Determination of lead in rocks by radiometric isotope dilution and substoichiometric extraction

A rapid procedure is described for the determination of lead in rocks by an isotope-dilution substoichiometric method. After the sample has been digested with acid in the presence of ²¹⁰Pb tracer, the lead is separated by dithizone extractions. After the lead has been back-extracted into aqueous solution, it is reacted with a substoichiometric amount of EDTA. Excess of unreacted lead is removed by extraction with dithizone in carbon tetrachloride, and the specific activity of the aqueous complex is determined by counting ²¹⁰Pb. The standard deviation of the method is less than 10 % for replicate determinations of lead in several U.S. Geological Survey standard rocks. The agreement with literature values indicates that the method is accurate.     

Substoichiometric isotope dilution analysis of iron in biological materials by the 8-quinolinol-extraction

A highly precise and accurate method for the determination of minor amounts of iron by substoichiometric isotope dilution analysis is described. The constant amount of Fe(III) is substoichiometrically extracted with 2·10⁻⁴M oxine in chloroform from the aqueous phase of pH 9.2–10.0 containing 6·10⁻³M tartrate. The interfering ions such as Mn(II), Co(II), Ni(II), Cu(II), and Zn(II), can be removed by the preliminary extraction of Fe(III) from 7.5M hydrochloric acid solutions into isopropyl ether. The present method has been applied to the determination of iron in biological standard reference materials, i.e., the NBS Spinach (SRM-1570) and the NIES Pepperbush (SRM No. 1), and the results obtained are 548±9 ppm (NBS certified value: 550±20 ppm) and 193±4 ppm, respectively.     

A substoichiometric radioisotope dilution study using210Pb

A radioisotope dilution procedure has been developed which permits the determination of lead over a concentration range of 0.1 to 10 ppm. Samples in an ammoniacal cyanide/sulfite medium are labelled with²¹⁰Pb, followed by addition of substoichiometric amount of dithizone. The Pb/HDz/₂ formed is extracted into CH₂Cl₂, and aliquot portions are taken for liquid scintillation counting. Count rate is plotted vs. the reciprocal of the lead concentration, yielding a straight line. An average error of ±3.5% is estimated, based on a linear least squares fit.     

Determination of mercury and arsenic in fresh water by neutron activation analysis

Neutron activation analysis has been applied for the determination of Hg and As in freshwater samples. Preconcentration of Hg and As from the samples before irradiation by using active carbon for scavenging the chelate complex of Hg with dithizone at pH 1 and Fe(OH)₃ for co-precipitating arsenic was used. After irridiation, mercury was determined by direct counting of the irradiated active carbon. Arsenic was separated from Fe(OH)₃ by precipitating arsenic in the metal form after removing¹²²Sb by extraction in 2N HCl with Ni-diethyldithiophosphoric acid in carbon tetrachloride. The method is simple and reliable.     

Substoichiometric isotope dilution analysis of copper traces in zinc by adsorptive sampling

The spontaneous deposition of Cu²⁺ from aqueous solutions on a hydrogen-saturated platinum surface as a possibility for the substoichiometric sampling of copper is shown. A sensitive isotope dilution method has been developed for the determination of traces of copper in high purity zinc making use of the spontaneous deposition of microquantities of Cu²⁺ from aqueous solutions of zinc salts on a cathodically polarized platinum surface. If the same platinum surface is used in each run, the saturation values of the deposited copper are practically independent of the concentrations and contents of copper and zinc in the solution. The copper traces were labelled with the product of the⁶⁴Zn(n,p)⁶⁴Cu nuclear reaction. A copper content of 0.18±0.03 ppm in zinc was determined by this method.     

Flame atomic absorption spectrometric determination of Cd(II), Ni(II), Co(II) and Cu(II) in tea and water samples after simultaneous preconentration of dithizone loaded on naphthalene

