The determination of platinum and palladium in rocks and soils by electrothermal atomic absorption spectrometry of extracts of their iodo complexes

The method developed for determining platinum and palladium in rocks and soils is based on extraction of iodo complexes of these elements into methyl isobutyl ketone (MIBK), followed by electrothermal atomic absorption spectrometry of the extracts. The limit of detection is 10 ng g^?1 for platinum and 3 ng g^?1 for palladium. Analysis of the standard noble metal ore PTC-1 with recommended values of 12.7 μg g^?1 for palladium and 3.0 μg g^?1 for platinum gave precisions of 4.4% and 5.6%, respectively, and deviations of 5.0% and 1.2% from the recommended values. The method is applicable to the determination of both elements in a wide variety of rocks and soils.     

Sensitive determination of traces of boron in waters,fertilizers na geological and biological materials by isotope-dilution mass spectrometry

A method is described for determining traces of boron in water, fertilizers, geological and biological (reference) materials by isotope-dilution mass spectrometry after separation on an Amberlite IRA-743 borate-selective ion-exchange column. Boron (–250 ng g^?1) in water can be determined with an accuracy of 5–20% (computed on a 2s basis). After correction for weighing errors and for moisture, content, which varied from 0 to 8% for the samples tested, 1–35 μg g^?1 boron in “dry” fertilizer, biological or geological sample can be assayed with an accuracy of 5–30% (2s). In an IAEA interlaboratory program on a simulated fresh water, the method yielded a value of 24.3 +? 2 μg l^?1, compared to the make-up value of 25 μg l^?1.     

Atomic absorption spectrometric determination of copper in calcium carbonate scale and carbonate rocks by direct atomization of solid samples

Powdered samples (1 mg) are mixed with 1 mg of powdered graphite and copper is determined by atomic absorption spectrometry in a miniature graphite cup placed in a graphite crucible. Optimum conditions were drying at 200 °C (30 s), ashing at 900 °C (30 s), atomizing at 2700 °C (15 s) and cleaning at 2800 °C (10 s). Samples were powdered to 1–10 μm particle size. Magnesium, manganese and iron did not interfere. The effect of calcium carbonate was eliminated by the graphite addition. Results for copper (0.5–5 μg g^?1) in the scale and rocks agreed well with values obtained for dissolved samples. Relative standard deviations (n=10) were 4.9% for 1.2 μg g^?1 copper and 14.8% for 0.577 μg g^?1.     

Determination of arsenic by hydride generation with a long absorption cell for atomic absorption spectrometry

A method is described for the determination of arsenic involving hydride generation and atomic absorption spectrometry with an improved long graphite-tube furnace capable of considerably higher temperatures than the conventional quartz-tube heaters. Arsine is generated with sodium tetrahydroborate, held in a nitrogen-cooled trap and then swept with helium into an alumina tube (19 cm long) placed within the graphite furnace. The optimum conditions for determination of arsenic are given. The detection limit is 0.2 ng ml^?1 with RSD of 2–3%. Results for various NBS Standard Reference Materials agreed well with expected values and were as follows: orchard leaves, 10 ± 1 μg g^?1; tomato leaves, 0.28 ± 0.03 μg g^?1; bovine liver, 0.046 ± 0.005 μg g^?1.     

Determination of molybdenum in infant formula and human milk by electrothermal atomic absorption spectrometry with barium difluoride as matrix modifier

A method for the determination of molybdenum in infant formula and human milk by electrothermal atomic absorption spectrometry was developed and optimized. Samples were injected directly in the graphite tube with barium difluoride as the matrix modifier. The detection limit was 0.89 μg Mo l^?1. The molybdenum levels found in infant formula and human milk were 0.09–2.23 μg Mo g^?1 and 2.32–8.38 μg Mo l^?1, respectively.     

