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).     

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 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 calcium, potassium, manganese, iron, copper and zinc levels in representative samples of two onion cultivars using total reflection X-ray fluorescence and ultrasound extraction procedure

The chemical characterization of onion cultivar samples is an important tool for the enhancement of their productivity due to the fact that chemical composition is closed related to the quality of the products. A new sample preparation procedure for elemental characterization is proposed, involving the acid extraction of the analytes from crude samples by means of an ultrasonic bath, avoiding the required digestion of samples in vegetable tissue analysis. The technique of total reflection X-ray fluorescence (TXRF) was successfully applied for the simultaneous determination of the elements Ca, K, Mn, Fe, Cu and Zn. The procedure was compared with the wet ashing and dry ashing procedures for all the elements using multivariate analysis and the Scheffé test. The technique of flame atomic absorption spectrometry (FAAS) was employed for comparison purposes and accuracy evaluation of the proposed analysis method. A good agreement between the two techniques was found when using the dry ashing and ultrasound leaching procedures. The levels of each element found for representative samples of two onion cultivars (Yellow Granex PRR 502 and 438 Granex) were also compared by the same method. Levels of K, Mn and Zn were significantly higher in the 438 Granex cultivar, while levels of Ca, Fe and Cu were significantly higher in the Yellow Granex PRR 502 cultivar.     

Determination of essential metals in complete diet feed by flow injection and flame atomic absorption spectrometry

A prior study of different sample pre-treatments for the determination of metallic elements in complete diet feeds was performed in order to choose the most suitable for these samples. The studied pre-treatment were: acid extraction (lixiviation), wet digestion (on microwave oven) and dry ashing mineralization (calcination). Lixiviation (acid extraction) with hydrochloric acid was selected due to its accuracy, fast and simple pre-treatment procedure. Due of the different levels of concentration of the metallic elements in the samples, the same manifold was used but with small variations. Copper (with on-line pre-concentration by chelating Chelex-100 resin), calcium (with on-line dilution) and iron determination gave suitable accuracy and precision and required a little time for analysis. Five different samples were analyzed by flow injection and the results were contrasted with dry ashing mineralization in batch procedure and with the labeled contents.     

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.     

Development and validation of routine analysis methods for the determination of essential, nonessential, and toxic minor and trace elements in cereal and cereal flour samples by inductively coupled plasma-atomic emission spectrometry

Various digestion procedures were carefully investigated and accurately evaluated with respect to their effect on the analysis of cereals and cereal flours. Multielement methods were selected and well developed for the determination of essential (Cr, Cu, Fe, Mg, Mn, and Zn), nonessential (Ag, Al, Ba, Bi, In, and Ga), and toxic (Cd and Pb) minor and trace elements by inductively coupled plasma-atomic emission spectrometry. Only Ag could be determined, either with aqueous standard or standard addition calibration methods, while the standard addition methods were more accurate for the determination of other elements. The recoveries were mostly within the range of 84.1-113% for the expected values of all analytes with respect to certified reference material NIST SRM 1586a (rice flour). The results proved that, for cereals and cereal flours, the use of H2O2 for wet digestion and HNO3 for dry ashing were not necessary. Linear regression analysis and Student's paired t-test were applied to evaluate the significant differences between different procedures and type of samples.     

Cadmium losses on wet and dry ashing of plant materials

Cadmium losses on wet and dry ashing were studied using tomato leaves with metabolized¹⁰⁹Cd radiotracer. The most appreciable Cd losses (up to 35%) occured when sulphuric acid was used on wet ashing due to Cd retention in the CaSO₄ precipitate formed. Only trace amounts of Cd were retained in a silicaceous precipitate resulting from wet ashing in the absence of sulphuric and hydrofluoric acids in the decomposition mixtures employed. Small Cd losses (up to 7%) were observed on dry ashing in the air in open systems at temperatures not exceeding 500°C. Cd losses increased, however, to 30% when the final ashing temperature was raised to 900°C. Incorporation of the¹⁰⁹Cd radiotracer into various parts of tomato plants and its distribution between soil and the plants are also briefly reported.     

The Determination of Co in Plant Materials by Radiochemical Neutron Activation Analysis

The influence of irradiation conditions on the results of Co determination in plant samples by radiochemical neutron activation analysis (RNAA), after the conventional and microwave assisted wet digestion, has been investigated. Nine CRMs of botanical origin were examined. The study has demonstrated that the effectiveness of mineralization depended significantly on the kind of sample and the irradiation conditions. When analyzed CRMs were subjected to long-term irradiation in a high neutron flux, the mineralization using the microwave technique was necessary to obtain the correct results of Co determination in some of the plant samples. It has been proved that microwave digestion in a mixture of HNO₃+H₂O₂+HF should be a standard method of wet ashing, independent on matrix and irradiation conditions.     

