodic (DPCSV) and anodic stripping voltammetry (DPASV) are employed for determining simultaneously selenium, arsenic and copper, lead, cadmium, zinc, respectively, while mercury determination is carried out by the cold vapour atomic absorption spectrometry (CV-AAS) with reduction with SnCl2. The voltammetric measurements were performed using a conventional three-electrode cell and the ammonia-ammonium chloride buffer (pH 9.3) as supporting electrolyte. For all the elements, in addition to the detection limits, precision and accuracy data are also reported: the former, expressed as relative standard deviation (Sr), and the latter, expressed as relative error (e), are in all cases between 3 to 6%.     

New human hair certified reference material for methylmercury and trace elements

A new human hair certified reference material (NIES CRM No. 13) for mercury speciation and trace element analysis was prepared at the National Institute for Environmental Studies (NIES), Environmental Agency of Japan. Scalp hair from Japanese males, which is identical with the original material for the previous human hair CRM (NIES CRM No. 5), was used. Special attention was paid to reduce contamination from a grinding vessel during the preparation procedure. A newly-prepared ceramic/Teflon disc mill was used for cryogenic grinding of the hair. 1, 000 bottles (3 g each) were produced after sieving and blending of the hair powder. Certified values for total mercury and methylmercury, as well as other trace elements of toxicological and nutritional significance (antimony, cadmium, copper, lead, selenium, and zinc), were determined based on analyses from extensive collaborations. Reference values for 12 elements (aluminium, arsenic, barium, calcium, cobalt, iron, magnesium, manganese, silver, sodium, sulfur and vanadium) were also given.     

微波消解-ICP-MS法测定硫磺中18种微量元素

建立了用微波消解-电感耦合等离子体质谱法(ICP-MS)同时测定硫磺中18种微量元素(锂、镁、铝、钙、钒、铬、锰、铁、钴、镍、铜、锌、镉、砷、硒、钡、铅和汞)的定量分析方法。通过对消解所用试剂及条件进行研究,确定最佳的样品处理条件;为了获得最佳的信噪比并降低光谱干扰,研究采用单变量方法,对ICP-MS的射频功率和雾化气体流量等因素进行了性能优化。结果显示：该方法各元素的校准曲线线性相关系数在0.999以上,所有元素的检出限(LODs) 在0.001-0.962 mg/Kg之间,测定下限范围在0.004-3.85 mg/Kg之间,回收率在82.9 %~115 %之间,相对标准偏差均小于3 %。     

New human hair certified reference material for methylmercury and trace elements

 A new human hair certified reference material (NIES CRM No. 13) for mercury speciation and trace element analysis was prepared at the National Institute for Environmental Studies (NIES), Environmental Agency of Japan. Scalp hair from Japanese males, which is identical with the original material for the previous human hair CRM (NIES CRM No. 5), was used. Special attention was paid to reduce contamination from a grinding vessel during the preparation procedure. A newly-prepared ceramic/Teflon disc mill was used for cryogenic grinding of the hair. 1,000 bottles (3 g each) were produced after sieving and blending of the hair powder. Certified values for total mercury and methylmercury, as well as other trace elements of toxicological and nutritional significance (antimony, cadmium, copper, lead, selenium, and zinc), were determined based on analyses from extensive collaborations. Reference values for 12 elements (aluminium, arsenic, barium, calcium, cobalt, iron, magnesium, manganese, silver, sodium, sulfur and vanadium) were also given. Received: 8 February 1996/Accepted: 4 April 1996     

Direct analysis of solids for trace elements by combined electrothermal furnace/quartz T-tube/flame atomic absorption spectrometry

The analysis of solid samples by a combined graphite-furnace/air-acetylene flame technique based on generally available atomic absorption instrumentation is described. Samples are injected into the furnace and atomized via a slotted T-tube in the flame. Non-specific absorption is greatly reduced compared to that obtained in graphite-furnace atomic absorption spectrometry (a.a.s.). Sensitivity is reduced by 10–200 times compared to the direct graphite-furnace method, so that large sample sizes (up to 0.2 g) can be used; this minimizes problems caused by sample inhomogeneity. The elements considered are cadmium, lead, copper, arsenic, cobalt, mercury, antimony and selenium. Volatile elements such as mercury and arsenic can be determined without the need for a char step. Simple calibration procedures are possible in some cases and the precision is usually better than 10%. Background reduction capabilities are compared with those of conventional graphite-furnace a.a.s., the isothermal-furnace and the hollow graphite T-tube techniques. Analytical capabilities and results are presented for the direct determination of trace elements in numerous biological and some geological samples.     