A simultaneous preconcentration procedure for the determination of Cd(II), Ni(II), Co(II) and Cu(II) by atomic absorption spectrometry is described. The method is based on solid phase extraction of the metal ions on dithizone loaded on naphthalene in a mini-column, elution with nitric acid and determination by flame atomic absorption spectrometry. The sorption conditions including NaOH concentration, sample volume and the amount of dithizone were optimized in order to attain the highest sensitivity. The calibration graph was linear in the range of 0.5–75.0 ng ml^?1 for Cd(II), 1.0–150.0 ng ml^?1 for Ni(II), 1.0–150.0 ng ml^?1 for Co(II) and 1.0–125.0 ng ml^?1 for Cu(II) in the initial solution. The limit of detection based on 3S_b was 0.13, 0.32, 0.33 and 0.43 ng ml^?1 for Cd(II), Ni(II), Co(II) and Cu(II), respectively. The relative standard deviations (R.S.D) for ten replicate measurements of 20 ng ml^?1of Cd(II), 100 ng ml^?1 of Ni(II), Co(II) and 75 ng ml^?1 of Cu(II) were 3.46, 2.43, 2.45 and 3.26%, respectively. The method was applied to the determination of Cd(II), Ni(II), Co(II) and Cu(II) in black tea, tap and river water samples.     

Determination of nickel,gold and silver in gallium arsenide by radioactivation analysis based on the quantitative isotope dilution principle

A method of radioactivation analysis has been developed for the determination of Ni, Au and Ag impurities in gallium arsenide. The separation and substoichiometric extraction of these elements were studied and analytical procedures are suggested for their determination. All components are separated by suitable procedures and determined by substoichiometric methods. Ni is extracted as diethyldithiocarbamate into toluene, Au as a complex of rhodamine-B in chloroform, and Ag as dithizonate in carbon tetrachloride. The contents of Ni, Au and Ag in a gallium arsenide crystal with a carrier concentration of 1.8·10¹⁶/cm³ were 0.05–0.08, 0.006–0.008 and 0.002–0.005 ppm, respectively.     

Preconcentration of trace metals from acidic solutions by coprecipitation with dithizone

Traces of Ag, Bi, Cd, Cu, Hg, Pb, Pd and Zn are separated by carrier precipitation with dithizone from diluted HNO₃ and HCl solutions. The separated trace elements are determined by flame AAS and/or by spectrophotometry. The preconcentration recovery is dependent on the acid concentration of the sample solution. The amount of dithizone precipitated is optimized. The detection limits (ng/ml) are 15.0 (Pb, Zn), 12.0 (Pd), 10.0 (Bi), 6.0 (Ag), 5.0 (Hg), 2.0 (Cu) and 1.0 (Cd). Aluminium, aluminium sulfate and gallium are analyzed with the method. The accuracy of the results was checked by differential pulse voltammetry.     

Substoichiometric determination of trace impurities in zinc selenide

Determination of trace impurities in zinc selenide was carried out by substoichiometric neutron activation analysis. Trace impurities were separated from matrix elements by suitable procedures and determined by substoichiometric methods, i.e., Au was extracted with rhodamine-B, Ag and Cu with dithizone, Cr with sodium diethyldithiocarbamate, Co with 1-nitroso-2-naphthol, and Sb with cupferron. Two sorts of zinc selenide single crystals were supplied for analysis and the following values were obtained as impurity concentration; Au 0.36, 0.076 ppb, Ag 42, 32 ppb, Cr. 1.8, 0.63 ppm, Co 0.16, 0.0079 ppm, Sb 8.5, 5.9 ppb and Cu 1.4, 0.44 ppm. The behavior of copper by heat-treatment of zinc selenide was also studied by means of substoichiometric isotope dilution analysis.     

Substoichiometric isotope dilution determination of manganese in biological smples using 2-thenoyltrifluoroacetone in isobutyl methyl ketone

A substoichiometric isotope dilution method was developed for the determination of microgram amounts of manganese. The method involves the use of carrier-free ⁵⁴Mn with Mn(II) carrier and its complexation with 2-thenoyltrifluoroacetone (TTA) at pH 8.5, the complex then being extracted into isobutyl methyl ketone. A minimum of 50 ng of manganese can be determined. The method was applied to the determination of manganese in several standard reference materials and biological samples such as tea leaves, spices and condiments. The method is simple and fast and yields results with high accuracy and precision.     

