Slurry Sampling Electrothermal Atomic Absorption Research Articles

Determination of Mercury in Sediments by Slurry Sampling Electrothermal Atomic Absorption Spectrometry

The concentration of mercury in suspensions of sediments is determined by electrothermal atomic absorption spectrometry (ET-AAS) using a novel chemical modifier (ChM) based on activated carbon treated by iron(II) formate. The efficiency of chemical modifiers based on activated carbon, also modified by Ag(I), Au(III), Pd(II), Co(II), and Ni(II) compounds is studied. The optimum conditions are found for the temperature and time program of the atomizer; they prevent mercury losses at the stage of drying sample suspensions and also exclude spectral interferences at the stage of atomization and measurement of the analytical signals. The minimum characteristic mass of mercury (52 pg) is reached using an iron-containing chemical modifier based on activated carbon. The conditions of ET-AAS analysis using this ChM are tested on certified reference materials of sediments and a sample selected near the sea port of Temryuk (Sea of Azov). The limit of detection found by the 3s-test was 0.05 mg/kg and the relative standard deviation was 5% at the concentration of mercury in the sample 149 mg/kg.

Determination of Cu, Cd, Pb and Cr in yogurt by slurry sampling electrothermal atomic absorption spectrometry: A case study for Brazilian yogurt

A slurry sampling electrothermal atomic absorption spectrometric method is proposed for the determination of trace elements such as Cu, Cr, Cd and Pb in yogurt. The main factors affecting the slurry preparation were optimized: nature and concentration of acid solution and sonication time. The analytical method was validated in-house by calibration, linearity, limits of detection and quantification, precision and accuracy test obtaining satisfactory results in all cases. The proposed method was applied for the determination of Cd, Cr, Cu and Pb in some Brazilian yogurt samples. For these samples, the concentrations ranged from 2.5±0.2 to 12.4±0.2ngg−1; 34±3 to 899±7ngg−1; <8.3 to 12±1ngg−1; and <35.4 to 210±16ngg−1 for Cd, Cu, Cr and Pb, respectively. The daily intake of Cd, Cu, Cr and Pb via consumption of these samples was estimated.

Heated Slurry Sampling for the Determination of Cadmium in Food by Electrothermal Atomic Absorption Spectrometry

A heating procedure is reported with slurry sampling electrothermal atomic absorption spectrometry to improve the accuracy of cadmium determination in food. In comparison to conventional slurry sampling, the heating significantly increased cadmium recovery and improved the precision. For the optimized procedure, 25–250 mg of food were treated with 2% HNO3 and 1% H2O2 with heating at 120°C for 20 min, followed by the addition of 50 µL of 10% Triton X-100, and homogenization in an ultrasonic bath prior to analysis. Tungsten and rhodium were employed as a permanent modifier with optimum pyrolysis and atomization temperatures of 500°C and 1500°C. Calibration with aqueous standards resulted in good agreement between certified or information values and measured results at the 95% confidence level. A characteristic mass of 0.8 ± 0.1 pg and a detection limit of 0.7 ng g−1 for a 2% slurry were obtained. The method was employed for the direct determination of cadmium in food certified reference materials.

Determination of cadmium and lead in urine samples after dispersive solid–liquid extraction on multiwalled carbon nanotubes by slurry sampling electrothermal atomic absorption spectrometry

A new method for the determination of Cd and Pb in urine samples has been developed. The method involves dispersive solid-phase extraction (DSPE), slurry sampling (SS), and subsequent electrothermal atomic absorption spectrometry (ETAAS). Oxidized multiwalled carbon nanotubes (MWCNTs) were used as the sorbent material. The isolated MWCNT/analyte aggregates were treated with nitric acid to form a slurry and both metals were determined directly by injecting the slurry into the ETAAS-atomizer. The parameters that influence the adsorption of the metals on MWCNTs in the DSPE process, the formation and extraction of the slurry, and the ETAAS conditions were studied by different factorial design strategies. The detection and quantification limits obtained for Cd under optimized conditions were 9.7 and 32.3ngL−1, respectively, and for Pb these limits were 0.13 and 0.43μgL−1. The preconcentration factors achieved were 3.9 and 5.4. The RSD values (n=10) were less than 4.1% and 5.9% for Cd and Pb, respectively. The accuracy of the method was assessed in recovery studies, with values in the range 96–102% obtained for Cd and 97–101% for Pb. In addition, the analysis of certified reference materials gave consistent results. The DSPE–SS–ETAAS method is a novel and useful strategy for the determination of Pb and Cd at low levels in human urine samples. The method is sensitive, fast, and free of matrix interferences, and it avoids the tedious and time-consuming on-column adsorption and elution steps associated with commonly used SPE procedures. The proposed method was used to determine Cd and Pb in urine samples of unexposed healthy people and satisfactory results were obtained.