Determination of silver, antimony, bismuth, copper, cadmium and indium in ores, concentrates and related materials by atomic-absorption spectrophotometry after methyl isobutyl ketone extraction as iodides

Methods for determining ~ 0.2 mug g or more of silver and cadmium, ~ 0.5 mug g or more of copper and ~ 5 mug g or more of antimony, bismuth and indium in ores, concentrates and related materials are described. After sample decomposition and recovery of antimony and bismuth retained by lead and calcium sulphates, by co-precipitation with hydrous ferric oxide at pH 6.20 +/- 0.05, iron(III) is reduced to iron(II) with ascorbic acid, and antimony, bismuth, copper, cadmium and indium are separated from the remaining matrix elements by a single methyl isobutyl ketone extraction of their iodides from ~2M sulphuric acid-0.1M potassium iodide. The extract is washed with a sulphuric acid-potassium iodide solution of the same composition to remove residual iron and co-extracted zinc, and the extracted elements are stripped from the extract with 20% v v nitric acid-20% v v hydrogen peroxide. Alternatively, after the removal of lead sulphate by filtration, silver, copper, cadmium and indium can be extracted under the same conditions and stripped with 40% v v nitric acid-25% v v hydrochloric acid. The strip solutions are treated with sulphuric and perchloric acids and ultimately evaporated to dry ness. The individual elements are determined in a 24% v v hydrochloric acid medium containing 1000 mug of potassium per ml by atomic-absorption spectrophotometry with an air-acetylene flame. Tin, arsenic and molybdenum are not co-extracted under the conditions above. Results obtained for silver, antimony, bismuth and indium in some Canadian certified reference materials by these methods are compared with those obtained earlier by previously published methods.     

Separation of gallium, indium and thallium by extraction with n-octylaniline in chloroform

Extraction of gallium(III), indium(III) and thallium(III) with n-octylaniline in chloroform at various concentrations of hydrogen halide acids (HCl, HBr, HI) has been studied and a scheme for their separation proposed. The procedure can be successfully applied to the separation and determination of gallium in presence of mercury, bismuth, manganese, zinc and lead; indium in presence of bismuth, antimony, lead, mercury, cadmium and zinc; and thallium in presence of mercury, cadmium, manganese, aluminium, tin and antimony. The advantage of the method is that the reagent can be recovered for reuse. The method is simple, rapid, and effects clear-cut separation.     

Automated chemical separations in routine activation analysis

In recent years increased information is required about the distribution of elements at low concentration levels in the biosphere. Neutron activation analysis can play an important role if it can supply many data at relatively low cost. As some of the concentrations are too low for determination by non-destructive techniques, equipment for chemical separations on a routine basis is necessary. For environmental studies a separation scheme has been developed successfully for arsenic, antimony, cadmium, copper, mercury, selenium and zinc. It is based on a combination of distillation and ion-exchange. Special attention is paid to the prevention of interference from bromine and sodium. Additional information about chromium, cobalt, nickel and tungsten can easily be obtained. Experience gathered with an automated instrument for fifty samples a week is described.     

Heavy metals in human urinary calculi

Summary Heavy metals are incorporated in human urinary calculi during a complex pathological process. The trace metals cadmium, lead, chromium, nickel and mercury are determined with regard to significance in pathogenesis and therapy. The amounts of cadmium, lead and chromium were determined as well directly in the solid sample as after chemical digestion by Zeeman-GFAAS. Both analyzing techniques show corresponding results. Nickel could be determined after chemical digestion only, while mercury was determined by a solid sampling technique. The evaluation of the results of trace metal analysis in the pilot study of 11 urinary calculi showed increased amounts of lead and cadmium compared to the results of tartar and salivary calculi.     

微波消解-电感耦合等离子体质谱法测定血液中30种微量元素

建立了微波消解-电感耦合等离子体质谱法定量测定血液中微量元素的方法.采用微波消解进行样品前处理,在硝酸-双氧水混合体系中消解后稀释,电感耦合等离子体质谱法(ICP-MS)测定全血中铜(Cu)、铅(Pb)、锌(Zn)、银(Ag)、钡(Ba)、锡(Sn)、镍(Ni)、钴(Co)、钒(V)、锑(Sb)、铊(Tl)、汞(Hg)、锰(Mn)、钼(Mo)、硒(Se)、铬(Cr)、镉(Cd)、钍(Th)、钛(Ti)、铝(Al)、砷(As)、铁(Fe)、钙(Ca)、镓(Ga)、锶(Sr)、锂(Li)、镁(Mg)、铍(Be)、钠(Na)和钾(K)元素的含量.对样品前处理过程和仪器工作参数进行了优化,通过内标校正法降低基体效应.结果表明,上述元素相关系数R^(2)均大于0.9998,检测精密度为0.142%~12.856%.方法简单、准确、快速,可精确测定全血中多种微量元素的含量,为全血中元素含量的测定提供了高效可靠的分析手段.     

Determination of volatile hydride-forming metals in steel by atomic absorption spectrometry

A scheme of analysis is presented for the determination of arsenic, antimony, bismuth, lead, selenium, tellurium and tin in steel by evolution of their volatile hydrides and subsequent atomic absorption spectrometry in an argon—hydrogen-entrained air flame. The method is rapid and applicable to a wide range of steels. Detection limits in steel of 1 p.p.m. for arsenic, antimony, bismuth, selenium and tellurium, 2 p.p.m. for tin and 7 p.p.m. for lead are reported. There is some interference in the determination of lead from copper and nickel, but the method could become a viable alternative to existing procedures in the determination of lead in steels of low alloy content, and in irons. Accuracy and precision data are presented.