Determination of lead in drinking waters by hydride generation and atomic-absorption spectroscopy, and three other methods

Simultaneous presence of copper and nickel in potable waters interferes with the determination of lead at trace levels by the hydride-atomic-absorption spectrophotometric method. This interference is eliminated by co-precipitating lead with manganese dioxide from acidic solution. The precipitate is dissolved in 0.85% nitric acid and analysed by the automated hydride-atomic-absorption method. This method has been applied to 22 representative water samples and results compared with those obtained by using differential pulse anodic-stripping voltammetry, flame atomic-absorption and graphite-furnace atomic-absorption spectrophotometry. The precision of the three methods is reported and their accuracy checked by the analysis of reference standard water samples. The sensitivity of the three methods is of the order of 1 mug/l., compared to 100 mug/l. for flame atomic-absorption. The merits of each method are discussed.     

Accuracy of the direct determination of cadmium in urine by carbon-furnace atomic-absorption spectrometry

The optimization of the conditions of use of three commercial carbon-furnace atomic-absorption spectrometers for the determination of cadmium in urine is described. The performance of each instrument is evaluated with respect to sensitivity, precision, detection limit and accuracy. All three instruments could be used for the determination of cadmium at levels greater than 0.2 mug/l. in the urine of exposed and "normal" subjects. A sample can be analysed in duplicate in 15 min. No sample pretreatment is required.     

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.     

Spectrophotometric determination of micro amounts of cadmium in waste water with cadion and triton X-100

A spectrophotometric method for determination of micro amounts of cadmium in waste water with Cadion and Triton X-100 is described. The interference of foreign ions can be eliminated by masking with an ascorbic acid-Rochelle salt-potassium cyanide-potassium fluoride mixture. After demasking with formalin, cadmium is determined directly in aqueous solution without separation. Beer's law is obeyed for 0-8 mug of Cd in 25 ml of solution. The method is more sensitive than the dithizone method, its apparent molar absorptivity at 480 nm being 1.19 x 10(5) 1. mole(-1). cm(-1). Results obtained by using the proposed method on waste water samples agree well with those obtained by atomic-absorption spectrophotometry.     

Indirect determination of cyanide in water by atomic-absorption spectrophotometry

An indirect method for determination of trace cyanide in water by atomic-absorption spectrophotometry is described. Cyanide forms a stable complex anion with Pd in alkaline solution. This complex anion can form an ion-association complex with tetra-alkylammonium ions which can be extracted into n-butyl alcohol with an efficiency higher than 90%. The extract can be analysed directly for palladium (and hence indirectly for cyanide) by flame atomic-absorption spectrophotometry. The detection limit for cyanide by this method is 0.1 mug ml in the n-butyl alcohol extract. Beer's law is obeyed for 0.13-9 mug of CN(-) per ml of n-butyl alcohol. Several foreign ions do not interfere.     

Determination of cadmium and lead in urine and other biological samples by graphite-furnace atomic-absorption spectrometry

A method for determining cadmium and lead in urine and other biological samples by graphite-furnace atomic-absorption spectrometry is reported. Samples were analysed after wet or dry ashing and without extraction or matrix-modification techniques, in laminar-flow clean-room; negligible blank contributions were found. Matrix interference effects were observed only for lead and were resolved by the method of standard additions. Five NBS biological reference materials were used as internal quality-control standards. The urinary levels for non-exposed volunteers ranged from 0.16 +/- 0.01 to 1.65 +/- 0.20 and from 6 +/- 1 to 31 +/- 6 ng/ml for cadmium and lead, respectively; this corresponds to 0.15 +/- 0.02 to 2.01 +/- 0.16 and 7 +/- 1 to 31 +/- 3 mug/day. The average relative standard deviation for 60 urine samples was 10% for cadmium and 13% for lead.     

Determination of cadmium in soils by neutron-activation analysis

A radiochemical neutron-activation method for the determination of cadmium in soils is presented. The irradiation is carried out in a neutron flux with a high epithermal component, taking advantage of the high ratio of the resonance-activation integral to the thermal-neutron cross-section for (114)Cd to obtain an increased sensitivity. The irradiated samples are decomposed with hydrofluoric acid-nitric acid and cadmium is separated by anion-exchange. Zinc may also be determined. There is good agreement with results obtained by atomic-absorption spectrophotometry based on solvent extraction separation of cadmium.     

