Optimised method of coal digestion for trace metal determination by atomic absorption spectroscopy

Understanding the transport of trace elements through a coal-fired power plant requires reliable analytical methods for these elements in all the ingoing and outgoing mass streams. Coal and different kinds of ashes comprise the most abundant mass streams in such a plant. As a continuation of our previous work, we have optimised a digestion method for the AAS determination of heavy metals in coal samples. It has become evident that complete dissolution of metals in coal samples and accurate results in subsequent analysis can be obtained by means of applying pressurised digestion under microwave heating. The combination of HNO₃ (conc.) and HF (conc.) in the volume ratio of 50?:?1 attacked the sample well enough, and good recoveries for all the metals studied were obtained. Surprisingly good results were obtained also when HNO₃ alone was used as the digestion acid.     

Method performance of the closed vessel microwave-assisted acid extraction using 50% HNO3?:?HCl (3?:?2) with positive pressure Teflon membrane filtration

The recovery from soil of 22 metals on the U.S. Environmental Protection Agency’s (EPA) Target inorganic analyte list is described. The extraction method was developed to provide a safe, rapid, and analytically reliable means of leaching metals from soils and sediments in one procedure. The influence of digestion matrices, filtration media, reference standard types and instrument performance of inductively coupled plasma/optical emission spectroscopy is presented. The method employs a closed vessel, temperature and pressure controlled, microwave acid digestion using 20 mL of 50% HNO₃ : HCl in a ratio of (3 : 2). The digestate was filtered through a positive pressure Teflon membrane cartridge. This procedure recovered all metals at concentrations equal to or greater than what is possible by EPA standardized methods or other methods published in the literature. Excellent method precision and accuracy was obtained for all metals, especially Ag and Sb. Results show that the positive Teflon membrane filtration system yielded higher and statistically different concentrations of Mn, Zn, Cu, Fe, As, Cd, Pb, Ag, and Sb than paper filtration in half the time. These findings were produced from standard reference soils and soil collected from a hazardous waste site landfill. Received: 6 August 1998 / Revised: 14 January 1999 / Accepted: 19 January 1999     

Boron determination in biological materials by inductively coupled plasma atomic emission and mass spectrometry: effects of sample dissolution methods

This study compares four sample dissolution methods for Boron determination in two National Institute of Standard and Technology (NIST) botanical Standard Reference Materials (SRMs) and three Agriculture Canada/NIST RMs, each having a reference (certified or best estimate) B concentration. The dissolution treatments consisted of: 1) dry ashing at 500° C, 2) wet digestion with HNO₃ + H₂O₂, 3) extraction with hot HNO₃ and 4) closed vessel microwave dissolution. The samples were spiked before and after imposing dissolution treatments to study B recovery by inductively coupled plasma mass spectrometric (ICP-MS) analysis. Microwave digests of NIST SRM 1515 and some in-house RMs were also used to compare the B values of ICP-MS and ICP-AES (atomic emission spectrometry). While all three digestion methods (dry ashing, wet ashing and microwave) dissolved botanical samples, only the microwave method worked well for animal tissues. In terms of B values in these materials, there was no significant difference among the three digestion treatments. Near 100% recovery of B spiked before and after the sample dissolution indicates that there may not be a significant loss of B during the dissolution process used in this study. Extraction with hot HNO₃ was as effective as the three digestion treatments, and B values for this method agreed well with reference values. For the botanical materials studied, the B values determined by ICP-AES were not significantly different from ICP-MS values. This study shows that a simple, time and labor efficient hot HNO₃ extraction is as effective as other digestion/dissolution methods for quantitative B recovery from biological materials. Received: 13 June 1996 / Revised: 17 September 1996 / Accepted: 19 September 1996     

Dissolution of Al-Fe materials and analysis by inductively coupled plasma – atomic emission spectrometry

A technique was developed for the dissolution of Al-Fe materials containing difficult to dissolve Al₂O₃. The developed procedure uses HCl and HNO₃ for initial sample attack followed by digestion with a mixture of H₃PO₄ and H₂SO₄ at 200 °C. This procedure was employe to dissolve Al-Fe material samples before the determination of Al and Fe. Minor and trace elements (B, Cr, Cu, Mo, Si, Zr) were determined after dissolution in HCl and HNO₃. Results of a round robin study verified the procedure accuracy. The developed methods have the required accuracy and precision to be used as a quality control procedure for Al-Fe materials analysis. Received: 9 February 1998 / Revised: 1 April 1998 / Accepted: 4 April 1998     

Comparative study of different digestion procedures using supplementary analytical methods for multielement-screening of more than 50 elements in sediments of the river Elbe