Determination of bismuth,lead and tellurium in copper by atomic absorption spectrometry with introduction of solid samples into an induction furnace

Atomic absorption spectrometry with an induction furnace is used for the determination of bismuth (0.015–10 μg g^-1), lead (0.2–15 μg g^-1) and tellurium (0.04–5 μg g^-1) in 2–30-mg samples of copper and low-alloy copper dropped into the furnace. Calibration graphs of peak area versus mass of element were constructed by use of standardised alloys. The accuracy, precision and limits of detection of the method are described for numerous copper samples. With alloys containing more than 0.1 μg Bi g^-1, 0.2 μg Pb g^-1 and 0.8 μg Te g^-1, average relative standard deviations are 7%, 6% and 8%, respectively. The limits of detection for bismuth, lead and tellurium are 0.01, 0.1 and 0.02 μg g^-1, respectively.     

Headspace single-drop microextraction coupled with gas chromatography electron capture detection of butanone derivative for determination of iodine in milk powder and urine

A new detection method using headspace single-drop microextraction (HS-SDME) coupled to gas chromatography (GC) was established to determine the iodine in milk powder and urine. The derivative from the reaction between iodine and butanone in the acidic media was extracted into a micro-drop then determined by GC-ECD. With the optimisation of HS-SDME and derivatisation, the calibration curve showed good linearity within the range of 0.004–0.1 μg mL^?1 (0.004–0.1 μg g^?1) (R ² = 0.9991), and the limits of detection for milk powder and urine were 0.0018 μg g^?1 and 0.36 μg L^?1, respectively. The mean recoveries of milk powder and urine were 90.0–107 % and 89.4–101 % with mean RSD of 1.7–3.4 % and 2.7–3.3 %, respectively. This detection method affords a number of advantages, such as being simple, rapid, and inexpensive, with low organic solvent consumption, and is remarkably free from interference effects, rendering it an efficient method for the determination of iodine in milk powder and urine samples.     

Effect of six triorganotin(IV) compounds on nitrification and ammonification in soil

The effects of six triorganotin(IV) compounds and of Thiram on nitrification and ammonification in soil were investigated. Low concentrations of up to 50 μg g^?1 of the triorganotin(IV) compounds enhanced nitrate-nitrogen (NO₃^?-N) production in soil. Except for diphenylbutyltin bromide, which inhibited nitrification at 250 μg g^?1, the other triorganotin(IV) compounds were inhibitory at concentrations of 100 μg g^?1 to less than 250 μg g^?1. At 10 μg g^?1, only triphenyltin acetate was less inhibitory towards nitrification compared with Thiram. At 250 μg g^?1, Thiram exerted a strongly persistent inhibitory effect towards nitrification. The NO₃^?-N level recorded 28 days after application was only 0.10 μg g^?1 soil. With the triorganotin compounds NO₃^?-N levels of 7.05–12.06 μg g^?1 soil were recorded 28 days following their application. The deleterious effects of the triorganotin(IV) compounds were less persistent and recovery of nitrification was evident seven days after application. Low concentrations of Thiram and triorganotin(IV) compounds inhibited ammonification, whereas higher concentrations enhanced ammonification. Complete inhibition of ammonification was attained 21–28 days after application of Thiram at 50 μg g^?1. On the other hand, with the triorganotin(IV) compounds, except for diphenylbutyltin bromide at 10–50 μg g^?1, ammonification persisted at all concentrations 28 days after application.     

Determination of calcium and barium in steel by electrothermal atomic emission spectrometry

A simple and rapid method is described for the determination of 1–40 μg g^?1 calcium in steels by electrothermal atomic emission spectrometry. The sample is dissolved in nitric acid and does not need preconcentration. The use of a recessed platform is shown to improve reproducibility and sensitivity in the determination of calcium. A similar procedure for the determination of barium (< 1 μg g^?1 in steel is described.     

Sensitivity enhancement by palladium addition in the electrothermal atomic absorption spectrometry of mercury

In graphite-furnace atomic absorption spectrometry of mercury, addition of 50 μg ml^?1 palladium improves the peak height for 5 μg Hg ml^?1 50 times. Further addition of 20 μg ml^?1 platinum doubles the enhanced peak height. The effect is due to amalgam formation. The best sensitivity is 0.3 ng (1% absorption) and the detection limit is 0.1 ng. The method allows higher ashing temperatures than for solutions without noble metal addition and can be applied to solutions containing substantial amount of organic matter.     

