A Radiochemical Method for Selective Determination of Traces of Lead

Abstract

A very simple and rapid radiochemical method for the determination of 0.01–1 meg of lead has been developed. It consists of adding carrier-free ²¹²Pb to the analysed sample, followed by shaking with a standard lead diethyldithiocarbamate solution in carbon tetrachloride. The amount of non-active lead in the sample is determined from activities of the organic and aqueous phases. A 10-fold excess of bismuth and more than 50–100-fold excess of other metals extractable as diethyldithiocarbamates do not interfere in the determination.     

Colorimetric determination of manganese(II) in natural and waste waters after preconcentration on a polymeric adsorbent

A combined procedure has been developed for the colorimetric determination of manganese(II) in natural and waste waters based on the selective preconcentration of metal ions on a polymer complexing adsorbent,—polystyrene-2-oxy-〈1-azo-1′〉-2′-oxy-3′-sulfo-5′-nitrobenzene, followed by the digital detection of the analytical signal. Manganese(II) is extracted (95–100%) in the batch mode in the pH range from 4.9 to 6.8. The determination is not interfered by n × 10⁵-fold excess (by weight) of K, Na; n × 10⁴-fold excess of Ca, Mg; n × 10³-fold excess of Ba, Sr, Al, Fe(III); n × 10²-fold excess of Ti(IV), Ni, Co, Zn, Pb, Cu. The accuracy of the procedure has been examined by the standard addition method. The relative standard deviation varies from 9 to 16%. The advantages of the procedure include simplicity, availability of the apparatus, rapidity, and the possibility of its application in field conditions.     

Spectrofluorimetric determination of iridium(IV) traces using 4-pyridone derivatives

A new spectrofluorimetric determination of iridium(IV) with 3-hydroxy-2-methyl-1-phenyl-4-pyridone (HX) or 3-hydroxy-2-methyl-1-(4-tolyl)-4-pyridone (HY) is reported. Iridium(IV) react with HX or HY and chelates were extracted into chloroform or dichloromethane. The organic phase showed fluorescence. The fluorescence measurements to quantify iridium were carried out in its fluorescent band centred at λ_ex=373 nm and λ_em=480 nm. Under optimal conditions, the calibration graphs were linear over the concentration range of 0.1-7.6 μg ml⁻¹ of iridium for Ir(IV)-HX and 0.1-5.8 μg ml⁻¹ for Ir(IV)-HY with a correlation coefficients of 0.999 and 0.992 and relative standard deviation of ±1.1%.The method is free from interference by Rh(III) and Pt(IV), which normally interfere with other methods. Iridium can be determined in the presence of 300-fold excess of rhodium(III) and 10-fold excess of platinum(IV).The method was applied successfully to the determination of iridium in some synthetic mixtures and mineral sample gave satisfactory results.     

Determination of dimethylarsinic acid in seawater in the sub-ppb range by electrothermal atomic absorption spectrometry after preconcentration on an io

Dimethylarsinate (DMA) is preconcentrated on a strong cation-exchange resin. By optimizing the elution parameters, DMA can be separated from other arsenicals and sample components, such as group I and II metals, which can interfere in the final determination. Graphite-furnace atomic absorption spectrometry is used as a sensitive and specific detector for arsenic. The described technique allows DMA to be determined in a sample (20 ml) containing a 10⁵-fold excess of inorganic arsenic with a detection limit of 0.02 ng As ml^-1.     