The suitability of four different digestion procedures, i.e. i.) an aqua regia digestion according to DIN 38 414-S7, ii.) a pressure digestion using HNO₃/HF in PTFE-vessels, iii.) a HNO₃/HF + HCl-pressure digestion in PTFE-vessels and iv.) a HNO₃/HF + HCl-pressure digestion using microwave induction, has been evaluated with regard to the quantitative determination of about 50 elements in environmental samples. Three sediments of the river Elbe and two standard reference materials (MESS-1 and NIST 1645) have been employed. The analytical results from the dissolved samples, obtained using inductively coupled plasma mass- and optical emission spectrometry as well as total reflection X-ray fluorescence spectrometry, have been compared with those obtained by instrumental neutron activation analysis. Only digestion procedures using HNO₃/HF with a subsequent evaporation to dryness and dissolution in HCl have led to appropriate results for a wide range of elements (more than 50 elements in total). Because of its low contamination risk and its time saving, the microwave digestion is preferred. For this digestion procedure the accordance among the different instrumental methods used is high (better than 15% deviation) in general. A few elements (16) could be determined quantitatively only by a single method.     

The effect of sample preparation on metal determination in soil by FAAS

Different methods for the determination of several metals in soils by flame atomic absorption spectrometry (FAAS) were investigated. Different procedures for total dissolution of soil: I – HF+HClO₄, H₃BO₃, HCl digestion (conventional heating), II – HF+HClO₄, H₃BO₃ digestion followed by fusion with LiBO₂ (conventional heating) and III – HF+HCl+HNO₃, H₃BO₃ digestion (microwave heating), as well as a leaching procedure with HNO₃+HClO₄, HCl were tested and compared. For quality assessment, the certified reference material S-1 soil was used. For most of the investigated metals, the best accuracy and precision were achieved when the procedure I or III were used. The developed procedure was applied to the analysis of soil samples from crude oil refinery and dump of petroleum origin wastes regions. Received: 22 Dezember 1997 / Revised: 9 February 1998 / Accepted: 12 February 1998     

Optimized microwave preparation procedure for the elemental analysis of aquatic sediment

 This paper summarizes several key points in applying the microwave preparation technique to the elemental analysis of aquatic sediments and reports systematic experiments in searching for an optimal microwave preparation procedure for element analysis in sediment samples. The determination of the elements Cu, Pb and Cd in a standard reference aquatic sediment sample (CRM 280, COMEUR) was achieved by first digesting the samples in a microwave oven equipped with PFA advanced composite vessels, followed by AAS measurement. The influence of microwave power, digestion time, various dissolution reagents and the HF removing conditions was studied. It has been shown that for a 0.1 g sediment sample the optimal microwave preparation conditions are: 4–5ml HNO₃/HF/H₂O₂ as solvent, digesting time 30 min with 100% microwave power and evaporating the residual acid within 8 min in an open vessel at 80 °C. The element recovery rates with AAS measurement can reach up to 92.4–100.6%. Received: 23 July 1996/Revised: 23 September 1996/Accepted: 25 September 1996     

The role of different soil sample digestion methods on trace elements analysis: a comparison of ICP-MS and INAA measurement results

The measurement of trace-element concentration in soil, sediment and waste, is generally a combination of a digestion procedure for dissolution of elements and a subsequent measurement of the dissolved elements. “Partial” and “total” digestion methods can be used in environmental monitoring activities. To compare measurement results obtained by different methods, it is crucial to determine and to maintain control of the bias of the results obtained by these methods. In this paper, ICP-MS results obtained after matrix digestion with modified aqua regia (HCl+HNO₃+H₂O₂) method and two “total” digestion methods (microwave aqua regia+HF and HNO₃+HF) are compared with those obtained by instrumental neutron activation analysis, a non-destructive analytical method for the determination of the total mass concentrations of inorganic components in environmental matrices. The comparison was carried out on eight agricultural soil samples collected in one test area and measured by k₀-INAA and ICP-MS to determine As, Co, Cr, Sb and Zn mass concentration. The bias of results for As, Cd, Co, Cr, Cu, Ni, Pb, Sb and Zn of the three digestion methods were assessed using selected measurement standards. This paper highlights that the digestion procedure is an integral part of the measurement and can affect the measurement result in environmental analysis.     