Determination of antimony in steel by hydride generation and by electrothermal zeeman atomic absorption spectrometry

Procedures are described for the determination of antimony in steel. Samples by decomposed with a nitric/perchloric acid mixture and antimony is determined either by a.a.s. after hydride generation with sodium tetrahydroborate or by graphite-furnace a.a.s. with Zeeman background correction. Some reference steel samples were analyzed by both methods and by instrumental neutron activation. The results obtained (45–680 μg g^?1 antimony) were in very good agreement; detection limits were about 3 μg g^?1. The relative standard deviation for samples with > 50 μg g^?1 antimony was 〈 5%.     

Determination of indium in minerals,river sediments and coal fly ash by electrothermal atomic absorption spectrometry with palladium as a matrix modifier

A method is described for the determination of indium (10–40 μg g^?1) in lead-zinc ores and magnetic pyrites. Graphite furnace atomic absorption spectrometry is used with palladium as a matrix modifier. Indium (down to 0.085 μg g^?1) in river sediments and coal fly ash can be determined after pre-extraction with ammonium iodide into 4-methyl-2-pentanone. In the presence of palladium, the maximum tolerable ashing temperatures for indium in aqueous solution or organic extract can be raised to 1200°C or 1000°C, respectively, and the sensitivity is greatly improved.     

Determination of hydrogen in stainless steels by spark-source mass spectrometry

A spark-source mass spectrometric (SSMS) method capable of determining traces of hydrogen in micro-volumes of metals was developed by using a pointed metal probe technique. The hydrogen background was decreased to μg g^?1 levels by the combination of a method in which the sample in the ion source is baked under vacuum at 323–343 K for more than 25 ks and a liquid nitrogen or liquid helium cryogenic pump method. This method was applied to the analysis of austenitic stainless steels at μg g^?1 hydrogen levels, and the relative standard deviation was within 20% for samples with hydrogen concentrations ranging from 2 to 4 μg g^?1. The relative sensitivity coefficent was 2.3 (Fe=1).     

Determination of bismuth in nickel-base alloys by atomic absorption spectrometry with introduction of solid samples into an induction furnace

Atomic absorption spectrometry with an induction furnace is applicable'to the determination of bismuth at 0.02–10 μg g^-1 levels in 1–30-mg samples of nickel-base alloys dropped into the furnace. Calibration graphs of peak absorbance versus mass of bismuth are constructed by use of standardised alloys. Samples of alloys can be added to the furnace at 2.5-min intervals. Calibration graphs, accuracy, precision and limits of detection of the method are discussed for 26 alloys. Accuracy is assessed by comparing the induction furnace results with results supplied with the alloys, and with results obtained for solutions of the alloys by atomic absorption spectrometry in association with hydride generation or a mini-Massmann furnace. With alloys containing more than 0.1 μg Bi g^-1, relative standard deviations by the induction furnace method are usually < 15%. The limit of detection for bismuth is 0.02 μg g^-1     

The determination of platinum and palladium in copperbased standard reference materials by neutron activation analysis

The determination of palladium and platinum by n.a.a. in 100-1 μg g^?1 Pd-Cu and Pt-Cu alloys is described. To avoid systematic errors, standards with approximately the same shape and composition as the samples were prepared by quantitative deposition of the noble metals from dilute hydrochloric acid medium on copper powder; after ignition in hydrogen, the powder was pressed to standard pellets. Platinum was determined by i.n.a.a. via ¹⁹⁹Au. For palladium an instrumental analysis via ¹¹¹Ag was possible only for the 100 μg g^?1 samples. For the lower concentrations copper was removed by cation exchange and palladium was determined via the ¹⁰⁹Pd-^109mAg isotopes. The precision for each analysis was 2–3 % relative. The accuracy was checked by comparison with results from other laboratories.     