Direct determination of cadmium in geological samples by slurry sampling electrothermal atomic absorption spectrometry

An accurate and high throughput method involving slurry sampling ETAAS was developed to detect trace Cd content in various geological samples.

Direct determination of Cd, Pb and Cr in honey by slurry sampling electrothermal atomic absorption spectrometry

Slurry sampling electrothermal atomic absorption spectrometry was used for direct determination of Cr, Pb and Cd in honey without sample pretreatment. The honey slurries were prepared in aqueous solution containing hydrogen peroxide and nitric acid. The slurries were directly introduced in the pyrolytic graphite tubes. Pd–Mg was used as a chemical modifier only for Cd determination. Analytical curves were performed with aqueous standards for Pb and Cr and with addition of fructose for Cd. The quantification limits for Cd, Pb and Cr were 2.0, 5.4 and 9.4ngg−1, respectively. Acceptable precision of the methodology was obtained through repeatability and intermediate precision. In the accuracy study, recoveries were satisfactory (94–101%) for the three elements. The methodology was applied in honey from Paraná (Brazil). The concentrations of Pb, Cd and Cr ranged from 141 to 228ngg−1, <2.0 to 8ngg−1 and 83 to 94ngg−1, respectively.

Slurry sampling electrothermal atomic absorption spectrometric determination of chromium after separation/enrichment by mercaptoundecanoic acid modified gold coated TiO2 nanoparticles

In this study, a novel preconcentration/separation technique based on the slurry analysis of chromium loaded on mercaptoundecanoic acid modified TiO2 core-Au shell nanoparticles prior to its determination by electrothermal atomic absorption spectrometry was described. For this purpose, at first, TiO2 nanoparticles were coated with gold shell and then modified with mercaptoundecanoic acid (MUA). Cr (III) was collected on the prepared sorbent by conventional batch technique. After separation of liquid phase, slurry of the sorbent was prepared and directly introduced into graphite furnace of atomic absorption spectrometry. By this way, all drawbacks due to elution procedure were eliminated. Optimum conditions for quantitative sorption and preparation of the slurry were investigated. The chromium in certificated sea-water and spiked drinking water was recovered in the range of 95% confidence level. The proposed technique was fast and simple as well as the risks of contamination and loss during elution were low. The limit of detection (3σ, N=10) was 0.34μgL−1.

Determination of toxic elements in plastics from waste electrical and electronic equipment by slurry sampling electrothermal atomic absorption spectrometry

Cadmium, chromium, lead and antimony were determined in slurries prepared using pulverized samples of personal computers and mobile phones dispersed in dimethylformamide medium. Determinations were carried out by electrothermal atomic absorption spectrometry (ETAAS) using a graphite furnace atomic absorption spectrometer. The optimization of the experimental conditions (chemical modifier, pyrolysis time, pyrolysis temperature and atomization temperatures) was accomplished by evaluating pyrolysis and atomization curves. Optimization was also used to determine the temperatures corresponding to the best sensitivities and the lowest background signals. The pyrolysis temperatures were fixed at 600 °C (for Cd), 700 °C (for Pb), 1100 °C (for Sb), and 1200 °C (for Cr); atomization temperatures were established as 1400 °C (for Cd), 1300 °C (for Pb), 1900 °C (for Sb), and 2300 °C (for Cr), and the chemical modifier (50 μg NH 4H 2PO 4 + 3 μg Mg(NO 3) 2 was used for Cd and Pb while 5 μg Pd + 3 μg Mg(NO 3) 2 was used for Sb). The use of a chemical modifier for Cr determination was not necessary. The characteristic masses were 1.9 pg for Cd, 32.3 pg for Pb, 54.1 pg for Sb, and 9.1 pg for Cr. Calibration was performed using standard additions in a range of 5–20 μg L −1 for Cd, 5–30 μg L −1 for Cr, 12.5–50 μg L −1 for Pb, and 25–100 μg L −1 for Sb with linear correlation coefficients higher than 0.99. Limits of detection were 0.9, 1.4, 6.8, and 2.9 μg L −1 for Cd, Pb, Sb, and Cr, respectively. The results indicate that recoveries for all metals agreed at a 95% confidence level when a paired t-test was applied and presented good precision. The accuracy of the proposed method was evaluated by addition–recovery experiments, showing results in the 96–112% range, and also by comparison of the results using Student's t-test with another method developed using ETAAS for digested samples. Analyte concentrations in the samples investigated varied from 5 to 525, 51 to 611, and 30 to 458 mg kg −1 for Cd, Cr, and Pb, respectively, while the content of Sb was in the 0.2–1.65% range.