Preconcentration of trace lead by adsorption onto a tantalum wire for electrothermal atomization atomic absorption spectrometry with a tungsten tube atomizer

A preconcentration method of lead in waters by adsorption on a tantalum wire was developed for electrothermal atomization atomic absorption spectrometry with a tungsten tube atomizer. After the preconcentration, the tantalum wire was directly inserted into the tungsten tube atomizer. In the preconcentration (adsorption) process for lead, the optimal immersing time was 90 s and the best pH was 4. Under the optimal conditions, the detection limit for lead by the tantalum wire preconcentration method was 6.0 pg mL^− 1 (3S/N) and the relative standard deviation was 6.1%. The influences of large amounts of concomitants on the preconcentration of lead were evaluated. Even though 10³ to 10⁴-fold excess of matrix elements existed in aqueous solution, the lead absorption signal was not significantly affected by the matrix elements. The method with preconcentration on a tantalum wire was applied to the determination of lead in river waters and proved to be sensitive, simple, and convenient. Because this preconcentration method can be utilized in the in-situ treatment of trace lead in environmental water samples, it was unnecessary to carry the water samples to the analytical work place. The present technique was shown to be useful for the determination of lead in environmental water samples at 0.1−1 μg L^− 1.     

Invers-voltammetrische Bestimmung von Zinn und Blei nebeneinander an der Kohlepaste-Elektrode

Zusammenfassung Die invers-voltammetrisehe Bestimmung von Zinn kann bei einem 10⁵fachen Bleiüberschuß nach der Oxydation des Zinn-Hämateinkomplexes an einer Kohlepaste-Elektrode durchgeführt werden. Dazu wird die bleihaltige salzsaure Zinnlösung mit einer Lösung von Hämatein in Dioxan versetzt und nach einer Vorelektrolyse bei offenem Stromkreis das Voltammogramm zwischen ±0,0 und +1,0 V (GSE) aufgenommen. Das Strommaximum des Oxydationspeaks liegt bei +0,72 V. Die Peakhöhe ist bei einem 10⁴- bis 10⁵fachen Bleiüberschuß der Zinnkonzentration zwischen 10 und 100 ng/ml proportional. Das Bestimmungsverfahren wird an einem Bleistandard mit einem Zinngehalt von 0,005% erprobt. Die relative Standardabweichung der Analysenergebnisse beträgt 4,6%. Die Bestimmung kann auch in Gegenwart eines 10⁵fachen Überschusses von Zink vorgenommen werden. Fe(III), Cu(II), Sb(III) und Sb(V) stören, wenn sie in zu hoher Konzentration vorhegen. — Zur Bestimmung von Blei in Gegenwart von Zinn wird Pb(II) zu Pb(IV) oxydiert, das als Bleidioxid während der Vorelektrolyse abgeschieden und durch kathodischen Spannungsablauf wieder gelöst wird. Die Bestimmung kann in Gegenwart eines 100fachen Zinnüberschusses erfolgen, wenn die Zusatzmethode angewandt wird. — Es werden einige von der üblichen invers-voltammetrischen Praxis abweichenden Besonderheiten und die Reaktionsfolgen beider Bestimmungsverfahren diskutiert.

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Inverse-voltammetric determination of tin and lead in the presence of each other at the carbon-paste electrode

The inverse-voltammetric determination of tin can be carried out in the presence of a 10⁵-fold excess of lead by oxydation of the tin hematein complex on the carbon-paste electrode. For that purpose, to the solution containing tin and lead a solution of hematein in dioxane is added and the voltammogram is recorded between 0.0 and +1.0 V (SSE). Pre-electrolysis is performed at ±0.0 V without polarizing the electrode. The peak potential of the oxydation signal appears near +0.72 V. The peak height is proportional to the concentration of tin in the range between 10 and 100 ng/ml. The determination is not disturbed by a 10⁴- to 10⁵-fold excess of lead and zinc. The method is applied to a standard sample of lead containing 0.005% tin. The standard deviation was 4.6%. Fe(III), Cu(II), Sb(III) and Sb(V) interfere if these elements are present in too high a concentration. — In the determination of lead in the presence of tin, Pb(II) is oxidized forming PbO₂ which is deposited on the surface of the electrode and redissolved by subsequent cathodic voltage scanning. The determination of lead can be carried out by the addition technique in the presence of a 100-fold excess of tin.— The order of the reactions and some further details of both methods are discussed.

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Vorgetragen auf der GDCh-Hauptversammlung in Hamburg im September 1969.     

