Atom-trapping atomic absorption spectrometry of arsenic,cadmium, lead,selenium and zinc in air—acetylene and air—propane flames

Atom trapping atomic absorption spectrometry has been applied to the determination of Cd, Pb, Se and Zn in an air—acetylene flame and arsenic in an air—propane flame to yield sensitivities that are, respectively, 18, 48, 3, 80 and 60-fold better than those of the conventional technique. Slitting down the zone of observation above the atom-trap to measure in the region of highest atom density further increases the sensitivity for Cd, Cu, Pb, Se and Zn by factors of 4.5, 2.5, 2.5, 5.5 and 1.5-fold, respectively. The sensitivity for cadmium may be increased 2-fold by precoating the silica collector tube with 1000 ppm vanadium or 3-fold with 1000 ppm copper.     

Determination of selenium by atomic absorption spectrometry with miniaturized suction-flow hydride generation and on-line removal of interferences

On-line removal of transition metal interferences in microscale suction-flow hydride generation atomic absorption spectrometry is described for the determination of selenium at μg l^?1 levels. A mini-column of a chelating resin with iminodiacetate groups is used. Selenium in solutions containing ? 2.5 mg of copper or nickel was determined at a rate of 30 samples per hour; the detection limit was 0.1 ng of selenium. The relative standard deviation for ten replicate measurements of 5 ng of selenium was 3.8%. The method was applied successfully to the determination of selenium in standard copper alloys and nickel sponge.     

An investigation of atom collection phenomena in the atomic absorption spectrometry of copper

Analyte collection within a premixed air—acetylene flame for atomic absorption spectometric measurements is described. Copper species of the aspirated solution are collected for fixed periods of time on a water-cooled silica tube positioned within the flame, with the flame burning normally. At the end of a specified time, collection is stopped, the coolant water is quickly flushed out of the silica tube, and the copper species that evaporate into the analyzing radiation beam in the flame, and are atomized, are measured by atomic absorption at 324.8 nm. Aqueous and hydrochloric acid solutions were examined, and the effects of varying flame conditions, positions of the collector and signal measurement, etc., are discussed. A characteristic concentration of 0.0008 ppm was obtained for 0.01 ppm Cu²⁺ solution. With the same equipment in the absence of a collector tube, the value was 0.04 ppm. The presence of a 10,000-fold amount of Al³⁺ enhanced the sensitivity of the collection technique slightly.     

The determination of selenium by atom-trapping atomic absorption spectrometry

The application of atom-trapping atomic absorption spectrometry to the determination of selenium has been studied in detail. The optimum experimental parameters were established and the interference of major elements on the determination of selenium was studied using collection on a cold silica tube. The atom-trapping atomic absorption technique gives a detection limit of 0.03 ppm after 2-min collection on silica in an air—acetylene flame. This compares with ca. 1 ppm by the conventional absorption technique at the same 196.1-nm line. Methods to minimize interferences were examined, including the use of a double tube arrangement, an aluminium oxide-coated silica tube and ion-exchange separation. A combination of combustion in an oxygen flask and collection from an air—acetylene flame on the aluminium oxide-coated silica tube yielded satisfactory results in the analysis of four plant tissue samples.     

Optimization of the determination of selenium in marine samples by atomic absorption spectrometry: Comparison of a flameless graphite furnace atomic absorption system with a hydride generation atomic absorption system

A comparison has been made between a graphite furnace system based on nickel as a matrix stabilizing metal and an automated hydride generation system with a heated quartz cell. The effect of nickel as a matrix modifier was studied in pure selenite solutions as well as in biological matrixes by different charring temperatures. The suppression effect of different acids on the response of the analyte is reported and discussed. The use of an electrically heated quartz tube as an alternative to the argon hydrogen flame method unproved the selenium determination by hydride generation atomic absorption. The effect of hydrochloric acid to secure quantitative formation of selenium (IV) and the interference of copper in the response measurements have been studied. Further a comparison has been made between three different digestion procedures when the hydride generation atomic absorption system was applied. The results of the graphite furnace atomic absorption and the hydride generation atomic absorption were found to be equally accurate, but the graphite furnace technique gave better reproducibility.     

