Determination of heavy metals in soil, mushroom and plant samples by atomic absorption spectrometry

The concentrations of heavy metals in the soil, mushroom and plant samples collected from Tokat, Turkey have been determined by flame and graphite furnace atomic absorption spectrometry after dry ashing, wet ashing and microwave digestion. The study of sample preparation procedures showed that the microwave digestion method was the best. Good accuracy was assured by the analysis of standard reference materials. The relative standard deviations for all measured metal concentrations were lower than 10%. In all cases, quantitative analytical recoveries ranging from 95 to 103% were obtained. Metal accumulation factors were calculated for mushroom and plant samples. High ratio of plants to soil cadmium, zinc and copper concentrations indicate that these elements are accumulated by mushrooms. Results obtained are in agreement with data reported in the literature.     

Determination of selenium, zinc and cadmium in antidandruff shampoos by atomic spectrometry after microwave assisted sample digestion

Microwave assisted pre-treatments for atomic spectrometric determination (inductive coupled plasma-optical emission spectrometry, ICP-OES or flame atomic absorption spectrometry, FAAS) of metallic elements, usually present in antidandruff shampoos, are proposed. They are based on the digestion of the sample with HNO₃ into a closed reactor, which is irradiated at 800 W for a few minutes. Selenium was determined by ICP-OES. The limit of detection was 0.11 mg l⁻¹; the relative standard deviation (R.S.D.) for the selenium content in the samples was in the 0.6–3.6% range. The results obtained were in agreement with the label contents and the recovery of the proposed method was in the 100–106% range. Zinc and cadmium were determined by FAAS. The limit of detection for zinc determination was 0.078 mg l⁻¹; the R.S.D. for zinc contents was in the 0.8–8.6% range. A limit of detection of 0.09 mg l⁻¹ was obtained for cadmium determination; the R.S.D. for cadmium contents was in the 0.7–2.7% range. The determinations were performed after two different sample mineralization pre-treatments — dry ashing (in an electric furnace) and wet mineralization (in a microwave oven). Both methodologies provided comparable results for zinc and cadmium determination in shampoos. The proposed microwave assisted digestion procedures allow a precise and accurate determination of selenium, zinc and cadmium in commercial antidandruff shampoos, and the sample pre-treatment is less time-consuming than the classic methods.     

Arsenic determination in certifiable color additives by dry ashing followed by hydride generation atomic absorption spectrometry

The preparations of digested samples of certifiable color additives by dry ashing and wet digestion for arsenic analysis by hydride generation atomic absorption spectrometry (AAS) were compared. The dry ashing technique was based on the preparation used in ASTM D4606-86 for determination of As and Se in coal. The acid digestion method used nitric and sulfuric acids heated by microwaves in sealed vessels. The digested color additives were analyzed for As by using hydride generated from sodium borohydride mixed with the acidified solution on a flow injection system leading to an atomic absorption spectrometer. Dry ashing was preferable to wet digestion because wet digestion yielded poor recoveries of added As. Dry ashing followed by hydride generation AAS gave determination limits of 0.5 ppm As in the color additives. At a specification level of 3 ppm As, the precision of the method using dry ashing was +/- 0.4 ppm (95% confidence interval).     

微波消解-GFAAS法测定菠菜粉和蘑菇粉中微量镉的研究

应用微波消解-石墨炉原子吸收光谱法对菠菜粉和蘑菇粉中微量镉的含量进行测定。菠菜粉和蘑菇粉经HNO3+H2O2微波消解体系消解后,采用磷酸二氢铵作为基体改进剂,灰化温度为900℃,原子化温度为1 350℃,镉含量在0~2 ng/mL范围内与吸光度呈线性关系,线性相关系数为0.999 4,检出限为0.02 mg/kg。该法测定结果的相对标准偏差小于4%(n=6),加标回收率为96.7%~103.2%。     

Determination of thirteen common elements in food samples by inductively coupled plasma atomic emission spectrometry: comparison of five digestion methods