The determination of oxygen in copper by α-particle activation analysis

The determination of oxygen in copper by activation analysis with 45-MeV α-particles is described. The chemical separation of ¹⁸F produced from oxygen consists of steam distillation as fluosilicic acid, followed by precipitation of the interfering gallium activities as the hydroxide and of the fluoride as lead chlorofluoride or of cation exchange followed by lead chlorofluoride precipitation. This allows a total decontamination from matrix radiation in excess of 10⁶. As standard, mica foils are used, while, for the purp?ose of flux monitoring, the activity induced in a thin copper or mica foil, placed before the sample is counted. Alternatively, the intensity of the particle beam is measured. The method, which allows determination of oxygen at the 1 μg g^-1 level with a precision of about 10%, is applied to the determination of a concentration of 1.2 μg g^-1. Analysis of a reference material containing 70 μg O g^-1 proves the accuracy of the standardization methods applied.     

Narrow span coulometric analysis of neptunium

A narrow span (E _o ±0.1 V) controlled potential coulometric method has been developed for the determination of neptunium in 1M H₂SO₄ with a RSD of 0.2%. The main advantage of this method over the existing coulometric methods is that it can tolerate up to a 5-fold excess of plutonium. The method involves carrying out the electrolysis to about 97% and calculating by an iterative computation the formal electrode potential in situ, which is used to calculate the total amount present in the sample. The method consists in oxidation of all the neptunium to Np (VI) by Ce(IV), destruction of excess Ce(IV) and reduction of Np(VI) to Np(V) by NaNO₂, destruction of excess nitrite by sulfamic acid followed by coulometric titration of Np(V) to Np(VI).     

The trace determination of some heavy metals in waters by flow-injection spectrophotometry and potentiometry

Three automated flow-injection systems are proposed for the determination of traces of manganese(II), lead and copper(II) in waters. The first system utilizes the catalytic effect of manganese(II) on the oxidation of N,N-diethylaniline by potassium periodate at pH 6.86–7.10 (30°C) and is used for spectrophotometric determination at 475 nm in the range 0.02–1.00 μg1^?1; the system involves reagent injection and stopped flow. The determination of lead in the range 0.7–100 μg1^?1 is based on spectrophotometric detection of the lead 4/(2-pyridylazo)resorcinol complex at 525 nm after on-line preconcentration of the sample (5–50 ml) on a minicolumn filled with Chelex-100 or Dowex 1-X8 resin. A potentiometric flow-injection system with a copper ion-selective electrode is applied for the determination of 0.5–1000 μg 1^?1 copper(II) after on-line preconcentration of 50–500 ml of sample on Chelex-100 resin. The procedures are tested on synthetic and real water samples, including sea water and waste-waters.     

Determination of selenium(IV) by differential pulse voltammetry of the 3,3′-diaminobenzidine piazselenol

The determination of selenium(IV) by voltammetry through the formation of a piazselenol with 3,3′-diaminobenzidine (DAB) is described. At pH 1.5 and with a large excess of DAB, the formation of piazselenol is quantitative. In a borate-buffered electrolyte at pH 9, the piazselenol gives reduction peaks at potentials of ?0.64 V and ?0.82 V vs. SCE. The influence of DAB concentration on the sensitivity of the method is discussed. The calibration graphs are linear over the range 0–200 μg l^?1 Se(IV) and the detection limit is 0.10 μg l^?1. Copper(II) and lead(II) are tolerated in 500-fold amounts; the method is applicable to the determination of selenium in NBS Oyster Tissue.     

H-point standard addition method in the analysis by differential pulse anodic stripping voltammetry Simultaneous determination of lead and tin

The applicability of H-point standard addition method (HPSAM) to the resolving of overlapping differential pulse anodic stripping voltammetric peaks corresponding to the oxidation of lead and tin is verified. The results show that the H-point standard addition method is suitable for the simultaneous determination of lead and tin in aqueous media. The results of applying the H-point standard addition method showed that Sn²⁺ and Pb²⁺ could be determined simultaneously with the concentration ratios of Sn²⁺ to Pb²⁺ varying from 1:5 to 10:1 in the mixed sample. The proposed method has been successfully applied to the simultaneous determination of lead in the presence of tin in some synthetic samples. Moreover, the applicability of the method was demonstrated by the recovery of lead in a canned soft drink sample.     