Multi-elemental analysis of marine sediment reference material MESS-3: one-step microwave digestion and determination by high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS)

Single-step microwave digestion methods using four different acidic dissolving reagents were investigated with the main objective to obtain a simple, rapid method for multi-elemental analysis of marine sediment samples by high resolution inductively coupled plasma-mass spectrometry (HRICP-MS), especially for environmental studies. Closed-vessels microwave digestion procedures were carried out using the reagents as follows: HNO₃, mixture of HNO₃-HCl (φ _r = 9: 1), aqua regia, and mixture of HNO₃-HCl-HF (φ _r = 8: 1: 1). The elements analyzed were: Al, As, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, K, Li, Mn, Mo, Na, Ni, Pb, Sb, Sn, Sr, Ti, Tl, V, and Zn. Good recoveries were established for many of the metals analyzed even when only nitric acid was employed. However, for a good recovery of Sb and Tl, aqua regia should be employed.     

Determination of Arsenic,Cadmium, Cobalt,Chromium, Nickel,and Lead in Cosmetic Face-Powders: Optimization of Extraction and Validation

An analytical method for the quantification of toxic metals in face-powders is presented and discussed. Acid digestion with HNO₃-H₂O₂ or HNO₃-HCl was performed and compared with total digestion by HF. The digestion with HNO₃-H₂O₂ was the most suitable for these purposes. Analyses were performed by inductively coupled plasma atomic emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS), whose performances were compared by analyzing three different certified reference materials. The analysis of five commercial face-powders revealed the presence of all the considered metals in the range 0.06–8.0 µg/g. To simulate the bioaccessibility of metals in physiological conditions, a digestion with a simulated sweat solution was performed. In this case, the analysis of the same face-powder samples provided results below the limit of quantification, suggesting low bioaccessibility of the considered trace elements.     

Mercury analysis in environmental samples by EDXRF and CV-AAS

The analysis of total Hg in various environmental matrices was investigated using energy dispersive X-ray fluorescence (EDXRF) for both powdered and digested samples and cold vapor atomic absorption (CV-AAS) for digested samples. Several microwave decomposition procedures were evaluated with respect to the determination of Hg by CV-AAS and EDXRF. The use of different acid mixtures, microwave power settings and decomposition times were compared as well as the analysis on wet and freeze-dried samples. A set of standard reference samples were used to evaluate the procedures: NBS Citrus leaves (1572), NRC Pine needles (1575), NRC Dogfish muscle tissue (DORM-2), NRC Dogfish liver tissue (DOLM-2), BCR Human hair (397), BCR Coking coal (181) and NRC Marine sediment (PACS-1). An H₂SO₄/HNO₃/H₂O₂ acid mixture was found to be optimal for the complete mineralization and digestion of biological samples for Hg by CV-AAS whereas for EDXRF both the HNO₃/H₂O₂ and H₂SO₄/HNO₃/H₂O₂ acid mixture gave good results. The detection limit of EDXRF could significantly be decreased (from 0.2 μg/g to 0.058 μg/g) by performing the analysis with digested samples. A good agreement was obtained between CV-AAS and EDXRF analysis. The obtained results were also in good agreement with certified values. The methods were applied to environmental samples (coal, trees, leaves, spinach, fish, sediments) and human hair in a coal mining area and in places where they use coal for cooking in Vietnam. Received: 24 February 1997 / Revised: 13 June 1997 / Accepted: 18 June 1997     

Comparison of Pyrolysis and Microwave Acid Digestion Techniques for the Determination of Mercury in Biological and Environmental Materials

 Microwave digestion reduction-aeration and pyrolysis combined with cold vapour atomic absorption and cold vapour atomic fluorescence are compared for the determination of total mercury in several biological and environmental matrices. The biological samples were digested in a mixture of HNO₃/H₂O₂, the environmental samples in a mixture of HNO₃/HClO₄. After reduction with SnCl₂, the mercury was collected by two-stage gold amalgamation. After microwave digestion reduction-aeration, detection limits of 1.4 ng g⁻¹ and 0.6 ng g⁻¹ were obtained for cold vapour atomic absorption spectrometry (CVAAS) and cold vapour atomic fluorescence spectrometry (CVAFS), respectively, for 250 mg of environmental samples. For biological samples (500 mg) the detection limits were 0.7 ng g⁻¹ (CVAAS) and 0.4 ng g⁻¹ (CVAFS). After pyrolysis, detection limits of 3.5 ng g⁻¹ and 1.6 ng g⁻¹ for CVAAS and CVAFS, respectively, were obtained for a 10 mg sample. Pyrolysis can only be applied when the organic content of the sample is not too high. Accurate results were obtained for 8 certified reference materials of both environmental and biological origin. In addition, a real sludge sample was analysed. Author for correspondence. E-mail: richard.dams@rug.ac.be Received September 18, 2002; accepted December 3, 2002 Published online May 5, 2003     

Microwave digestion of sediment, soils and urban particulate matter for trace metal analysis

