A rapid radiochemical method for antimony and arsenic : Part I. Formation of stibine and arsine by flash electrolysis

The formation of stibine and arsine affords a clean, one-step, method of separating antimony and arsenic from fission products. The development of a high-current electrolytic cell for the rapid formation of these hydrides from a hydrochloric acid electrolyte, is described. A chemical yield of 45% was achieved for both antimony and arsenic in 10 sec. The effects of pH and antimony and arsenic oxidation states were also studied. In 5 N hydrochloric acid, the chemical yield is independent of the antimony oxidation state. For arsenic however, the yield of arsine is 7 times greater for As(III) than for As(V).     

Rapid chemical separation procedures

Fast, discontinuous separation procedures are described for zirconium, niobium, technetium and antimony from fission products. Other rapid separation methods from aqueous solutions are summarized. The combination of a gas jet recoil transport system with a continuous solvent extraction technique and with a thermochromatographic separation method is presented. The application of such procedures to the investigation of new and already known short-lived nuclides is illustrated by some examples.     

A fast separation for antimony produced in heavy-ion induced fission

Fission fragments from heavy ion induced fission were stopped in thin magnesium foils. A fast procedure based on evolution of stibine was developed to separate the antimony isotopes embedded in the foil. A separation system, and a glass pressure filtration system was constructed for this purpose. The chemical yield measured by three independent methods was 80–90%. The degree of decontamination from other fission products was >10². The whole separation took eight minutes.     

Simultaneous determination of arsenic and antimony in environmental samples by radiochemical neutron activation analysis

A radiochemical separation procedure using an inorganic exchanger, tin dioxide (TDO), for the separation of arsenic from antimony is reported here. This separation avoids the interference of 564 keV gamma-ray of¹²²Sb in the measurement of the 559 keV gamma-ray of⁷⁶As in neutron activation analysis. Environmental samples, after neutron irradiation and digestion, are taken up in 1M HCl–0.1M HF and passed through a TDO column which selectively retains arsenic. The effluent from the TDO column, after proper conditioning, is passed through an anion exchange column for quantitative retention of antimony. The procedure has been utilized for arsenic and antimony determination in NBS Orchard Leaves and NBS Albacore Tuna.     

Rapid separations of corrosion and fission products

A separation scheme of a complex mixture of radiohygienically important radionuclides of corrosion and fission products has been worked out. Rapid separation by means of solvent extractions with metal (sodium, antimony, zinc) diethyldithiocarbamates has been achieved. Chloroform containing metal diethyldithiocarbamates has been used as the organic phase. The procedure permits to separate selectively the representative radionuclides. The selectivity of separation was verified by gamma spectrometry.     

Determination of traces of indium, manganese, arsenic and antimony in zinc by neutron-activation analysis

Destructive activation determination of the trace elements indium, manganese, arsenic and antimony in different samples of pure zinc metal by solvent extraction techniques is described. Determination of indium and manganese is based on the quantitative co-precipitation of both elements with lanthanum hydroxide, followed by their extraction with sodium diethyldithiocarbamate in the presence of potassium cyanide and their subsequent separation by selective stripping. The quantitative determination of arsenic and antimony is based on the extraction of their iodides from sulphuric acid solution with toluene.     

A volumetric determination of arsenic and antimony in mixed manganese arsenide,antimonide and phosphide compounds

A procedure is described for the titrimetric determination, of arsenic and antimony without separation. Total combined arsenic and antimony were determined by reduction with tin(II) chloride and titration with permanganate; antimony is found by selective reduction with mercury(I) chloride and titration with permanganate. A precision of 0.1–0.2% was obtained for total combined arsenic and antimony, and approximately 1% for antimony alone (small amounts in the presence of large amounts of arsenic). The procedure was developed for and applied to the analysis of synthesized compounds of the type MnAs_1-xP_x and MnAs_1-ySb_y.     

Simultaneous determination of inorganic and organic antimony species by using anion exchange phases for HPLC-ICP-MS and their application to plant extracts of Pteris vittata

