Determination of cadmium and lead in biological samples by three ultrasonic-based samples treatment procedures followed by electrothermal atomic absorption spectrometry

The development of 3 different ultrasonic-based sample treatment methods, ultrasonic probe-assisted acid extraction, ultrasonic-assisted acid slurry, and ultrasonic-assisted acid pseudodigestion is presented. These methods were compared for the determination of Cd and Pb by electrothermal atomic absorption spectrometry in biological samples (blood and scalp hair) and validated by using certified materials BCR 397 human hair and BCR 185R bovine liver. The sample amounts chosen to perform the analysis were 100 mg and 0.5 mL for solids (human hair and bovine liver) and blood samples, respectively. An acid digestion induced by microwave energy was used to obtain the total metal concentrations and for comparative purposes. The best results were obtained with the ultrasonic-assisted acid pseudodigestion, with which it was possible to perform accurate and precise determination of the Cd and Pb contents in 2 certified reference materials and biological samples of 50 normal males of ages 25-40 years. The precision of the methods, together with their efficiency, rapidity, low cost, and environmental acceptability, make them good alternatives for the determination of trace metals from biological samples. The precision of the methods for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level, and the relative standard deviations were lower than 10% (n=10) for all determinations.     

Determination of gallium in biological materials by electrothermal atomic absorption spectrometry

In this determination of gallium, the condition of the graphite tubes influences the peak height. Common acids and salts seriously affect the results, but in the presence of EDTA, interferences of nitric and hydrochloric acids are suppressed completely, and interferences of phosphoric acid and some salts are suppressed partly. To compensate for the effects, a standard addition procedure is proposed, and is applied to healthy and tumor.bearing mice. A linear calibration is obtained for 0.12–12 ng Ga in 50-μl aliquots. The method is applied to tissues and body fluids with good recovery and precision.     

Determination of lead in biological materials by constant-temperature electrothermal atomic absorption spectrometry

A comparison is made between a platform-equipped Perkin-Elmer HGA-500 and a recently designed two-step constant-temperature graphite furnace with respect to susceptibility to interference effects as well as attainable detection limits. It is shown that larger quantities of biological samples can be used with the constant-temperature furnace without suppressing the analyte signal, resulting in lower detection limits. Materials studied include NBS Olyster Tissue and Bovine Liver, and human lung tissue and human blood.     

Methylmercury determination in biological samples using electrothermal atomic absorption spectrometry after acid leaching extraction

An efficient and sensitive method for the determination of methylmercury in biological samples was developed based on acid leaching extraction of methylmercury into toluene. Methylmercury in the organic phase was determined by electrothermal atomic absorption spectrometry (ETAAS). The methylmercury signal was enhanced and the reproducibility increased by formation of certain complexes and addition of Pd-DDC modifier. The complex of methylmercury with DDC produced the optimum analytical signal in terms of sensitivity and reproducibility compared to complexes with dithizone, cysteine, 1,10-phenanthroline, and diethyldithiocarbamate. Method performance was optimized by modifying parameters such as temperature of mineralization, atomization, and gas flow rate. The limit of detection for methylmercury determination was 0.015 μg g⁻¹ and the RSD of the whole procedure was 12% for human teeth samples (n=5) and 15.8% for hair samples (n=5). The method’s accuracy was investigated by using NIES-13 and by spiking the samples with different amounts of methylmercury. The results were in good agreement with the certified values and the recoveries were 88–95%.     

Determination of As,Cd, Cu,Hg and Pb in biological samples by modern electrothermal atomic absorption spectrometry

Pollution from heavy metals has increased in recent decades and has become an important concern for environmental agencies. Arsenic, cadmium, copper, mercury and lead are among the trace elements that have the greatest impact and carry the highest risk to human health. Electrothermal atomic absorption spectrometry (ETAAS) has long been used for trace element analyses and over the past few years, the main constraints of atomic absorption spectrometry (AAS) methods, namely matrix interferences that provoked high background absorption and interferences, have been reduced. The use of new, more efficient modifiers and in situ trapping methods for stabilization and pre-concentration of these analytes, progress in control of atomization temperatures, new designs of atomizers and advances in methods to correct background spectral interferences have permitted an improvement in sensitivity, an increase in detection power, reduction in sample manipulation, and increase in the reproducibility of the results. These advances have enhanced the utility of Electrothermal atomic absorption spectrometry (ETAAS) for trace element determination at μg L⁻¹ levels, especially in difficult matrices, giving rise to greater reproducibility, lower economic cost and ease of sample pre-treatment compared to other methods. Moreover, the recent introduction of high resolution continuum source Electrothermal atomic absorption spectrometry (HR-CS-ETAAS) has facilitated direct solid sampling, reducing background noise and opening the possibility of achieving even more rapid quantitation of some elements. The incorporation of flow injection analysis (FIA) systems for automation of sample pre-treatment, as well as chemical vapor generation renders (ETAAS) into a feasible option for detection of As and Hg in environmental and food control studies wherein large numbers of samples can be rapidly analyzed. A relatively inexpensive approach with low sample consumption provide additional advantages of this technique that reaches figures of merit equivalent to Inductively coupled plasma mass spectrometry (ICP-MS). Herein is presented an overview of recent advances and applications of (ETAAS) for the determination of As, Cd, Cu, Hg and Pb in biological samples drawn from studies over the last decade.     