A microwave digestion technique was developed to determine the content of nine heavy metals in sediments and soils. The digests were subsequently analysed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The metals determined were Ca, Mg, Fe, Mn, Zn, Cr, Cd, Cu, Pb and V. The digestion was achieved by using an acid mixture of HNO₃, HF and distilled H₂O. The experimental study was conducted using four standard reference materials (SRMs): sewage sludge (LGC6136), marine sediment (PACS-1), urban particulate matter (NIST 1648) and coal carbonisation site soil (LGC6138). Two different programs were examined to determine which was optimal for the digestion of real environmental samples. The accuracy and precision of the two digestion programs for the analysis of the SRMs were compared. From the results obtained, the microwave program providing a maximum of power of 650 W and a cycle time of 51 min resulted in the best analytical performance. The experimental results obtained were in good agreement with the certified values and demonstrated that the proposed method is precise and accurate.     

Comparative study of bulk and partial digestion methods for airborne PM10-bound elements in a high mineral dust urban site in Constantine,Algeria

When high mineral loads in atmospheric particulate matter (PM) are present, particular attention should be paid to the selection of appropriate acidic digestion protocols for wet chemical analysis. We report on a comparative study of elemental recovery yields from five different pre-analytical acid digestion procedures for mineral-rich urban background PM₁₀ samples collected in the city of Constantine (Northeastern Algeria). Five reference materials (NIST 1633b, UPM 1648, NAT-7, SO-2 and SO-4) were also digested according to the same protocols. The selected acidic digestion/extraction procedures are widely used for PM chemical analysis and comprise P1 (HNO₃/HF/HCl), P2 (HCl/HNO₃), P3 (HCl/H₂O₂/HNO₃), P4 (HNO₃/HF/HClO₄) and P5 (HNO₃/H₂O₂); the latter assisted with microwave digestion. Elemental recovery yields were compared for major and trace elements typically determined in PM for source apportionment analysis and the results evidenced large differences. For most elements, the bulk extraction procedures (requiring the use of HF) allowed a full elemental recovery, particularly for elements that are associated with aluminium silicate species and oxides that are resistant to mild acid attack. In contrast, in the extraction protocols without HF low recovery yields were obtained for elements such as Al, Ti, Zr, Sc and other aluminium silicate-related elements in PM₁₀ samples with high mineral dust load. We highlight that the European standard digestion method EN-14902:2005 should be applied specifically for the metals for which this method was developed, but caution should be taken when the analysis of other elements in PM is required, especially in urban areas where road and vehicle wear dust is likely to be a major component of ambient PM. When using wet chemistry analysis for PM source apportionment studies, we strongly recommend HF bulk dissolution of samples to ensure the reliability of the geochemical information when coupled with an appropriate analytical tool.     

Ultrasound assisted pseudo-digestion for determination of iron and manganese in citric acid fermentation mediums by electrothermal atomic absorption spectroscopy

A sensitive, simple and rapid method for ultra-trace determination of iron and manganese based on ultrasound assisted pseudodigestion in citric acid fermentation medium samples (beet and cane molasses and raw sugar based mediums) is described. Parameters influencing pseudo-digestion, such as sonication time, sample mass and solvent system were fully optimized. Final solutions obtained upon sonication were analyzed by electrothermal atomic absorption spectrometry (ETAAS). The best conditions for metal pseudo-digestion were as follows: a 25, 30 and 20 min sonication time for beet molasses, cane molasses and raw sugar based medium samples, respectively, 0.7 g sample mass of raw sugar based samples, 0.5 g sample mass of molasses based samples and an extraction mixture of concentrated HNO₃-H₂O₂, in 25 mL of solvent. Analytical results obtained for the two metals by ultrasound assisted pseudo-digestion and conventional wet digestion methods showed a good agreement. This method reduces the time required for all treatments (heating to dryness, cooling and separation) in comparison with conventional wet digestion method. The accuracy of the method was tested by comparing the obtained results with that of conventional wet digestion method.      