Antimony is a common contaminant at abandoned sites for non-ferrous ore mining and processing. Because of the possible risk of antimony by transfer to plants growing on contaminated sites, it is of importance to analyze antimony and its species in such biota. A method based on high performance liquid chromatographic separation and inductively coupled plasma mass spectrometric detection (HPLC-ICP-MS) was developed to determine inorganic antimony species such as Sb(III) and Sb(V) as well as possible antimony-organic metabolisation products of the antimony transferred into plant material within one chromatographic run. The separation is performed using anion chromatography on a strong anion exchange column (IonPac AS15/AG 15). Based on isocratic optimizations for the separation of Sb(III) and Sb(V) as well as Sb(V) and trimenthylated Sb(V) (TMSb(V)), a chromatographic method with an eluent gradient was developed. The suggested analytical method was applied to aqueous extracts of Chinese break fern Pteris vittata samples. The transfer of antimony from spiked soil composites into the fern, which is known as a hyperaccumulator for arsenic, was investigated under greenhouse conditions. Remarkable amounts of antimony were transferred into roots and leaves of P. vittata growing on spiked soil composites. Generally, P. vittata accumulates not only arsenic (as shown in a multiplicity of studies in the last decade), but also antimony to a lower extent. The main contaminant in the extracts was Sb(V), but also elevated concentrations of Sb(III) and TMSb(V) (all in μg L⁻¹ range). An unidentified Sb compound in the plant extracts was detected, which slightly differ in elution time from TMSb(V).     

Selective determination of trace arsenic and antimony species in natural waters by gas chromatography with a photoionization detector

Traces amounts of arsenic and antimony in water samples were determined by gas chromatography with a photoionization detector after liquidnitrogen cold trapping of their hydrides. The sample solution was treated with sodium hydroborate (NaBH₄) under weak-acid conditions for arsenic(III) and antimony(III) determination, and under strong-acid conditions for arsenic(III+V) and antimony(III+V) determination. Large amounts of carbon dioxide (CO₂) and water vapor obscured determination of arsine and stibine. Better separation from interference could be achieved by removing CO₂ and water vapor in two tubes containing sodium hydroxide pellets and calcium chloride, respectively. The detection limits of this method were 1.8 ng dm^?3 for arsenic and 9.4 ng dm^?3 for antimony in the case of 100-cm³ sample volumes. Therefore, it is suitable for determination of trace arsenic and antimony in natural waters.     

Determination of gold in low grade ores and concentrates by anion exchange separation followed by neutron activation

The beneficiation of tailings from Kolar Gold Mines involves the flotation of sulphides. Appreciable amounts of arsenic and antimony are expected to accompany gold in this process. The activation analysis of gold in these samples is facilitated by a preseparation of gold from arsenic and antimony. The present paper describes a method for the rapid analysis of gold in the concentration range 0.5 to 50 ppm using a simple pre-irradiation separation, with the recovery of gold being evaluated by an isotope dilution technique using¹⁹⁸Au tracer.     

Concentration and particle-size distribution of uranium and some trace elements in airborne dust collected in Tsukuba

Uranium and some other trace elements were determined in the size-separated airborne dust collected in Tsukuba with an Andersen-type high-volume cascade impactor. The fission track method and the instrumental neutron activation method were applied to the determination of uranium and other elements, respectively. Selenium, antimony, arsenic and zinc were found to be rich in particulates of smaller size, while scandium, iron and cobalt showed a reverse trend, depending on their main origins, i.e. whether industrial or terrestrial. Uranium was distributed in both the larger and smaller particles to the same extent, suggesting that it is derived from both the terrestrial and artificial sources.     

Determination of arsenic and antimony in electrolytic copper by anodic stripping voltammetry at a gold film electrode

A simple procedure is described for the determination of arsenic and antimony in electrolytic copper. The copper is digested with nitric acid and copper is separated from arsenic and antimony by passing an ammoniacal solution of the sample through a column of Chelex-100 resin. After digestion with sulphuric acid and reduction to arsenic(III) and antimony(III) with sodium sulphite in 7 M sulphuric acid at 80°C, both arsenic and antimony are deposited at-0.30V and their total is determined by anodic stripping; antimony is then selectively deposited at -0.05 V for anodic stripping. The lower limits of determination are 56 ng As and 28 ng Sb per gram of copper; relative standard deviations (n = 5) are in the ranges 6.1–15.0% for 5.5—0.5 ppm arsenic in copper and 4.1–6.8% for 2.6—0.6 ppm antimony.     

Neutron activation analysis of traces in electrolytic zinc sulphate solutions : Part III. Simultaneous determination of tellurium,selenium, arsenic and antimony

A neutron activation analysis is described for the simultaneous determination of tellurium, selenium, arsenic and antimony in an electrolytic zinc sulphate solution. The activity induced in the tellurium was measured by means of its radioactive daughter ¹³¹I. The chemical separation of iodine was performed by extraction into carbon tetrachloride. The interference due to the fission of uranium was minimised by a preseparation of uranium. The isotope ⁷⁵Se was measured by a γ, γ-coincidcnce technique, which allowed the determination of 0.002 μg Se/ml. Selenium was chemically separated by extraction as piazselenol. Arsenic and antimony were separated by precipitation as sulphide and distillation as chloride. The isotopes ⁷⁶As and ¹²²Sb were measured γ-spectrometrically, amounts of 0.02 μg/ml being determined. The method is also suitable, although not very sensitive, for the simultaneous determination of tin and germanium.     