Five sample digestion procedures were evaluated for the determination of Al, B, Ca, Cu, Fe, K, Mg, Mn, Na, P, S, Sr, and Zn in food samples by inductively coupled plasma atomic emission spectrometry. The 5 procedures include dry ashing at 500 degrees C, wet digestion with HNO3-HClO4, microwave digestion with HNO3, microwave digestion with HNO3-H2O2, and microwave digestion with HNO3-H2O2-HF. For microwave digestion with HNO3-H2O2-HF, silicon (IV) oxide was used to eliminate the excess HF, making it possible to determine total Al, B, and other common elements accurately and simultaneously. Seven National Institute of Standards and Technology standard reference materials (SRMs) were analyzed to compare the recovery of 13 elements with above digestion procedures. The results demonstrated that the microwave digestion procedure with HNO3-H2O2-HF yielded the best recoveries for all 13 elements in the selected SRMs. The determined concentrations of most elements were close for all 3 microwave digestion procedures with the exception of Al in oyster tissue, bovine liver, and spinach. Notably, the wet digestion with HNO3-HClO4 is the simplest and the most effective procedure for the selected elements except Al and B. Although there are several concerns with the dry ashing procedure, it might be a preferable procedure for those analyses where only nonvolatile elements are to be determined and the concentrations of the elements are low.     

Microwave digestion and matrix separation for the determination of cadmium in urine samples by electrothermal atomization atomic absorption spectrometry using a fast temperature program

 A method is proposed which involves sample pretreatment followed by electrothermal atomic absorption spectrometry (ETAAS) for determination of cadmium in human urine. A microwave digestion system was devised to accommodate double-closed vessels for simultaneous digestion of batches of up to 24 urine samples in about 20 min. After digestion, matrix substances which might interfere were removed using silica-immobilized 8-hydroxyquinoline (I-8HOQ) columns. The analyte adsorbed on the column was then eluted with dilute nitric acid solution and determined by ETAAS using a fast temperature program. Neither ashing steps in the furnace heating program nor use of matrix modifiers was necessary. The accuracy, precision, limit of detection, and sample throughput of the method were evaluated. With meticulous control of systematic errors which may be introduced in the pretreatment procedures, the present method can serve as a reference technique for the analysis of Cd in urine samples. Received: 29 July 1996/Revised: 30 September 1996/Accepted: 13 October 1996     

Microwave digestion and matrix separation for the determination of cadmium in urine samples by electrothermal atomization atomic absorption spectrometry using a fast temperature program

 A method is proposed which involves sample pretreatment followed by electrothermal atomic absorption spectrometry (ETAAS) for determination of cadmium in human urine. A microwave digestion system was devised to accommodate double-closed vessels for simultaneous digestion of batches of up to 24 urine samples in about 20 min. After digestion, matrix substances which might interfere were removed using silica-immobilized 8-hydroxyquinoline (I-8HOQ) columns. The analyte adsorbed on the column was then eluted with dilute nitric acid solution and determined by ETAAS using a fast temperature program. Neither ashing steps in the furnace heating program nor use of matrix modifiers was necessary. The accuracy, precision, limit of detection, and sample throughput of the method were evaluated. With meticulous control of systematic errors which may be introduced in the pretreatment procedures, the present method can serve as a reference technique for the analysis of Cd in urine samples. Received: 29 July 1996/Revised: 30 September 1996/Accepted: 13 October 1996     

虾粉中总砷测定方法的探讨

用氢化物原子荧光光度法测定虾粉中总砷含量时,对干法灰化、湿法消解、微波消解3种样品处理方法对虾粉中砷元素测定结果的影响进行了比较。通过试验确定了最佳消解条件。砷元素浓度在0~10μg/L的范围内与荧光强度呈线性关系,线性相关系数r=0.999 6,检出限为0.2μg/L。比对结果表明,干法灰化适合于测定虾粉中总砷的含量,湿法消解测定总砷的含量偏低,微波消解不适合测定虾粉中总砷的含量。采用干法灰化-氢化物原子荧光光度法测定虾粉中总砷含量,加标回收率为76.2%~106.0%。     

金汞捕集冷原子吸收法测定生物样品中痕量汞的试样预处理方法比较

采用微波炉分解和湿法分解进行生物样品的预处理，结合高灵敏的金汞捕集冷原子吸收法测定了生物样品中的痕量汞。对采用不同分解方法获得的试样进行了空白值、精密度、加标回收，准确度及检出限等性能方面的试验和比较，方法成功地用于生物样品中痕量汞的测定。     