A study of sample mineralization methods for arsenic analysis of blood and urine by hydride generation and graphite furnace atomic absorption spectrometry

Mineralization procedures for blood and urine suitable for the determination of arsenic by Hydride Generation Atomic Absorption Spectrometry (HGAAS) are studied on model samples, and the results are utilized in biological monitoring investigations. The objective of this work is to obtain good total As recoveries for both matrices regardless of added As species (As(III), As(V), DMA, MMA, AsB, or AsC). Prior to the HGAAS analyses, preparation procedures were controlled under optimised conditions by graphite furnace atomic absorption spectrometry (GFAAS). Two preparation procedures for urine give As recoveries close to 100% by HGAAS: a) dry ashing at 420°C with Mg(NO₃)₂ on a hot plate, and b) microwave oven decomposition with (NH₄)₂S₂O₈. For blood samples, As recoveries by HGAAS range between 95 and 108% for all species when using dry ashing after a pretreatment of samples with HNO₃ and H₂O₂ in a microwave oven. Wet digestion with (NH₄)₂S₂O₈ in a microwave oven gives recoveries very near 100% for As _inorg. and MMA. For other As species in spiked blood samples, recoveries of less than 20% As are found. Precision and detection limits obtained by both techniques are evaluated as well. For arsenic concentrations of 20 μg dm⁻³ or more in blood and urine, a chemical modifier is recommended for GFAAS analysis; it may or may not be proceeded by a mineralization step. For low As levels encountered in the unexposed population, the HGAAS technique provides reliable results only if a very complete mineralization procedure is used.     

Determination of trace elements by inductively coupled plasma mass spectrometry of biomass and fuel oil reference materials using milligram sample sizes

Most of the analytical techniques used to quantify elements associated with solid samples suffer from high detection limits and cannot be used for trace elements in biomass samples, particularly when only 20 mg are available for analysis. Inductively coupled plasma mass spectrometry (ICP-MS) can achieve detection limits of parts-per-trillion with liquid sample introduction by solution nebulisation. This technique was therefore tested with two standard biomass reference materials: oriental tobacco leaves and cabbage leaves. Two preparations successfully used on coal standards were used to digest the solid samples: a total digestion method (wet ashing digestion) and a partial leaching (microwave extraction). The concentrations of up to seventeen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, Sn, V and Zn) were measured after the two preparations. The accuracy and sensitivity of the measurements improved when the dilution factor decreased from 5000 to 1000 and to 500. Since the proportion of mineral matter in biomass samples is small (5%), the microwave digestion extracted elements that are generally not completely extracted from coal samples (e.g. Sb). However, some trace element concentrations were below the limit of quantification after microwave extraction, even with a reduced dilution factor (As, Se and Mo) and could not be quantified. A fuel oil was also digested. The trace element concentrations were very low (between 28 and 0.1 microgram g(-1)) but acceptable results were obtained by applying a dilution factor of 100. Only six elements in the fuel oil (As, Ba, Co, Ni, Se and V) had certified or indicated values. Factors affecting the accuracy and sensitivity of the analyses are discussed. The reproducibility of analysis of the tobacco leaf standard was checked over a period of nine months by both digestion methods. The wet ashing method gave acceptable reproducibility for Ba, Cd, Co, Cu, Ga, Mn, Mo, Ni, Pb, V and Zn but poor precision for Cr, Se and Sn and showed evidence of residual chloride interference for As. The microwave extraction gave good reproducibility for As, Ba, Cd, Co, Cr, Cu, Mo, Ni and Zn but poor precision for Se and low recoveries for Ga, Mn, Sn and V. In spite of the small quantities of material analysed, it proved possible to determine the trace elements at levels down to 0.1 microgram g(-1) in the reference materials.     

Comparison of recoveries of inogranic and organic incorporated75Se by four mineralization methods of biological material

The recovery of selenium⁷⁵Se added as selenite to human blood and to mixed food, and the recovery of biologically incorporated⁷⁵Se from different rat tissues were determined by using four mineralization methods. The recoveries of⁷⁵Se after dry ashing /HNO₃, Mg/NO₃/₂/ and after three wet digestion methods — 1. HNO₃, HClO₄ 2. HNO₃, HClO₄, H₂SO₄ 3. HNO₃, HClO₄, MgCl₂ were as follows: 50–106%, 96–99%, 92–99% and 97–100%, resp. Losses of⁷⁵Se in wet digestion /HNO₃, HClO₄/ were observed at the end of the procedure, when an excess of acids was evaporated. The addition of MgCl₂ to the digestion mixture prevented the escape of⁷⁵Se and thus permitted the total evaporation of the digest without any loss of selenium.     