Use of sodium tungstate as a permanent chemical modifier for slurry sampling electrothermal atomic absorption spectrometric determination of indium in soils

A number of chemical modifiers have been assessed for the direct determination of indium in soils using electrothermal atomic absorption spectrometry and slurry sampling. The best results were obtained when the graphite atomizer was impregnated with sodium tungstate, which acts as a permanent chemical modifier. Slurries were prepared by suspending 100 mg sample in a solution containing 1% (v/v) concentrated nitric acid and 10% (v/v) concentrated hydrofluoric acid and then 15-microL aliquots were directly introduced into the atomizer. Standard indium solutions prepared in the suspension medium in the range 4-80 microg L(-1) indium were used for calibration. The relative standard deviation for ten consecutive measurements of a 40 microg L(-1) indium solution was 2.8%. The limit of detection in soils was 0.1 microg g(-1). The reliability of the procedures was confirmed by analysing two standard reference materials and by using an alternative procedure.

The use of slurry sampling for the determination of manganese and copper in various samples by electrothermal atomic absorption spectrometry

Manganese and copper in multivitamin–mineral supplements and standard reference materials were determined by slurry sampling electrothermal atomic absorption spectrometry. Slurries were prepared in an aqueous solution containing Triton X-100. The effects of different parameters such as ratio of solid to liquid phase volume, total slurry volume and addition of Triton X-100 as a dispersant on the analytical results were investigated. The graphite furnace programs were optimized for slurry sampling depending on the analytes and their concentrations in the samples. The linear calibration method with aqueous standard solutions was used for the quantification. At optimum experimental conditions, R.S.D. values were below 5%. The analytes were determined in the limits of 95% confidence level with respect to certified values in coal and soil standard reference materials and to those found by wet-digestion in multivitamin–mineral supplements. Detection limits (3 δ) for Mn and Cu were 0.10 μg L −1 and 1.82 μg L −1 for 10 μL coal standard reference material slurry, respectively.

Determination of vanadium content in soils by slurry sampling electrothermal atomic absorption spectrometry using KO300G as the stabilizing agent

Abstract A direct and sensitive method for the determination of vanadium concentrations in soil is developed using ultrasonic slurry sampling electrothermal atomic absorption spectrometry (USSSETAAS). The surfactant, KO300G, is used as the stabilizing agent. The precision and accuracy of the method are investigated. The detection limits are 0.6 and 0.7 µg 1−1 for SRM Montana Soil 2711 and SRM Soil — S, respectively. The method is applied to determine the vanadium content in 10 soil samples from the Wielkopolska region.

Feasibility of employing permanent chemical modifiers for the determination of cadmium in coal using slurry sampling electrothermal atomic absorption spectrometry

Iridium and ruthenium, alone and in combination with tungsten, thermally deposited on the platform of a transversely heated graphite tube, were investigated for their suitability as permanent chemical modifiers for the determination of cadmium in coal slurries by electrothermal atomic absorption spectrometry (ET AAS). The conventional mixed palladium and magnesium nitrates (Pd–Mg) modifiers, added in solution, were also investigated for comparison. The latter one showed the best performance for aqueous solutions, and the mixed W–Ir and W–Ru permanent modifiers had the lowest stabilizing power. All of the investigated modifiers lost some of their stabilizing power when coal slurries were investigated. The Pd–Mg modifier, pure Ir and Ru, and a mixture of 300 μg W + 200 μg Ir could stabilize Cd at least to a pyrolysis temperature of 600 °C, whereas all the other combinations already failed at temperatures above 500–550 °C. Additional investigations of the supernatant liquid of the slurries supported the assumption that the high acid concentration of the slurries and/or a concomitant leaching out of the coal might be responsible for the reduced stabilizing power of the modifiers. The maximum applicable pyrolysis temperature of 600 °C was not sufficient to reduce the background absorption to a manageable level in the majority of the coal samples. High-resolution continuum source ET AAS revealed that the continuous background absorption was exceeding values of A = 2, and was overlapping with the analyte signal. Although the latter technique could correct for this background absorption, some analyte was apparently lost with the rapidly vaporizing matrix so that the method could not be considered to be rugged. A characteristic mass of 1.0 pg and a detection limit of 0.6 ng g − 1 could be obtained under these conditions.