Determination of vanadium in mussels by electrothermal atomic absorption spectrometry without chemical modifiers

A method was developed for the quantitative determination of total vanadium concentration in mussels via electrothermal atomic absorption spectrometry (ETAAS). After the microwave digestion of the samples, a program using temperatures of 1600 °C and 2600 °C for ashing and atomization respectively, without any matrix modifiers, allowed us to obtain results that were satisfactory since they agreed closely with certified reference material values. The detection limit was 0.03 mg kg^–1 (dry weight), indicating that the method is suitable for the analysis of mussel samples. This determination was compared with matrix modifiers that have been reported previously. The method was applied to various cultivated and wild mussels from the Galician coast, yielding levels below 1 mg kg^–1 (wet weight).     

ICP-AES测定铀污染土壤植物中铀的研究

采用电感耦合等离子体发射光谱(ICP-AES)对铀污染土壤植物中铀的测定方法进行了研究.在λU385.958 nm处,选择了仪器的最佳工作条件,考察了酸度和常见共存元素对测定的干扰情况,并且对比了干灰化消解和湿式消解对测定的影响.研究发现2%硝酸溶液为最佳介质,干扰离子对测定没有显著影响,干灰化消解比湿式消解得彻底.在选定条件下,方法检出限为0.18 mg·L-1,测定下限为0.61 mg·L-1,5.0000 mg·L-1的铀标准溶液的相对标准偏差RSD(n=10)为0.81%,方法回收率为96.2%～106.2%.该方法操作简单,快速.结果表明,用ICP-AES测定铀污染土壤植物样品中的铀是可行的.     

Preparation of conducting electrodes from biological samples for multi-element trace analysis by spark-source mass spectrometry or emission spectrometry

Four decomposition procedures frequently used for biological material (dry ashing, open wet digestion, wet digestion in a teflon bomb and low-temperature ashing) are optimized for the conversion of biological samples to conducting electrodes suitable for multi-element trace determinations by spark-source mass spectrometry or emission spectrometry. The optimized procedures are evaluated with respect to contamination, retention and preconcentration of the trace elements, homogeneity of the electrodes and precision of the final results. Both dry-ashing methods are prone to losses by volatilization; simple dry ashing suffers from contamination problems during electrode preparation. Wet digestion gives better precision; digestion with nitric/sulfuric acids in an open flask is the method of choice for most elements being simpler and giving lower blanks than the bomb method.     

Determination of traces of molybdenum in foods by electrothermal atomic absorption spectrometry

Low levels of molybdenum in different food samples were determined by atomic absorption spectrometry with electrothermal atomization after destruction of organic matter using four different methods, involving dry ashing at 600°C, wet digestion with heating with nitric/sulphuric and nitric/sulphuric/perchloric acid mixtures or direct extraction with dilute hydrochloric acid. In all cases the working conditions, reproducibility, precision and accuracy were investigated. The dry ashing method was generally the optimum destruction method.     

Comparison of sample preparation procedures for the determination of trace heavy metals in house dust, tobacco and tea samples by atomic absorption spectrometry

The effect of wet ashing, dry ashing and microwave procedure for the determination of trace metal levels was investigated in house dust, tobacco and tea samples by atomic absorption spectrometry. The study of sample preparation procedures showed that the microwave method was the best. The recovery of trace metals was very good and precision and accuracy were compatible with standard reference material. The relative standard deviations for all measured metal concentrations were lower than 10%. The digestions of HNO3/H2SO4/HClO4 (4: 1: 1) mixture for house dust, HNO3/H2SO4/H2O2 (2: 2: 2) mixture for tea and HNO3/H2O2 (4: 2) mixture for tobacco were very efficient.     

Rapid determination of lead in biological tissues by microsampling-cup atomic absorption spectrometry

Lead can be determined in kidney, liver, and lung tissues by a rapid technique which does not require ashing or acid digestion of the sample. The tissue is homogenized with water, an aliquot of the homogenate is pipetted into a microsampling cup, and lead is determined directly by atomic absorption spectrometry. Calibration is by lead standards in a whole blood matrix. Results correlate well with those obtained by a wet-ashing procedure. The sensitivity (0.01 μg Pb g^-1 wet tissue) permits the analysis of typical tissues with good precision. The procedure is rapid, and its simplicity minimizes the risk of contamination by extraneous lead during sample preparation.     