Determination of total tin and tributyltin in marine biological materials by electrothermal atomic absorption spectrometry

Total tin and tributyltin in marine biological tissue are determined at the sub-μg g^?1 level by graphite-furnace atomic absorption spectrometry. Total tin is extracted by digestion with nitric acid, and tributyltin is extracted by n-hexane after treatment with hydrochloric acid. A matrix modifier (ammonium dihydrogenphosphate), and a stabilized-temperature platform furnace are used to overcome matrix effects. Zeeman background correction is used. Results of analyses of oyster (Crassostrea gigas), salmon (Salmo salar) and a reference material (Bowen's kale) are presented. The detection limit for both methods is ca. 30 ng of tin with a relative standard deviation (n = 6) of 7.8% for a sample containing 200 ng of tin.     

Determination of arsenic in biological fluids by electrothermal atomic absorption spectrometry

A procedure for the determination of the total content of arsenic in urine, serum and blood by electrothermal atomic absorption spectrometry (ETAAS) is described. Zeeman correction is used to compensate the high background signals. The samples are diluted (1 + 1 for urine and 1 + 3 for both serum and blood samples) in a medium containing 0.1% w/v Triton X-100 before being introduced directly into the furnace. A solution containing 15% w/v hydrogen peroxide, 0.65% w/v nitric acid and 0.5% w/v nickel is also introduced into the atomizer by means of a separate injection. Calibration is carried out against aqueous standards for blood and serum samples and using the standard additions method for urine samples. The detection limit is 20 pg (2 ng ml-1). The reliability of the procedure is checked by analyzing three certified reference materials and by recovery studies.     

Determination of Cd by electrothermal atomic absorption spectrometry after electrodeposition on a graphite probe modified with palladium

Traces of Cd were determined by electrothermal atomic absorption spectrometry after electrochemical preconcentration on a commercial graphite ridge probe modified with Pd. The Pd electrochemically deposited on the probe surface served not only as the modifier but it also protected the graphite surface. Cd was electrodeposited at a controlled potential − 1.2 V (vs. saturated calomel electrode) using the Pd-modified graphite probe as a working electrode. The sensitivity of Cd determination remained unchanged for 300 electrodeposition and atomization cycles. The detection limit (3σ_blank) was improved with increasing time of electrolysis and was 1.2 ng l^− 1 for a 10 min electrolysis time in the presence of 0.1 mol l^− 1 NaNO₃. The procedure was applied for the determination of Cd in (1 + 1) diluted seawater and in (1 + 1) diluted urine samples using the standard addition method.     

Determination of total mercury in environmental and biological samples by flow injection cold vapour atomic absorption spectrometry

A simple and accurate method has been developed for the determination of total mercury in environmental and biological samples. The method utilises an off-line microwave digestion stage followed by analysis using a flow injection system with detection by cold vapour atomic absorption spectrometry.

The method has been validated using two certified reference materials (DORM-1 dogfish and MESS-2 estuarine sediment) and the results agreed well with the certified values. A detection limit of 0.2 ng g⁻¹ Hg was obtained and no significant interference was observed. The method was finally applied to the determination of mercury in river sediments and canned tuna fish, and gave results in the range 0.1–3.0 mg kg⁻¹.     