Determination of Iodine in Cereal Grains and Standard Reference Materials by Neutron Activation Anaylsis

Abstract

Trace amounts of iodine in thirty-eight cereal grain samples cultivated at different locations in Austria were determined for the first time in this study by radiochemical neutron activation analysis. For the dissolution of cereal grain samples and standard reference materials, two different procedures, alkaline and acidic dissolution, were applied in the presence of an iodine carrier. Rapid and simple dissolution procedure with acidic solution was demonstrated in this study. The analytical values in the cereal grain as well as in the standard reference materials obtained by the different dissolution procedures were in good agreement within one standard deviation. The iodine in cereal grains and the standard reference materials ranged from 0.002 to 0.03 μg g^?-1 and 0.0015 to 0.30 μg g^?-1, respectively. The distribution of relative standard deviation (RSD) for iodine concentration below 0.01 μg g^?-1 were 21% and 24% of all data for the range 1–10% RSD and 11–20% RSD, respectively. The RSD for 0.1 μg g^?1 of iodine concentrations were around 10%     

Determination of cadmium,indium and zinc in nickel—base alloys by atomic absorption spectrometry with introduction of solid samples into furnaces

Atomic absorption spectrometry with an induction furnace is used for the determination of cadmium (0.002–2 μg g^-1), indium (0.6–350 μg g^-1) and zinc (0.05–26 μg g^-1) in 0.8–35 mg samples of nickel—base alloys dropped into the furnace. A resistively-heated furnace is employed for the determination of lower concentrations of indium (<0.6 μg g^-1). Standardised alloys were used for calibration. Accuracy, precision and detection limits are described for numerous nickel—base alloys. With alloys containing zinc, > 0.1 μg Cd g^-1 and >0.6 &,mu;g In g^-1, the relative standard deviations are 12%, 8% and 7%, respectively. Calculated detection limits for cadmium, indium and zinc are 2 ng g^-1, 10 ng g^-1 and 10 ng g^-1, respectively.     

Automated method for the determination of boron in water by flow-injection analysis with in-line preconcentration and spectrophotometric detection

A sensitive, automated method for the determination of boron in water samples is described, involving flow injection with on-line ion-exchange preconcentration and spectrophotometric detection of the azomethine-H—boron complex. The method is applicable to various water samples and is free from interferences, even in coloured samples. Detection limits of 5 μg l^?1 at 20 samples h^?1 and 1 μg l^?1 at 10 samples h^?1 with relative standard deviations of < 10% at 1–10 μg l^?1 and < 5%at 10–200 μg l^?1 levels of boron were achieved. The recoveries for spiked natural water samples ranged from 96 to 101%. The method compares favourably with inductively coupled plasma atomic emission spectrometry.     

The determination of low lead levels in the bone of lead-depleted mice by graphite furnace atomic absorption spectrometry

Low lead levels in the femurs of mice fed with a lead-depleted diet have been determined by use of electrothermal atomic absorption spectrometry with Zeeman-effect background correction. The method is based on the use of Mg(NO₃)₂/Pd as matrix modifier which enables significant reduction of the spectral interferences prevalent if chemical modifiers based on NH₄H₂PO₄ with either Ca or Mg are used for samples rich in Ca₃(PO₄)₂ matrix. The method was developed and validated by use of the NIST standard reference material 1486 bone. Bones were decomposed in a pressurized microwave-heated system using 70% nitric acid. Forty-three mice femurs, with a mass of 74.62 ± 12.54 mg, were dissolved in concentrated nitric acid. The lead results found in SRM 1486 (1.25 ± 0.15 μg g^–1, n = 9) were in good agreement with the certificate (1.335 ± 0.014 μg g^–1). Recoveries of 200 ng lead added to the SRM before or after digestion were 99.0 ± 1.4% and 98.5 ± 1.6%, respectively. The lead detection limit in bone samples is 0.06 μg g^–1 dry mass. This method is, therefore, suitable for the determination of very low lead levels (0.06–0.20 μg Pb kg^–1 bone) in the femurs of mice fed a diet with lead level of < 20μg kg^–1.     

Substoichiometric isotope-dilution analysis for strontium by liquid-liquid extraction with a macrocyclic crown ether or cryptand

Strontium(II) is substoichiometrically extracted into 1,2-dichloroethane with 1.0 × 10^?4 M cryptand-2.2.2 or 18-crown-6 in the presence of 1.0 ×10.2 M picrate at pH 8–10 or 7–9, respectively. A constant substoichiometric amount of strontium(II) is extracted (relative standard deviation, 0.5%). The method combined with isotope dilution is applied to determine strontium(II) in a seaweed sample (Laminaria religiosa Miyabe); the values obtained were 546 ± 9 μg g^?1 with cryptand-2.2.2 and 546 ± 7 μg g^?1 with 18-crown-6.