双硫腙包覆钛酸锶钡粉体对水中铅的吸附行为

用草酸化学共沉淀法合成了钛酸锶钡(BST)粉体, 以双硫腙为表面修饰剂, 采用静态浸渍法对钛酸锶钡粉体进行表面包覆修饰, 制备出新型固态粉体吸附剂. 利用X射线衍射(XRD)、扫描电镜(SEM)和傅立叶变换红外光谱(FTIR)进行了表征. 研究了该吸附剂对水中铅的吸附行为. 结果表明: 双硫腙通过与钛酸锶钡表面羟基形成氢键作用包覆于该粉体上; 当吸附介质pH值大于4时, 该吸附剂对水中的铅有较强的吸附能力; 室温下, 5 min内吸附达到平衡. 其吸附行为符合Langmuir吸附等温模型和HO准二级动力学方程式, 吸附焓变(ΔH)为19.42 kJ•mol^－1, 活化能(E_a)为22.187 kJ•mol^－1, 该吸附过程是吸热的物理过程. 吸附在双硫腙包覆钛酸锶钡粉体上的铅, 可用1 mol•L^－1的硝酸溶液进行洗脱. 建立了吸附富集、火焰原子吸收法测定水中铅的新方法, 应用于地表水和自来水中铅的测定, 取得了令人满意的结果.     

Multi-element characterization of high-purity titanium dioxide by neutron activation analysis

A radiochemical neutron activation analysis method for the determination of 34 elements in titanium dioxide has been developed. For the assay of indicator radionuclides with short and with long half-lives, the radiochemical separation was performed by anion exchange on a Dowex 1 × 8 column and by combination of cation and anion exchange on a Dowex 50W × 8 and a Dowex 1 × 8 column from HF- and HF/NH₄F-medium, respectively. With both separation modes, a selective removal of the matrix-produced radionuclides ⁴⁶Sc, ⁴⁷Sc and ⁴⁸Sc was achieved. A selective extraction of copper with dithizone from 15 mol/L HF enabled counting the intensive but unspecific 511-keV rays of ⁶⁴Cu for the determination of Cu. The limits of detection achieved were between 0.004 ng/g for Sm and 0.8 μg/g for Sn (via ¹²⁵Sb). The elements La, Mn and Th were determined by instrumental neutron activation analysis only. These techniques were applied to the analysis of two titanium dioxide samples of different purity grade. The results and limits of detection are compared with those of other methods.     

Bestimmung von Rutheniumspuren mit Dithizon Mittels substöchiometrischer Isotopenverdünnungsanalyse

Hexachlororuthenat (III) and the ruthenylion (RuO²⁺) react with dithizone on heating in weak acid water—ethanol solution. The complexes formed can be extracted into chloroform. Based on this reaction, a reproducible, selective determination of ruthenium (20 ppb) is achieved by means of substoichiometric isotope dilution analysis, using¹⁰⁶Ru.     

Substoichiometric determination of traces of palladium by radioactive isotope-dilution analysis

A radioactive isotope-dilution method for the determination of traces of palladium has been developed. It is based on the solvent extraction of palladium dithizonate from acid solution by means of a substoichiometric amount of dithizone in carbon tetrachloride. The separation has been applied to the determination of traces of palladium in platinum, the rocks W-1 and PCC-1 and a biological material (kale). Amounts of palladium down to 3 ng have been determined.     

Bestimmung von Kupfer, Quecksilber und Silber in reinen Uranverbindungen

Zusammenfassung Ein Verfahren zur Bestimmung von Kupfer, Silber und Quecksilber in reinen Uranverbindungen wird mitgeteilt. Die Methode benutzt die selektive Extraktion dieser Elemente mit Dithizon. Es ist möglich, bis zu 1 ppm Hg²⁺ und Ag⁺ und bis zu 0,5 ppm Cu²⁺ zu bestimmen. Der gesamte Analysengang dauert 1 Std. Wegen ihrer hohen Selektivität und Empfindlichkeit kann die Methode auch bei anderen Materialen benutzt werden.

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Summary A method for the determination of copper, mercury and silver in pure uranium compounds is described. It is based on the selective extraction of these elements by dithizone. Concentrations as low as 1 ppm of Hg and Ag and 0.5 ppm of Cu may be determined. Only Pd^II and Au^III and higher concentration of chloride interfere. One analysis requires about 1 hour. Because of its excellent selectivity and sensitivity the method may be used for analyses of other materials, too.