Determination of total and methyl mercury in human permanent healthy teeth by electrothermal atomic absorption spectrometry after extraction in organic phase

A simple and sensitive method has been developed for determination of inorganic and methyl mercury in biological samples by ETAAS. For determination of methyl mercury; it was transferred to toluene phase by acid leaching extraction method. For total mercury after digestion of samples; it was extracted to toluene phase by means of the chelating agent diethyldithiocarbamate. Formation of complex between MeHg and diethyldithiocarbamate enhance the MeHg signal and increases the reproducibility. Furthermore, Pd-DDC was used as modifier for both mercury and methyl mercury determinations. The optimization performance was independently carried out by modifying the parameters such as temperature of mineralization, atomization and gas flow rate for methylmercury and inorganic mercury in ETAAS. The limits of detection were 0.15 and 0.12 μg g⁻¹ for methyl mercury and total mercury, respectively. The repeatability of the measurements of whole procedure were 15.8% for methyl mercury and 16.9% for total mercury determination. The accuracy of the method has been investigated by means of spiking different amounts of methylmercury and inorganic mercury to the samples. The recoveries were found within the range of 88-95% for methyl mercury and 85-92% for total mercury. For determination of total mercury, the method was validated by CVAAS. The obtained results by the present procedure were in good agreement with those of the CVAAS. The proposed method was applied for 30 human permanent healthy teeth (without filling) which significant positive correlations were found among number of amalgam filling and total mercury and MeHg.     

Determination of gold in biological materials by electrothermal atomic absorption spectrometry with a molybdenum tube atomizer

Electrothermal atomic absorption spectrometry (ETA-ASS) of gold with a molybdenum tube atomizer has been investigated. A sensitive ETA-AAS method was developed. The gold absorption signal became higher with the heating rate of the tube atomizer and as the ratio of hydrogen in the argon purge gas decreased. The optimal heating rate and the optimal gas flow rate were 5.5 C/msec and Ar 480 ml/min + H(2) 20 ml/min, respectively. The absolute characteristic mass (the mass of element giving 0.0044 abs.) of gold by the atomizer was 1.8 pg and the detection limit was 130 pg/ml (3S/N). These values were > 10 times better than those obtained with graphite atomizers, ICP and ICP-MS. The interferences caused by large amounts of interferents were evaluated. The addition of thiourea served to eliminate severe interferences. The recovery of spiked gold in biological materials was in the range of 101-106%.     

Determination of total tin in geological materials by electrothermal atomic absorption spectrometry

A graphite-furnace atomic-absorption spectrometric method is described for the determination of total tin in geological materials. Samples are decomposed by fusion with lithium metaborate and the melt is dissolved in diluted (1 + 9) nitric acid. Spectral and non-spectral interferences are minimized by a combination of platform volatilization, “normal” heating rate, addition of ammonia as chemical modifier, use of integrated absorbance values and Zeeman background correction. Results are reported for six reference materials showing good accuracy and a precision of 12% at the 3 μg g^?1 level. The detection limit for tin in the original materials in 0.7 μg g^?1.     

Determination of thallium in geological materials by extraction and electrothermal atomic absorption spectrometry

Thallium is determined in geological reference materials by acid digestion, extraction of thallium(III) from 0.5 M HBr solution into methyl isobutyl ketone and direct electrothermal atomic absorption spectrometry. The method yields results that agree with published values, has a detection limit of 0.04 μg Tl g^-1, and is relatively free of interferences.     

Determination of Cd, Cu, Pb and Zn in environmental samples: microwave-assisted total digestion versus aqua regia and nitric acid extraction

We validated the determination of the content of Cd, Cu, Pb and Zn using two digestion protocols: a microwave-assisted total digestion and an aqua regia extraction procedure based on the International Organization for Standardisation (ISO) 11466 method. Our goal in validating these two protocols, along with a nitric acid digestion, is to propose a rapid, cheap and easily automated digestion method for monitoring heavy metal content in environmental samples. We applied the digestion protocols to samples with a wide range of organic matter such as sediments, soils, sludges and plant material.For samples with a low carbonate or organic matter contents, such as sediments and agricultural soils, aqua regia digestion in an aluminium block was revealed to be an optimum estimator for the total metal content. For samples with a high organic matter content, such as organic horizons of forest floor layers, plant material and organic soils, nitric acid digestion could substitute microwave (MW)-hydrofluoric acid (HF) digestion. Except in a few samples with high organic matter or low heavy metal content, the RSD values obtained after the application of the proposed digestion procedures were lower than 5%. Based on the obtained results, a decision flow chart for choosing the fit-for-purpose digestion procedure is suggested.     