Preparation and testing of standard solutions of cadmium, copper and lead

 Solutions of Cd, Cu and Pb at concentrations of about 1000 mg/l were prepared by dissolving the pure metals in HNO₃. Their concentration was verified by complexometric titration and by gravimetric analysis (Cu with salicylaldoxime, Cd with quinaldinic acid and Pb with 8-hydroxyquinoline). The results of the two methods were very similar and the uncertainty values were equal. However, the gravimetric determination can be regarded as more reliable, because titrimetric analysis is more prone to error due to inaccurate end-point reading. The expanded uncertainty of the concentrations of Cd and Cu attained 1 mg/l, which is half the value typically obtained for similar solutions from commercial manufacturers. To achieve such precise results, the bias had to be reduced by the highest possible extent, particularly by calibrating both the balance and the volumetric glassware. In addition to the uncertainty of the basic operations (volumetric and gravimetric), the uncertainty of the atomic and molecular weights constituted an appreciable component in the combined standard uncertainty; this manifested itself in the determination of Pb, where the expanded uncertainty was 2 mg/l. Received: 24 September 1998 / Accepted: 25 January 1999     

A Sequential Extraction Method Measures the Toxic Metal Content in Fly Ash from a Municipal Solid Waste Incinerator

The purpose of this research was to develop an optimized pretreatment procedure for toxic metals (Pb, Cd, Zn and Cu) content in fly ash from a municipal waste incinerator. In addition, modified sequential extraction procedures were used to characterize the chemical composition of the fly ash samples. The sequential extraction resolved the fly ash elements into the following chemical forms: soluble, exchangeable, carbonate, oxide, organic, and silicate compounds. Certified reference city waste incineration ash (BCR.176) was used as target ash samples. A H₂O₂+HNO₃+HF mixed acid digestion solution with a low temperature evaporation procedure was selected as optimal for the fly ash digestion. The digested solution was analyzed by inductively coupled plasma mass spectrometry (ICP‐MS), which effectively determined the concentrations of the toxic metal elements in BCR.176. Except for Cd, the recovery of Pb, Zn, and Cu under H₂O₂+HNO₃+HF digestion and their sequential extraction procedures were higher than 95%. The relative standard deviations (RSD) for recoveries of the four elements were within 10%. Furthermore, the sequential extraction procedure's results provided information on the potential mobility of the studied elements. Most of the Cd was bound to water‐soluble and carbonate material in the fly ash samples. Most of the Pb, Zn, and Cu was released to carbonates and bound to organic matter in the fly ash samples.     

Determination of cadmium in coal fly ash, soil and sediment samples by GFAAS with evaluation of different matrix modifiers

The determination of cadmium in different samples such as coal fly ashes, soils and sediments by Graphite Furnace Atomic Absorption Spectrometry (GFAAS) was studied. The best analytical conditions and instrumental parameters were deduced. Different types of matrix modifiers were tested and an optimization of several conditions (pyrolysis and atomization temperatures, heating rate, use of L’vov platform, etc.) was carried out. A mixture of 2% NH₄H₂PO₄ + 0.4% Mg(NO₃)₂ in 0.5 mol L^–1 HNO₃ as matrix modifier provided the highest sensitivity and an efficient behaviour for the three types of samples. A detection limit of 26 ng g^–1 was achieved and other figures of merit are shown. Analytical results obtained by direct calibration using standard samples prepared in the laboratory and by standard addition method were comparable. Received: 6 November 1998 / Revised: 4 February 1999 / Accepted: 9 February 1999     

Direct Analysis of Coffee and Tea for Aluminium Determinationby Electrothermal Atomic Absorption Spectrometry

 A method for direct analysis of tea and coffee samples by using electrothermal atomic absorption spectrometry is described. Coffee and tea from different sources were analyzed without digestion step. For slurry analyses the samples were ground, sieved at 105 μm and then suspended in 0.2% v/v HNO₃ and 10% v/v Triton X-100 medium. For liquid phase aluminium determination the samples were prepared in the same way and only the liquid is introduced directly into the graphite furnace. Calibration was performed by aqueous standards for both cases and the determinations were carried out in the linear range between 50 and 250 μg L⁻¹. The characteristic mass of aluminium and the detection limit were 45 pg and 2 μg L⁻¹, respectively. Using a typical 0.1% m/v coffee slurry sample, the relative standard deviation of measurements (n=15) for repeatability was about 8.2%. Received December 27, 1998. Revision March 18, 1999.     

In-situ concentration and determination of mercury by graphite furnace atomic absorption spectrometry with Pd-Rh as the chemical modifier

A method has been proposed for the determination of mercury by cold vapor generation graphite furnace atomic absorption spectrometry (CV-GFAAS) with Pd-Rh as coating and chemical modifier. The trapping efficiency for mercury with Pd-Rh was higher than with Pd alone. The characteristic mass of the method, which gives an integrated absorbance of 0.0044 s, was found to be 55 pg and the absolute detection limit (3 σ) of 37 pg was obtained with the proposed modifier. The method was successfully applied to the determination of mercury in standard reference water samples, wastewater samples and cosmetics with a recovery range of 95–104%. Received: 10 April 1998 / Revised: 20 August 1998 / Accepted: 23 September 1998