Indirect Potentiometric Determination of Chlorpromazine with an Oxidative Column In a Flow Injection System

Abstract

A flow-injection method is proposed for the determination of chlorpromazine and other N-substituted phenothiazines. The procedure is based on the oxidation of analyte with lead dioxide entrapped into polymeric material in a packed-bed reactor. The oxidation of the drug yields soluble Pb^2-, which is monitored by means of the lead ion selective electrode in the wall-jet configuration. The calibration graph is linear over the range of 0.01 – 2 μg ml^?1 of chlorpromazine with relative standard deviation of 1.4% and sample throughput 20 h^?1. The developed method was applied to the determination of chlorpromazine in pharmaceutical preparations.     

Continuous potentiometric determination of sulphate in a differential flow system

Continuous monitoring of sulphate in a differential flow system equipped with two lead ion-selective electrodes is described. All solutions contained 75% methanol and were adjusted to pH 4. In the flow cell, a standard solution of lead(II) is pumped past the first sensing electrode and is mixed with the sample stream containing sulphate in a small mixing chamber; the mixture containing excess of lead(II) and lead sulphate precipitate then flows through the second sensing electrode chamber. The potential difference depends on the sulphate content in the sample. The effects of lead electrode passivation and the interferences of calcium and chloride are discussed. The system is useful for routine sulphate determination in the range 30–400 mg l^-1 with an accuracy of ±5%     

Determination of cadmium,zinc, and lead by non-dispersive atomic fluorescence spectrometry with a new graphite furnace atomizer

A new graphite furnace atomizer has been developed and applied to the determination of cadmium, zinc, and lead by non-dispersive atomic fluorescence spectrometry. A solar-blind photomultiplier, a lock-in amplifier, and microwave-excited electrodeless discharge lamps are used. The detection limits for cadmium, zinc, and lead in the non-dispersive atomic fluorescence mode are 1·10^?13g, 2·10^?13g, and 2·10^?11g, respectively, which are 20-, 10-, and 2-fold better than those in the atomic absorption mode. The analytical working curves are linear over about three decades of concentration from the detection limits.     

Trace Analysis of Iron in Environmental Water and Snow Samples from Poland

Abstract

A voltammetric method for the determination of iron at detection limit of 4 μg/l is described, using the catalytic current of the reduction of the Fe(III)-triethanolamine (TEA) complex in the presence of bromate ions. the determination was performed at a mercury hanging drop electrode without preconcentration, using the TEA alkaline solution as a supporting electrolyte and the differential pulse technique. A peak current for the Fe(III)-TEA catalytic reduction was observed at a potential of-1.0 V (Ag/AgCl saturated electrode). the influence of TEA, BrO³ and NaOH concentrations on the peak height was studied. It was found that a 100-fold excess of Mn, a 50-fold excess of Cr(VI) and Zn did not interfere in the determination. This method was applied to the determination of iron in water, snow and waste water samples.     

Sensitivity enhancement for inductively-coupled plasma atomic emission spectrometry of cadmium by suction-flow on-line ion-exchange preconcentration

A column of iminodiacetate chelating resin is used to preconcentrate cadmium by a factor of 25-fold for a 5-ml sample. The sampling rate was 25 h^?1, and the detection limit 0.05 ng Cd²⁺ ml^?1. The r.s.d. for 0.1 μg Cd²⁺ ml^?1 was 2.2% (n = 10). This technique was applied to the determination of cadmium in certified biological reference materials and waste-water samples.     