Determination of trace Cd and Pb in natural waters by direct single drop microextraction combined with electrothermal atomic absorption spectrometry

A new method of direct single-drop microextraction combined with electrothermal atomic absorption spectrometry (ETAAS) is presented for the determination of trace Cd and Pb with dithizone (H₂DZ) as chelating reagent. Factors influencing the microextraction efficiency and determination, such as pH, microdrop volume, stirring rate, extraction time were evaluated. Under the optimized experimental conditions, the detection limits of the method are 2 and 90 pg mL⁻¹ for Cd and Pb, and the relative standards deviations for 0.5 ng mL⁻¹ Cd and 10 ng mL⁻¹ Pb are 11 and 12.8%. After 10 min of extraction, the enrichment factors for Cd and Pb are 118 and 90, respectively. The results for the determination of Cd and Pb in tap water, spring water, river water, pond water, lake water and spiked water samples demonstrate the accuracy, recovery and applicability of the method. An environmental water certified reference material (GSBZ 50009-88) was analyzed, and the determined values are in a good agreement with the certified values. Correspondence: Bin Hu, Department of Chemistry, Wuhan University, Wuhan 430072, P.R. China     

螺旋藻中铅镉的ICP-MS测定

采用微波消解、高压罐消化以及HNO3 HClO4消化3种方法对螺旋藻样品进行处理,比较了不同方法产生的空白值和加标回收率。建立了微波消解-电感耦合等离子体质谱法测定螺旋藻样品中的铅镉的方法。铅镉检出限分别为0.06ng mL和0.05ng mL,RSD均小于3%,加标回收率在98%～101%之间。方法用于实际样品分析。     

Determination of cadmium in biological and environmental samples by slurry electrothermal atomic absorption spectrometry

The retention of cadmium by the bacteria Escherichia coli and Pseudomonas putida was optimized in order to develop a rapid and selective preconcentration method for cadmium from biological and environmental samples prior to determination by electrothermal atomic absorption spectrometry. Living and lyophilized cells for both bacteria were used, but the method using dead cells shows better analytical capabilities. Cadmium from aqueous solutions is easily retained on the outer membrane of both bacteria in the pH range 4-10, although the selected working pHs for E. coli and P. putida were 5 and 9, respectively. Cadmium retained by the bacteria was dispersed in 3.5 M nitric acid and the slurry was introduced directly into the graphite tube. The best sensitivity and detection limit were obtained for E. coli (0.03 ng ml(-1) and 0.04 ng ml(-1) respectively, in the absence of any chemical modifier). A strong spectral interference from nickel chloride was found and methods to overcome it were developed. The proposed extraction procedure was tested by the determination of cadmium in different standard biological and environmental samples.     

Determination of iron in seawater by electrothermal atomic absorption spectrometry and atomic fluorescence spectrometry: A comparative study

Two methods available for direct determination of total Fe in seawater at low concentration level have been examined: electrothermal atomization atomic absorption spectrometry (ETAAS) and electrothermal atomization laser excited atomic fluorescence spectrometry (ETA-LEAFS). In a first part, we have optimized experimental conditions of ETAAS (electrothermal program, matrix chemical modification) for the determination of Fe in seawater by minimizing the chemical interference effects and the magnitude of the simultaneous background absorption signal. By using the best experimental conditions, a detection limit of 80 ng L⁻¹ (20 μL, 3σ) for total Fe concentration was obtained by ETAAS. Using similar experimental conditions (electrothermal program, chemical modification), we have optimized experimental conditions for the determination of Fe by LEAFS. The selected experimental conditions for ETA-LEAFS: excitation wavelength (296.69 nm), noise attenuation and adequate background correction led to a detection limit (3σ) of 3 ng L⁻¹ (i.e. 54 pM) for total Fe concentration with the use a 20 μL seawater sample. For the two methods, concentration values obtained for the analysis of Fe in a NASS-5 (0.2 μg L⁻¹) seawater sample were in good agreement with the certified values.     

A study of the direct determination of Cd, Cr, Cu, Pb and Zn in certified reference materials of soils by solid sampling electrothermal atomic absorption spectrometry

A simple and rapid method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil was developed. The method was developed using three certified reference materials of soil: Eutric Cambisol, Orthic Luvisols and Rendzina, which differed in their matrix composition. Chemical modifiers were essential to achieve reproducible and interference-free signals for the analytes studied. The best results were obtained with a Pd/Mg(NO₃)₂ admixture for the determination of Cd, Pb and Zn and NH₄F for Cu. The combination of W (as a permanent modifier) and Mg(NO₃)₂ provided well-defined signal profiles for Cr. The following spectral lines were used: Cd 228.8 nm, Cr 520.6 nm, Cu 218.2 nm, Pb 205.3 nm and Zn 307.6 nm. The limit of detection was 4.2 ng g^− 1 for Cd, 1.1 μg g^− 1 for Cr, 0.5 μg g^− 1 for Cu, 1.3 μg g^− 1 for Pb and 8.6 μg g^− 1 for Zn for the maximum sample mass used. Under optimized conditions, the analyte and matrix were separated effectively in situ, and aqueous standards could be used for calibration.