Identification of Cu and Ni indicator plants from mineralised locations in Botswana

Plant species that accumulate high levels of metals in proportion to the metal content in the soil are of considerable interest in biogeochemical and biogeobotanical prospecting. This study was aimed at investigating copper and nickel accumulation in the plants Helichrysum candolleanum and Blepharis diversispina, to assess their potential use as mineral indicators in biogeochemical prospecting. Soils and plants were collected from copper–nickel mineralised areas in Botswana. Analyses of the soils and the respective plant parts (roots, stem, leaves and flowers) were carried out using ultrasonic slurry sampling electrothermal atomic absorption spectrometry (ETAAS), which allowed rapid determination of copper and nickel in small amounts of the samples. The metal concentration in the soil was in the range ≈ 40 μg/g–4% (w/w) for Cu and ≈ 60 μg/g–0.3% (w/w) for Ni. The concentration ranges of the elements in the plant parts were ≈ 6 μg/g–0.2% Cu and ≈ 3–210 μg/g Ni. At high soil metal content (greater than 2.5% (w/w) Cu and 0.1% (w/w) Ni), high levels of both nickel and copper were found in the shoots (leaves and flowers) of H. candolleanum. Concentrations as high as 0.2% (w/w) Cu were found in the leaves and flowers of H. candolleanum, indicating hyperaccumulation for this plant. For B. diversispina, the metal concentrations did not exceed 100 μg/g for any plant part, for both metals. Both plant species tolerate high concentrations of metals and should therefore be categorized as metallophytes. In order to evaluate metal translocation from the soil to the shoots, metal leaf transfer coefficients (ratio of metal concentration in the leaf to metal concentration in the soil) were calculated. Our data suggest that the two plant species have different metal uptake and transport mechanisms, which needs to be investigated further. The present work also suggests that H. candolleanum may be used as a copper/nickel indicator plant in biogeochemical or biogeobotanical prospecting.

Slurry Sampling Techniques for the Determination of Lead in Bangladeshi Fish Samples by Electrothermal Atomic Absorption Spectrometry with a Metal Tube Atomizer

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis.

Determination of mercury in sewage sludge by direct slurry sampling graphite furnace atomic absorption spectrometry

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry (ETAAS) method was elaborated to the determination of Hg in sewage sludge samples with the use of KMnO 4+Pd modifier. The minimum sample amount required for slurry preparation with respect to sample homogeneity was evaluated by weighting masses between 3 and 30 mg directly into the autosampler cups. Validation of the proposed method was performed with the use of Certified Reference Materials of sewage sludge, CRM 007-040 and CRM 144R. Two sewage sludge samples from Poznañ (Poland) city were analysed using the present direct method and a method with sample digestion, resulting in no difference within statistical error.

Determination of lead in plants in controlling phytoremediation processes using slurry sampling electrothermal atomic absorption spectrometry

The comparative determination of lead in plant samples by two atomic spectrometric techniques is reported. At first, slurry sampling electrothermal atomisation atomic absorption spectrometry (ETAAS) was applied. The results obtained were compared with those found after a wet digestion procedure by flame atomic absorption spectrometry (FAAS) or ETAAS. The accuracy of the studied methods was checked using a certified reference material (CL − 1 CRM, Cabbage Leaves). The recovery of lead was 90% for slurry sampling ETAAS, and 86.6% for liquid sampling ETAAS. The advantages of the slurry sampling ETAAS method are the simplicity of sample preparation and very good sensitivity.