Preconcentration and determination of trace metals in synthetic sea water by flotation with inert organic collectors

The preconcentration and separation of copper, cadmium, cobalt and nickel 8-quinolinolates in solutions of high salinity including synthetic sea water is studied with phenolphthalein or 2-naphthol as collector and octadecylamine as surfactant. A simplex optimization is applied. Yields > 90% are achieved for Ni, Co and Cd with both collectors, but the copper yield is low. Flame atomic absorption spectrometry is used for the final measurements.     

Reduction des interferences sur la determination des metaux lourds dans les sediments de cours d'eau et les boues de stations d'epuration par spectrometrie d'absorption atomique en four graphite

(Reduction of interferences in the determination of trace heavy metals in river sediments and sewage sludges by electrothermal atomic absorption spectrometry.)The interferences of synthetic matrices of river sediments and sewage sludges in the determination of lead, copper, cadmium, chromium and nickel by electrothermal atomic absorption spectrometry were studied; Pb, Cd and Ni were the most sensitive to interferences. The effects of hydrochloric, nitric, perchloric and hydrofluoric acids were tested; perchloric acid was found to interfere most during the determinations. Hydrofluoric acid must be eliminated by evaporation. Techniques for reducing chemical interferences were evaluated. The best method was found to be matrix modification with ammonium dihydrogenphosphate and ascorbic acid for the determination of lead and nickel, and rapid heating (Max Power) for the determination of cadmium. Determinants of copper and chromium were less prone to interference.     

Sorption and preconcentration of copper and cadmium on silica gel modified with 3-aminopropyltriethoxysilane

3-Aminopropyltriethoxysilane, (C₂H₅O)₃ Si(CH₂)₃NH₂, loaded on silica gel was used as a pre-concentration sorbent for copper and cadmium prior to their determination by flame atomic absorption spectrometry (FAAS). Both batch and column methods were used for the separation of the above metals. The analytes are quantitatively retained on the proposed adsorbent at pH 6.5. The complexation capacity of the collector is 0.032 mmol Cu/g silica. In the batch method, the effects of shaking time and the ratio of metal/silica on the retention by the asorbent were investigated. Columns filled with the collector provided quantitative recovery of the above metals from standardized samples as well as from sodium chloride solutions.     

Determination of traces of lead,cadmium and zinc in copper by an arc-nebulization and flame atomic absorption technique

Arc-nebulization (a thermal nebulization technique) is used to form an aerosol of cadmium, lead and zinc. An open arc chamber of simple operation and an ejector of high efficiency are described which are adaptable for use with any flame atomic absorption spectrometer. Limits of detection better by one or two orders of magnitude than those achieved by conventional flame a.a.s. methods were obtained viz., 43 ng Pb, 5 ng Cd, 7 ng Zn (equivalent to 0.7, 0.08 and 0.11 ppm, respectively, in copper). Calibration with matrix-free solutions was possible for lead and cadmium but not for zinc. The spectral interference of copper on absorbance at the most sensitive zinc line (213.856nm) and the efficiency of arc nebulization of cadmium are also discussed.     

Etude critique de la determination par spectrometrie d'absorption atomique sans flamme du selenium dans les milieux complexes apres extraction a l'aide d'o-diamines aromatiques et ajout de nickel(II)

Critical study of the graphite-furnace atomic absorption determination of selenium in biological samples after extraction with aromatic o-diamines and addition of nickel(II)A new method for the determination of traces of selenium in natural samples is proposed. After digestion with nitric, sulfuric and perchloric acids, selenium is quantitatively converted to the tetravalent state with perhydrol. Reaction with an aromatic o-diamine gives the corresponding piazselenol which can be extracted into toluene and determined by atomic absorption spectrometry after addition of nickel(II). Calibration graphs are linear in the range 0–1.5 ppm Se. A critical study shows the advantages of the method.     