Comparison of wet microwave digestion methods of plant materials for the determination of metals by flame atomic absorption spectrometry

Microwave closed-system wet digestion procedures for plant samples were examined. Each procedure was tested with samples of tobacco and cabbage, and included digestion by the use of different acids composition, almost complete evaporation of the digest, and then dissolution of the residue in 1% nitric acid. Three microwave digestion programs that varied power, duration, and temperature were used. Closed-vessel reactions followed open-vessel reaction-delay time. Using flame atomic absorption spectrometry on the digests, four or five elements were determined to evaluate effectiveness, precision and accuracy of analytes extraction into solution. After a preliminary study of tobacco digests, the four most effective procedures were chosen, and detailed investigations were carried out on both tobacco and cabbage reference materials. Although all four of the final procedures were accurate, the most precise procedure, with the lowest errors of determination, was using reverse ‘aqua regia’ for tobacco and ‘aqua regia’ for cabbage.     

Determination of Al,B and 11 Other Trace Elements in Plants by Inductively Coupled Plasma-Atomic Emission Spectrometry:Comparison of Five Different Sample Digestion Procedures

For accurate determination of nutritional and toxic elements in plants by means of inductively coupled plasma atomic emission spectrometry (ICP-AES), sample preparation is a critical phase. Although some procedures such as dry ashing in a muffle furnace or wet digestion with HN0₃-HC10₄ on a hot plate have been available for many years, growing interest has been focused on the use of microwave-based digestion in recent years. Compared to the classical digesting procedures, microwave digestion has some significant advantages:the digestion is carried out in closed vessels so that the contamination and the loss of volatile elements are markedly minimized; the digestion is less time consuming due to the elevated pressure and temperature within the vessels. In addition, the use of polytetrafluoroethylene (PTFE) vessels for microwave digestion makes it both easy and safe to employ very corrosive reagents, such as HF.     

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%。     

Ashing and microwave digestion of aerosol samples with a polypropylene fibrous filter matrix

Radionuclide monitoring is one of the key techniques required by the International Monitoring System (IMS) and On-Site Inspection (OSI) in the Comprehensive Nuclear Test Ban Treaty (CTBT). There shall be a global network of 80 radionuclide monitoring stations. Atmospheric aerosols are collected generally on filters in the stations. A polypropylene (PP) fibrous filter is often used in sampling atmospheric aerosols. There might be much information to be obtained by measuring aerosol samples after digestion rather than nondestructive analysis directly by γ-spectrometry. The present work focused on pretreatment of the filter samples, which includes the influence of different ashing or microwave digestion conditions on the recoveries of analytes. The inductively coupled plasma-atomic emission spectrometric detection results indicated that the recoveries of elements in the PP fibrous filters by ashing were influenced by ashing time, temperature and the properties of the elements. High recoveries of volatile elements and consistent recovery for other elements were obtained by using a closed microwave system to digest the filters. Higher sensitivity was also obtained when the intercomparison sample was measured by a HPGe well detector after pretreatment by the recommended ashing and microwave digestion procedures.     

Critical comparison of wet and dry digestion procedures for trace metal analysis of meat and fish tissues

The efficiency of four methods of digestion was evaluated for trace metal analysis of pork meat and carp fish tissues. Two methods of dry and two methods of wet ashing were compared in terms of calculated variances. Mixtures of HCl+HNO₃ were applied for wet ashing of the samples at 100 °C, while dry ashing with or without H₂SO₄ at 450 °C were the alternative methods. The digests were subsequently analysed for Pb, Cd, Cu and Zn by graphite furnace atomic absorption spectrometry. Analysis of variance and Student's t-test were performed separately for meat and fish analytical results. Wet digestion with a (1+1) mixture of HCl+HNO₃ has given better recovery and repeatability for almost all metals than a (9+1) mixture of HCl+HNO₃. Also between the dry ashing methods, the use of H₂SO₄ has given better results than ashing of the tissues without H₂SO₄.     

Determination of Zn, B, Fe, Mg, Ca, Na and Si in anisette samples by inductively coupled plasma atomic emission spectrometry

A comparative study of several digestion methods of anisette samples has been carried out. Two dry ashing (DA) treatments as well as four wet ashing (WA) procedures using different mixtures of acids were applied for the sample mineralisation before analysis. Once the anisette samples were mineralised, the contents of Zn, B, Fe, Mg, Ca, Na and Si were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Each method has been studied statistically and also attending to their feasibility. After performing the optimisation of the different treatments tested, it was concluded that one wet ashing method employing a HNO₃:H₂O₂ (10:1) mixture was the most suitable. This method was applied to the analysis of anisette samples. Na, Ca, Mg and Si were present in concentrations up to 215 mg l⁻¹ for Na, 11.6 for Mg, 6.2 for Ca and 5.1 for Si. Fe and B concentrations were not higher than 0.12 mg l⁻¹ and lower for Zn.