Evaluation of two atomisation modes for direct determination of molybdenum in complex matrices by ultrasonic slurry sampling–electrothermal atomic absorption spectrometry

Tube wall (TWA) and L’vov platform (LPA) atomisations were compared for the direct determination of molybdenum (Mo) in coal fly ash by slurry sampling–electrothermal atomic absorption spectrometry (ETAAS). For both atomisation modes eight chemical modifiers were tested, namely HNO 3, Pd(NO 3) 2, Mg(NO 3) 2, Pd + Mg(NO 3) 2, reduced Pd, BaF 2, Ir and HF. The interfering effects of major and minor concomitants of samples on Mo signals and memory effects were also evaluated. BaF 2 and Pd(NO 3) 2 + Mg(NO 3) 2 mixture were selected for TWA and LPA, respectively. Standard addition calibration is needed in both cases. The best peak performance, memory effect reduction, within-run precision (6% versus 9% R.S.D.), and sensitivity ( m o = 7.5 pg versus 15.2 pg) were achieved with TWA compared to LPA. Both atomisation modes gave good analytical recoveries (94–102%), but the analysis of a certified coal fly ash (NIST SRM 1633a) only was accurate using TWA. Additionally, the urban dust NIST SRM 1629a was analysed.

Slurry sampling electrothermal atomic absorption spectrometry as screening method for chromium in compost

Ultrasonic slurry sample introduction was applied to the determination of total chromium in composted materials by electrothermal atomic absorption spectrometry (ETAAS). The effect of grinding on the heterogeneity of the test samples and on the attainable precision was studied. The repeatability was influenced by the heterogeneity of the test samples at the μg-level, the R.S.D. of the measurements being 15%. The reproducibility depended on the heterogeneity of the test sample at the mg level, and it could be improved from 11 to 7% by increasing the grinding time. The characteristic mass was 2.6pg and the detection limit for the optimised procedure at the 0.04% (w/v) slurry concentration, 370ngg−1. Good agreement with a certified reference material and with the conventional microwave assisted digestion method was found by using external calibration with aqueous standards. The performance of the method for screening purposes was evaluated.

Slurry sampling electrothermal atomic absorption spectrometry as screening method for chromium in compost

Ultrasonic slurry sample introduction was applied to the determination of total chromium in composted materials by electrothermal atomic absorption spectrometry (ETAAS). The effect of grinding on the heterogeneity of the test samples and on the attainable precision was studied. The repeatability was influenced by the heterogeneity of the test samples at the μg-level, the R.S.D. of the measurements being 15%. The reproducibility depended on the heterogeneity of the test sample at the mg level, and it could be improved from 11 to 7% by increasing the grinding time. The characteristic mass was 2.6 pg and the detection limit for the optimised procedure at the 0.04% (w/v) slurry concentration, 370 ng g−1. Good agreement with a certified reference material and with the conventional microwave assisted digestion method was found by using external calibration with aqueous standards. The performance of the method for screening purposes was evaluated.

Study of parameters associated with the determination of cadmium in lake sediments by slurry sampling electrothermal atomic absorption spectrometry

Cadmium concentration in lake sediments is determined by suspending the solid samples in a solution containing 5% (v/v) concentrated nitric acid and 0.1% (v/v) Triton X-100. Three modifiers were tested for the direct determination. The furnace temperature programmes and appropriate amount for each modifier were optimised to get the highest signal and the best separation between the atomic and background signals. The drying stage is performed by programming a 400 °C temperature, a ramp time of 25 s and hold time of 10 s on the power supply of the atomiser. No ashing step is used and platform atomisation is carried out at 2200 °C. W–Rh permanent modifier combined with conventional modifier by delivering 10 μl of 0.50% (w/v) NH 4H 2PO 4 solution was the best chemical modifier for cadmium determination. This modifier also acts as a liquid medium for the slurry, thus simplifying the procedure. Calibration is performed using aqueous standards in the 1–5 μg l −1 range. The optimised method gave a limit of detection of 0.56 ng ml −1, characteristic mass of 10.1±0.8 pg for aqueous standard, 9.6±0.7 pg for slurry samples containing different Cd concentrations and good precision (7.6–5.2%). The method was validated by analysing four certified reference lake sediment materials: LKSD-1, LKSD-2, LKSD-3 and LKSD-4; satisfactory recoveries were obtained (90.0–96.3%) and no statistical differences were observed between the experimental and the certified cadmium concentration. The developed methodology was used to determine cadmium in three ‘real’ sediment samples from lakes in the area of Wielkopolski National Park, Poland.