Determination of traces of calcium, magnesium, iron and nickel in aluminium salts by atomic-absorption spectrophotometry with a microwave-excited source and hollow-cathode lamps

The determination of trace amounts of calcium and magnesium in solutions containing large concentrations of aluminium salts may be accomplished by co-precipitating their hydroxides on iron(III) hydroxide, dissolving the precipitate, and extracting the 8-hydroxyquinolates of calcium and magnesium into methyl isobutyl ketone at about pH 11. The extract may be sprayed into the airpropane flame of a simple unmodulated spectrophotometer and atomic-absorption measurements for calcium and magnesium made at 4227 and 2852 A respectively. The limits of determination correspond to 10 and 1 ppm of calcium and magnesium in solid alumina. Iron and nickel may be co-precipitated on hydrated manganese(IV) oxide and their 8-hydroxyquinolates extracted at pH 4.5. Measurements of atomic absorption for these elements at 2483 and 2320 A respectively yield limits of determination corresponding to 10 ppm in alumina. Hollow-cathode lamps may be used for calcium, magnesium and nickel, but a simple microwave-excited discharge tube gives much better sensitivity than a hollow-cathode lamp for iron.     

Extraction chromatography of cobalt and some other metals an silica treated with a mixture of Aliquat 336 and nitroso-R-salt

Summary It was found that cobalt is strongly retained on silica treated with a mixture of Aliquat 336 and nitroso-R-salt and can be separated by column extraction chromatography from cadmium, lead, zinc, mangan, nickel, copper and iron (III) which were eluted with 0.05M solution of perchloric acid. Cobalt was quantitatively eluted with 1 M perchloric acid and subsequently determined by atomic absorption spectrophotometry Cobalt was also concentrated from very dilute aqueous solutions by frontal analysis on small columns packed with the same sorbent, eluted together with a stationary phase with methanol and subsequently determined spectrophotometrically at 466nm; in this way a 500 fold concentration of cobalt was achieved permitting the determination of cobalt at the ppb level.     

Atomic Absorption Spectrometry Analysis of Silicates by the Absorption Tube Technique

Abstract

By the combined use of the absorption tube technique and solvent extraction, determination of cadmium, cobalt, copper, iron, lead and nickel in silicate rocks was investigated.

Applicable concentration range was from 0.1 to 1.Oppm for all the elements except cadmium, for which the range was from 0.005 to 0.025ppm. The accuracy and recovery determined by the use of standard samples from the United States National Bureau of Standards and Geological Survey were satisfactory for practical purposes.     

Determination of Some Transition Metals by Atomic Absorption Spectroscopy after Extraction with Pyridine-2-aldehyde-2-quinolylhydrazone

The extraction of pyridine-2-aldehyde-2-quinolylhydrazone chelates of cadmium, cobalt, copper, nickel, and zinc into isoamyl alcohol (IAOL) and methylisobutyl ketone (MIBK) has been investigated as a basis for the determination of these metals. Below pH 6 the extraction is enhanced by the addition of perchlorate, suggesting that charged complexes are being extracted by ion-pair formation. Sensitivities (1% absorption) are reported for IAOL and MIBK solutions of the metals sprayed into an air-acetylene flame. A procedure for the determination of the above metals by atomic absorption spectroscopy after extraction is given. The procedure is applied to the analysis of tap water for cadmium, copper, and zinc.     

Determination of trace heavy metals in biological samples by inductively-coupled plasma atomic emission spectrometry after extraction with 1,5-bis-(di-2-pyridylmethylene)thiocarbonohydrazide

A sensitive inductively-coupled plasma atomic emission spectrometric sequential method for the determination of trace heavy metals (cadmium, cobalt, copper and nickel) in biological samples after extraction of the metals into isobutyl methyl ketone (IBMK) containing 1,5-bis-(di-2-pyridylmethylene)thiocarbonohydrazide (DPTH) is described. A systematic study was made to determine the optimum conditions for extraction of the metals into IBMK. The complexes formed are quite soluble in IBMK, so much so that this allows the use of aqueous-to-organic phase volume ratios of up to 40 and hence the determination of concentrations down to 40 times lower than those afforded by the direct non-extractive method. The method has been used for the determination of these elements in various biological materials with good results.     