Determination of phosphorous in organic compounds and metal complexes by inductively-coupled plasma atomic emission spectrometry

Phosphorus is determined by inductively-coupled plasma atomic emission spectrometry at 213.618 nm. Different types of organic and inorganic phosphorus compounds and metal complexes were examined after direct dissolution in water, aqueous ethanol or acid, or after decomposition by oxygen flask combustion or Kjeldahl digestion; results were within the usual limit of precision and accuracy for such determinations. The effect of small (<20%) ethanol concentrations in the aqueous solution on the signals obtained from a low-power (1200 W) argon plasma is examined and discussed.     

Solid sampling coupled to flame furnace atomic absorption spectrometry for Mn and Ni determination in petroleum coke

A solid sampling flame furnace atomic absorption spectrometry (SS-FF-AAS) system was developed for Mn and Ni determination in petroleum coke. The proposed system for solid sampling was a quartz cell with two perpendicular tubes (T-shaped tubes), positioned above the burner. Manganese and Ni determination was made using an atomic absorption spectrometer with deuterium background corrector, air-acetylene flame and a single slit burner. Powdered samples of coke were introduced as pellets (up to 62 mg) into the quartz cell with a movable hollow quartz piston. When the sample pellet reached the end of quartz cell (T-connection), in the presence of a constant oxygen flow, it quickly burned and the combustion products were transferred to the upper slit tube where the atomic absorption process occurs. Calibration was possible using aqueous reference solutions applied directly on high purity graphite pellets. Results obtained for Mn and Ni using the proposed SS-FF-AAS system were compared to those obtained by inductively coupled plasma optical emission spectrometry (ICP OES) and inductively coupled plasma mass spectrometry (ICP-MS) after sample decomposition by high pressure microwave assisted acid digestion and also by microwave induced combustion. Agreement better than 96% was obtained for both methods employing a previous step of sample digestion (ICP OES and ICP-MS) and by SS-FF-AAS. Accuracy was evaluated using certified reference materials and also recovery tests. The relative standard deviation was lower than 9% for both analytes. The characteristic mass was 18.3 and 14.7 ng and the limit of detection was 0.6 and 0.8 µg g^− 1 for Mn and Ni, respectively. The proposed SS-FF-AAS system can be applied for Mn and Ni determination in petroleum coke, combining a relatively high sample throughput (9 determinations per h), and a suitable precision and accuracy.     

Determination of ultratrace bismuth in milk samples by atomic fluorescence spectrometry

A sensitive procedure was developed for determination of bismuth (Bi) in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS) after microwave-assisted sample digestion with HNO3 and H2O2. The method provides a sensitivity of 1832 fluorescence units (ng/mL) with a detection limit of 0.01 ng/mL, which corresponds to 20 pg absolute limit of detection, equivalent to 0.50 ng/g in the original sample. Application of the methodology to cow milk samples from the Spanish market showed the presence of Bi at a concentration of 11.8-28.8 ng/g, which compared well with data obtained after dry ashing of samples and with data obtained by inductively coupled plasma-mass spectrometry after microwave-assisted digestion.     

Determination of silicon in biological samples by ICP-OES after non-oxidative decomposition under alkaline conditions.

A non-oxidative alkaline sample digestion procedure using tetramethylammonium hydroxide and a high pressure, microwave assisted autoclave digestion system was developed. The silicon concentrations of the digested samples were measured by inductively coupled axial plasma optical emission spectrometry (ICP-OES). Details of the digestion conditions as well as the optimised instrumental parameters for ICP-OES are described. The method was developed and tested using silicon-spiked ascorbic acid and applied to samples of animal tissue and organs. The total silicon content of two different reference materials, NIST 1577b Bovine liver and BCR 184 Bovine Muscle having neither certified nor informational values for Si was determined. The results obtained are compared with the results of independent methods such as wavelength dispersive x-ray fluorescence spectrometry (WDXRF) and solid sampling electrothermal atomic absorption spectrometry (ETAAS). The method described achieves a limit of detection of 2 mg kg(-1) using 100 mg of solid biological or organic material and covers a concentration range of up to 500 mg kg(-1).     

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.