The determination of traces of antimony,tin and arsenic in cadmium by pulse polarography

Traces of antimony, tin and arsenic in cadmium products were determined by pulse polarography. Arsenic was distilled, while antimony and tin were precipitated as hydroxides with manganese dioxide as carrier; some lead was coprecipitated with tin, hence these elements were further separated by distillation. In all cases quantitative recoveries were obtained. Antimony(III) was determined in a hydrochloric acid-sodium hypophosphite mixture, tin(IV) in a hydrochloric-hydrobromic acid mixture and arsenic(III) in sulphuric acid as supporting electrolytes; for arsenic(III), methylene blue had to be added. A sample weight of 10 g and an end volume of 10 ml allowed the determination down to about 0.004 p.p.m. antimony, 0.006 p.p.m. tin and 0.003 p.p.m. arsenic in cadmium. Several synthetic samples and commercially available cadmium products were analysed.     

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.     

复杂高铋物料中铅的Na2EDTA滴定法测定

复杂高铋物料中,铋、砷、锑、锡四元素含量高且共存时会影响铅的测定。特别是铋含量高时对铅的测定影响大。实验用EDTA—酒石酸联合掩蔽铋、砷、锑、锡,在稀硫酸介质中以硫酸钾为沉淀剂,使铅生成硫酸铅钾复盐沉淀而与铋、砷、锑、锡、铁、铜、锌、铝、钴、镍等干扰离子分离,沉淀以乙酸-乙酸钠浸取,二甲酚橙为指示剂,Na2EDTA滴定法测定铅。试验进一步优化了测定条件,确定最佳条件：硫酸（1 1）加入量为7mL、硫酸钾用量为5g、煮沸时为5min、沉淀陈化时间为2h、EDTA 50g/L 加入量为10mL、酒石酸用量为0.5g,铅的回收率99.70% ～100.65%。将实验方法应用于测定复杂高铋物料中铅,标样BY0111-1与给定值一致,相对标准偏差（n=11）RSD 0.20%～0.23%,满足生产测试要求。     

Miniaturised isotachophoretic analysis of inorganic arsenic speciation using a planar polymer chip with integrated conductivity detection

A new method allowing the analysis of inorganic arsenic species using isotachophoresis has been developed. This method has been shown to be suitable for use on both miniaturised planar polymer separation devices and capillary scale devices. A poly(methyl methacrylate) chip with integrated conductivity electrodes has been successfully used for the rapid analysis of inorganic arsenic species in under 600 s. Limits of detection of 1.8 mg l⁻¹ and 4.8 mg l⁻¹ for arsenic(V) and arsenic(III), respectively, have been achieved with the miniaturised device. The device has also been used to perform the simultaneous separation of arsenic(III), arsenic(V), antimony(III), molybdenum(VI) and tellurium(IV).     

Determination of arsenic and selenium in steel by an X-ray technique utilizing chemical preconcentration

A chemical X-ray method is proposed for determining trace amounts of arsenic and selenium in steel. The method utilizes a prechemical separation from the iron matrix and concentration of arsenic and selenium on a micr?pore membrane by reduction to the free metal by tin(II). Selenium was found to be a suitable carrier for arsenic (300 mug of selenium for the quantitative precipitation of 10-200 mug of arsenic). Arsenic (300 mug) was found to be a suitable carrier for up to 200 mug of selenium. Up to 200 mug of tellurium and antimony were experimentally found not to be co-precipitated with either arsenic or selenium.     

Application of radioisotopes in column chromatography on substituted celluloses-VI The separation of antimony from manganese, iron and other metals

The Chromatographic behaviour of nanogram amounts of antimony in ethyl ether medium was studied by radioisotope techniques on cellobiose, cellulose and seven substituted celluloses. It was found that antimony is strongly retained and can be separated from macro amounts of manganese, iron, gold, uranium, mercury, arsenic and several other metals. Antimony could be quantitatively recovered by elution from natural cellulose and cellobiose. The method can be applied in several analytical problems concerning the separation of traces of antimony.     

Radiochemical activation analysis of arsenic,selenium and antimony in biological samples

A method for the neutron activation analysis of arsenic, selenium and antimony has been developed. A radiochemical separation is performed by distillation followed by precipitation of the individual elements. Selenium and arsenic are precipitated by reduction to the elemental form while antimony is precipitated as sulfide. The chemical yields and detection limits using 0.5 g samples are the following: As 90–100%, 0.4 ppb, Se 80–100%, 8 ppb and Sb 50–70%, 0.2 ppb. Results from the analysis of nine international biological standard samples are given.