Determination of copper in urine by carbon-furnace atomic-emission spectrometry

A method is described for the direct determination of copper in urine at normal (10-30 mug l .) levels by carbon-furnace atomic-emission spectrometry. Wavelength modulation is used to achieve automatic background correction for scatter-signals produced by the furnace and matrix. The accuracy of the method has been assessed by comparison with continuum-source atomic-fluorescence and carbon-furnace atomic-absorption methods. Relative standard deviations of about 4-5% can be achieved for either the platform or probe atomization techniques.     

Determination of silver, bismuth, cadmium, copper, iron, nickel and zinc in lead- and tin-base solders and white-metal bearing alloys by atomic-absorption spectrophotometry

A simple atomic-absorption spectrophotometry method is described for the determination of silver, bismuth, cadmium, copper, iron, nickel and zinc in lead- and tin-base solders and white-metal bearing alloys, with use of a single sample solution. The sample is dissolved in a mixture of hydrobromic acid and bromine, then fumed with sulphuric acid. The lead sulphate is dissolved in concentrated hydrochloric acid. The method is particularly suitable for the determination of silver and bismuth, which are co-precipitated with lead sulphate. The other elements can also be determined after removal of the lead sulphate by filtration.     

Determination of trace quantities of selenium by indirect atomic-absorption spectrophotometry

The selenium(IV)-iodide interaction in acid medium, leading to the liberation of iodine, has been utilized for the indirect determination of selenium by atomic-absorption spectrophotometry (AAS). The iodine is extracted into benzene and subsequently reductively stripped into an aqueous solution of ascorbic acid. After extraction of the resulting iodide as tris(1,10-phenanthroline)cadmium(II) iodide into nitrobenzene, the cadmium content of the organic extract is determined by AAS. Beer's law is applicable up to 0.75 ppm of selenium. The few interferences are readily overcome. The chemical yield in the system is about 80% overall.     

Determination of traces of thallium in zinc and cadmium metals and process solutions by atomic-absorption spectrophotometry after extraction with di-isopropyl ether and reductive stripping

The bromo-complex of thallium(III) is extracted into di-isopropyl ether and reductively stripped into sodium sulphite solution, which is then analysed for thallium by atomic-absorption spectrophotometry. Thallium in zinc and cadmium metals and process solutions can be determined by this method.     

Rapid analysis of small glass fragments by atomic-absorption spectroscopy

A rapid method is described for the determination of magnesium, iron and manganese in small glass fragments (250-500 mug). The speed of the analytical procedure is made possible by the use of a convenient cold digestion stage allied to a discrete sampling method which permits the three elements of interest to be determined by flame atomic-absorption spectrophotometry.     

Separation of arsenic(III) and arsenic(V) in ground waters by ion-exchange

The predominant species of arsenic in ground water are probably arsenite and arsenate. These can be separated with a strong anion-exchange resin (Dowex 1 x 8; 100-200 mesh, acetate form) in a 10 cm x 7 mm column. Samples are filtered and acidified with concentrated hydrochloric acid (1 ml per 100 ml of sample) at the sample site. Five ml of the acidified sample are used for the separation. At this acidity, As(III) passes through the acetate-form resin, and As(V) is retained. As(V) is eluted by passage of 0.12M hydrochloric acid through the column (resulting in conversion of the resin back into the chloride form). Samples are collected in 5-ml portions up to a total of 20 ml. The arsenic concentration in each portion is determined by graphite-furnace atomic-absorption spectrophotometry. The first two fractions give the As(III) concentration and the last two the As(V) concentration. The detection limit for the concentration of each species is 1 mug l .     

Spectrophotometric determination of trace amounts of cadmium and zinc in waste water with 4-(2-pyridylazo)-resorcinol and mixed ionic and non-ionic surfactants

A spectrophotometric method for determination of trace amounts of cadmium and zinc in waste water with PAR and mixed ionic and non-ionic surfactants is described. The interferences of foreign ions can be eliminated by masking with a mixture of triethanolamine, potassium fluoride, ethylenediamine and sodium hexametaphosphate. By virtue of the difference between the absorbances before and after addition of a little sodium diethyldithiocarbamate, cadmium and zinc can be determined directly in aqueous solution without separation. Beer's law is obeyed for 0-20 microg of Cd or 0-12 microg of Zn in 25 ml of solution. The apparent molar absorptivities at 505 nm are 8.65 x 10(4) l.mole(-1).cm(-1) for Cd and 8.21 x 10(4) l.mole(-1).cm(-1) for Zn. Results obtained by applying the proposed method to waste-water samples agree well with those obtained by atomic-absorption spectrophotometry.     