     

Determination of impurities in high-purity niobium(V) oxide by high-resolution continuum source graphite furnace atomic absorption spectrometry after sorption preconcentration

Method of sorption–atomic-absorption determination of Co, Cr, Cu, Fe, Mn, and Ni in samples of high-purity Nb₂O₅ with heterochain S,N-containing sorbents was developed. The method is based on the sorption preconcentration of trace impurities followed by their determination by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS). Selectivity of three original inhouse synthesized S,N-containing heterochain sorbents was studied. The recoveries of Co, Cr, Cu, Fe, Mn, and Ni using heterochain sorbents OKS, MTH, and GLSH were 100, 80, and 76%, correspondingly. Sorbent “OKS”, which provided the quantitative recovery of trace impurities, was chosen for further research. The sorption conditions for chloride solutions of different acidities (0.1–3 M HCl) were studied and optimized. Using the conditions established for the sorption and HR CS GFAAS analysis, trace Co, Cr, Cu, Fe, Mn, and Ni were determined in high purity Nb₂O₅ with a relative error less than 5%. The trueness control of the obtained results is confirmed by the “added–found” method. The developed method allows us to determine concentrations of analytes: 0.02–0.20 ppm Co, 2.0–3.3 ppm Cr, 0.2–1.5 ppm Cu, 6.0–21.0 ppm Fe, 0.6–0.8 ppm Mn, and 2.8–3.5 ppm Ni. The proposed methodology can be successfully extended to the determination of various trace elements in other high-purity inorganic materials.     

Direct Determination of Zinc Using Dithizone in Micellar Solution

Abstract

A simple method for direct determination of Zn²⁺ by spectrophotometry using dithizone in micellar solutions is possible. Surfactants are used to overcome the solubility problems of dithizone in aqueous medium. The proposed method saves time and chemicals and is of extremely high sensitivity. Zn²⁺ concentrations of about 2×10^-7 M can be determined. The important analytical parameters and their effects on the reported system are investigated.     

Determination of zinc in environmental water by displacement substoichiometric isotope dilution analysis /DSIDA/

Trace amounts of Zn /ng.ml^–1/ were determined using a displacement reaction of /Zn²⁺/ org from the dithizone organic phase into the aqueous phase, with a substoichiometric amount of /Hg²⁺/ aq. The results were compared with direct substoichiometric IDA. Absorption spectrophotometry was used as a reference analysis.     

Determination of lead by continuous-flow hydride generation and atomic absorption spectrometry: Comparison of malic acid—dichromate,nitric acid—hydrogen peroxide and nitric acid—peroxodisulfate reaction matrices in combination with sodium tetrahydroborate

A continuous-flow hydride generator is combined with a heated quartz tube atomizeratomic absorption spectrometer system for the trace determination of lead. Malic acid K₂Cr₂O₇, HNO₃—H₂O₂ and HNO₃—(NH₄)₂S₂O₃ are all effective for plumbane generation by means of sodium tetrahydroborate. The relative merits of these systems are investigated in terms of sensitivity, efficiency of plumbane generation and interferences. The sensitivities (0.0044 absorbance) obtained under the recommended conditions for the three systems are 3.2, 1.7 and 1.1 ng Pb ml^-1, respectively, whereas plumbane generation efficiencies are 33%, 47% and >80%, respectively, for 1 μg Pb ml^-1. Silver, Au, Cu and Cd interfere seriously in all reaction systems. A dithizone extraction and back-extraction method is utilized to eliminate interfering ions, followed by reduction of the resulting solution in the peroxodisulphate system. The proposed method is applied to water samples and NBS 1566 oyster tissue.     

Determination of Silver by Flame Atomic Absorption Spectrometry after Preconcentration on Naphthalene Modified with Dithizone

A solid‐phase extraction method for preconcentration of silver and consequent determination by atomic absorption spectrometry is described. The method is based on the adsorption of silver on naphthalene modified with dithizone in a column. The adsorbed silver is eluted from the column with a thiourea solution and determined by flame atomic absorption spectrometry. The adsorption conditions including pH, reagent concentration, eluent volume, flow rate and interfering ions were investigated. The calibration graph was linear in the range 10–1000 ng mL^?1 of Ag in the initial solution with r = 0.9998. The limit of detection based on 3S_b was 3.9 ng mL^?1. The relative standard deviation for ten replicate measurements of 40 and 600 ng mL^?1 of Ag was 4.4% and 0.9%, respectively. The method was applied to the determination of silver in mineral, radiology film and wound dressing samples.