Preconcentration of trace metals in natural waters with 2,2′-dipyridyl-4-amino-3-hydrazino-5-mercapto-1,2,4-triazolehydrazone supported on silica gel

The new hydrazone, supported on silica gel, is used to preconcentrate traces of copper, zinc, lead, nickel, cobalt and cadmium from tap, lake and sea water. Conditions for quantitative retention are established. Copper, zinc, lead, cadmium and nickel are quantitatively eluted with 0.1 M EDTA, and cobalt with 2 M perchloric acid. The metals are measured by atomic absorption spectrometry.     

Determination of palladium and platinum by atomic absorption

Palladium and platinum are determined by atomic absorption after fire-assay concentration into a gold bead. The limit of determination is ~0.06 ppm in a 20-g sample. Serious depressive interelement interferences are removed by buffering the solutions with a mixture of cadmium and copper sulphates with cadmium and copper concentrations each at 0.5%. Substantial amounts of Ag, Al, Au, Bi, Ca, Co, Cr, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn, and the platinum metals do not interfere in the atomic-absorption determination.     

The sequential injection system with adsorptive stripping voltammetric detection

Two sequential injection systems have been developed for adsorptive stripping voltammetric measurement. One is for substances adsorbing at mercury, e.g. riboflavin. In this case, a simple arrangement with only sample aspiration is needed. Reproducibility was 3% and detection limit 0.07 μM. The measuring system was applied to determination of riboflavin in vitamin pills and to study the photodegradation process of riboflavin in aqueous solutions. In the second case, metal ions were determined. They have to be complexed before deposition on the mercury surface. Thus, both the sample and the ligand have to be aspirated in the system. In this case, the reproducibility was ≈6% and the detection limit <0.1 ppm for cadmium, lead and copper when complexation with oxine was used. Dimethylglyoxime was used in determination of nickel and cobalt and nioxime complexes were used in determination of nickel and copper. With these complexing agents, the reproducibility was the same as with oxine, but the metals could be determined at concentrations lower than 0.01 ppm. Application of two ligands in a SIA system with AdSV detection was also studied. Simultaneous determination of copper, lead, cadmium and cobalt was possible by using oxine and dimethylglyoxime. Copper and nickel were simultaneously determined by using dimethylglyoxime and nioxime.     

The uses of 1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin on the solid phase extraction of traces heavy metal ions and their determinations by atomic absorption spectrometry

1-(2-pyridylazo) 2-naphtol (PAN) impregnated Ambersorb 563 resin was used as solid phase extractor of copper, nickel, cadmium, lead, chromium and cobalt ions in aqueous solutions prior to their atomic absorption spectrometric determinations. The parameters including pH, sample volume, matrix effects were also investigated. The relative standard deviation (R.S.D.) of the combined method of sample treatment, preconcentration and determination with atomic absorption spectrometry is generally lower than 10%. The limit of detection was between 0.21 and 1.4 μg l⁻¹. The results were used for preconcentration of analyte ions from natural water samples. The method was also applied to a stream sediment standard reference material (GBW7309) for the determination of Cu, Ni, Cd, Pb, Cr and Co.     

Direct electrothermal atomic absorption spectrometric determination of selenium in serum

The effect of copper, iron, nickel and silver ions on the thermal stability of inorganic and metabolized forms of selenium in serum was studied with radioactive ⁷⁵Se. Copper and iron had no stabilizing effect but in the presence of nickel or silver the temperature could be raised to 1050°C or 1250°C, respectively, without loss of selenium. On this basis an electrothermal atomic absorption spectrometric method was developed for the direct determination of selenium in human serum; selenium is stabilized with nickel during ashing. In 12 samples of sera from unexposed individuals, the concentrations ranged from 92 pob to 140 ppb. The relative standard deviation of the method is 4%, and the detection limit is 5 ppb.