Determination of trace amounts of lead in mussels by flow-injection flame atomic-absorption spectrometry coupled with on-line minicolumn preconcentration

A minicolumn packed with poly(aminophosphonic acid) chelating resin incorporated in an on-line preconcentration system for flame atomic-absorption spectrometry was used to determine ultratrace amounts of lead in mussel samples at μg L^–1 level. The preconcentrated lead was eluted with hydrochloric acid and injected directly into the nebulizer for atomization in an air-acetylene flame for measurement. The performance characteristics of the determination of lead were: preconcentration factor 26.8 for 1 min preconcentration time, detection limit (3σ) in the sample digest was 0.25 μg g^–1 (dry weight) for a sample volume of 3.5 mL and 0.2 g sample (preconcentration time 1 min), precision (RSD) 2.3% for 25 μg L^–1 and 2.0% for 50 μg L^–1. The sampling frequency was 45 h^–1. The method was highly tolerant of interferences, and the results obtained for the determination of lead in a reference material testify to the applicability of the proposed procedure to the determination of lead at ultratrace level in biological materials such as mussel samples. Received: 1 November 2000 / Revised: 8 January 2001/ Accepted: 11 January 2001     

Radiometric trace analysis of lead with diethyldithiocarbamate and 204T1

Two methods for the determination of submugram amounts of lead are described. (A) Lead is selectively extracted with carbon tetrachloride from an alkaline solution containing exccss diethyl-dithiocarbamatc (DDC) and cyanide. Traces of DDC arc back-extracted. The lead in the DDC complex is exchanged with ²⁰⁴Tl and the amount of ²⁰⁴Tl in the organic layer acts as a measure for the lead. The limit of sensitivity is 0.1 mg; the standard deviation is 11% (for 0. 1μg). Bismuth and thallium interfere; their influence can be accounted for with the help of EDTA, however. (B) Excess cyanide is added to the alkaline sample solution and lead is exchanged selectively with ²⁰⁴Tl by shaking with a CHCl₃ solution containing ²⁰⁴T1(DDC)₁. As the process is not 100% effective (with a reasonable excess of the thallium complex) isotope dilution with ²¹⁰Pb is also carried out. The amount of ²⁰⁴Tl in the aqueous layer acts as a measure for the exchanged lead. The limit of sensitivity is 0.05 μg and the standard deviation is 12% (for 0.05 μg). Bismuth and thallium must be removed in advance, e.g. by anion exchange.     

Spectrophotometric determination of cobalt with isonitrosodimedon

An extraction procedure with iso-amylalcohol for the determination of traces of cobalt was developed using isonitrosodimedon. At 374mμ, the wavelength of maximal absorption, the molar extinction coefficient is as high as 19.680, allowing cobalt determination as low as 0.5μg/ml in the organic phase. The extraction is quantitative between pH 4 and 7. The most common ions in a 100-fold excess do not disturb the determination, though Fe⁺³, Cu⁺², Cr⁺³ and Ni⁺² should be absent.     

Differential determination of arsenic(III) and arsenic(V), and antimony(III) and antimony(V) by hydride generation-atomic absorption spectrophotometry,and its application to the determination of these species in sea water

A method is described for the differential determination of As(III) and As(V). and Sb(III) and Sb(V) by hydride generation-atomic absorption spectrophotometry with hydrogen-nitrogen flame using sodium borohydride solution as a reductant. For the determination of As(III) and Sb(III), most of the elements, other than Ag⁺, Cu²⁺, Sn²⁺, Se⁴⁺ and Te⁴⁺, do not interfere in an at least 30,000 fold excess with respect to As(III) or Sb(III). This method was applied to the determination of these species in sea water and it was found that a sample size of only 100 ml is enough to determine them with a precision of 1.5–2.5%. Analytical results for surface sea water of Hiroshima Bay were 0.72 μgl^?1, 0.27 μgl^?1 and 0.22 μgl^?1 for As(total), As(III) and Sb(total), respectively, but Sb(III) was not detected in the present sample. The effect of acidification on storage was also examined.