Determination of traces of lead and cadmium in high-purity tin by polarized zeeman atomic-absorption spectrometry with direct atomization of solid sample in a graphite-cup cuvette

Lead at the mug g level and cadmium at ng g -mug g levels in high-purity tin have been determined by polarized Zeeman atomic-absorption spectrometry with direct atomization of the solid sample. Pieces of high-purity tin weighing up to 5 mg for lead and 20 mg for cadmium were analysed. Calibration graphs were constructed by use of standard solutions of lead and cadmium in the presence of pure tin having lead and cadmium contents below the detection limit. The tin matrix remained in the graphite-cup cuvette after atomization and did not adhere to the wall of the cuvette, so it could be easily removed and the same cuvette repeatedly used.     

Atomic-absorption spectrophotometric determination of traces of manganese with thenoyltrifluoroacetone

An atomic-absorption spectrophotometric method for the determination of traces of manganese in solution with thenoyltrifluoroacetone (TTA) is described. Manganese(II) is extracted with 0.01M TTA in methyl isobutyl ketone (MIBK) at pH 9.5. The atomic-absorption of the organic phase at 279.5 nm is measured. Except for chromium, iron, hafnium, niobium, nickel, rhodium, tin, titanium and zirconium, microquantities of many other cations and anions do not interfere. Iron can be removed by MIBK extraction before the TTA extraction. The sensitivity of the method was 1.6 ng/ml for 1% absorption in aqueous solution. The method was successfully applied to the analysis of environmental waters. Manganese in the filtered fractions of water samples was reliably determined with relative standard deviations of 7% at the 5 mug/l. level and 1% at 50 mug/l.     

Determination of tellurium in copper, lead and selenium by atomic-absorption spectrometry after extraction of the trioctylmethylammonium-tellurium bromide complex

A simple, rapid and sensitive combined solvent extraction and atomic-absorption spectrometric method has been developed for the determination of tellurium in copper, lead, selenium and blister copper. Tellurium is extracted as the trioctylmethylammonium-tellurium(IV) bromide complex into butyl acetate and determined by flame atomic-absorption spectrometry of the extract. As little as 1 mug of tellurium in a sample can be determined. The extraction of tellurium from hydrobromic acid solution with trioctylamine has also been investigated.     

Indirect atomic-absorption determination of boron by solvent extraction as tris(1,10-phenanthroline)cadmium tetrafluoroborate

An indirect atomic-absorption method for boron has been developed. Boric acid is converted into tetrafluoroborate and extracted into nitrobenzene with Tris(1,10-phenanthroline)cadmium(II). The cadmium in the extract is determined by its atomic-absorption at 228s>d8 nm. A fivefold molar excess of the cadmium chelate is necessary for the extraction from pH 4>d3-6>d0 medium. The sensitivity for boron is thus made about the same as that of cadmium, 0>d005 ppm. Metal ions that react with fluoride or phenanthroline interfere. A procedure is described for determination of boron in steel.     

Determination of tin in ores, iron, steel and non-ferrous alloys by atomic-absorption spectrophotometry after separation by extraction as the iodide

A simple and moderately rapid method for determining 0.001% or more of tin in ores, concentrates and tailings, iron, steel and copper-, zinc-, aluminium-, titanium- and zirconium-base alloys is described. After sample decomposition, tin is separated from the matrix elements, except arsenic, by toluene extraction of its iodide from a 3M sulphuric acid-1.5M potassium iodide medium containing tartaric and ascorbic acids. It is finally back-extracted into a nitric-sulphuric acid solution containing hydrochloric acid to prevent the formation of an insoluble tin-arsenic compound and the resultant solution is evaporated to dryness. Tin is subsequently determined by atomic-absorption spectrophotometry in a nitrous oxide-acetylene flame, at 235.4 nm in a 10% hydrochloric-0.5% tartaric acid medium containing 250 mug of potassium per ml. Co-extracted arsenic does not interfere. Results obtained by this method are compared with those obtained spectrophotometrically with gallein after the separation of tin by iodide extraction.     

Indirect determination of iodate by atomic-absorption spectrophotometry

An indirect method for determination of trace iodate in certain high-purity chemicals by atomic-absorption spectrophotometry (AAS) is described. Iodate forms a stable ion-association complex [Hg(dipy)(2)](IO(3))(2) in neutral medium, which can be extracted into methyl isobutyl ketone with 99% efficiency. The extract can be analysed for mercury (and hence indirectly for iodate) by flameless AAS. The limit of detection for iodate by this method is 7.5 ng. Apparent recoveries of 92-112% have been obtained for spikes of 0.25-0.70 mug of iodate.