Investigation of microwave assisted drying of samples and evaporation of aqueous solutions in trace element analysis

Investigations of microwave assisted drying of sample materials and microwave assisted evaporation of aqueous sample solutions and acidic digestion residues were accomplished by means of special rotors for the microwave digestion system MULTIWAVE. To check the results obtained by microwave assisted drying, the samples were also conventionally dried at 105?°C in an oven. The following samples have been dried: 10 g each of meat, fish, apple, cucumber, potato, mustard, yogurt, clay and marl; 1 g each of certified reference material TORT 2 (lobster hepatopancreas), BCR 278 (mussel tissue) and BCR 422 (cod muscle); 500 g garden mould. Microwave assisted drying takes 40 min for organic samples and ¶30 min for inorganic material. Important is a slow increase of microwave power during the first 20 min. The results agree well with conventional drying at 105?°C. Losses of As, Se and Hg have been investigated for ¶3 CRMs. Only Se shows losses in the range of 20%. Losses of As, Be, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sr, Ti, Tl, V and Zn after evaporation of aqueous samples and acidic solutions after wet digestion, respectively, have been investigated. 50 mL aqueous solution was evaporated almost to dryness within 25 min. The recovery of Hg is 40–50%, of Se 90–95% and of the other elements 97–102%. 0.2 g each of TORT 2, BCR 278 and BCR 422 have been digested with 4 mL nitric acid and 1 mL hydrochloric acid by means of the microwave digestion system MULTIWAVE. The digestion residue was evaporated almost to dryness and dissolved again in 10 mL diluted nitric acid. In this case no element losses have been observed. The measured concentration of As, Cd, Cu, Fe, Mn, Hg, Pb, Mo, Ni, Se, Sr, V and Zn agree very well with the certified values. An important prerequisite for good recoveries is not to evaporate the solutions to complete dryness.     

微波消解ICP-MS快速测定生物样品中的多种元素

建立了微波辅助HNO3消解样品,ICP-MS快速测定生物样品中Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ge、As、Se、Sr、Mo、Ag、Cd、I、Ba、Hg、Tl、Pb、Bi共21种微量及痕量元素。通过在线加入内标来校正基体效应和信号漂移对测量所造成的影响。各元素线性相关系数在0.9990以上,RSD小于6.0%。用本方法对国家标准样品GBW07601a(头发),GBW10010(大米),GBW10016(茶叶),GBW10023(紫菜)进行分析,结果满意。方法能满足生物样品痕量分析的要求。     

Radiotracer analysis of the physico-chemical state of trace elements in aqueous solutions

The suitability of zone electrophoresis and of free-liquid electrophoresis for investigation of the physico-chemical forms of trace elements in aqueous solutions has been examined. Comparison of the electrophoretic mobilities of tervalent cerium determined by these two methods has demonstrated that adsorption of trace elements on the supporting medium renders zone electrophoresis unsuitable for investigation of hydrolytic and other reversible reactions of trace elements accompanied or preceded by significant adsorption. Free-liquid electrophoresis should be preferably used for this purpose as it is much less complicated by adsorption effects.     

Radiotracer analysis of the physico-chemical state of trace elements in aqueous solutions

Theoretical and experimental analysis of the open-ended capillary diffusion method for study of the state of trace elements in aqueous solutions is presented. It is shown by theoretical considerations that the use of the discontinuous capillary method of diffusion and the evaluation of single measurements using the classical Anderson-Saddington equation yields incorrect diffusion coefficients if two or more forms of the trace element with significantly different diffusion characteristics are simultaneously present in the solution. A new method for the evaluation of diffusion is suggested, which enables calculation of the abundance of two different forms of a trace element. The method employs a continuous measurement of diffusion combined with computer analysis of the data obtained. Verification of the method is carried out for a particular case using trace radiocerium. The effect of adsorption on the diffusion measurement and interpretation is discussed.     

Radiatracer analysis of the physico-chemical state of trace elements in aqueous solutions

Theoretical and experimental analysis of the diaphragm diffusion method for study of the state of trace elements in aqueous solutions is presented. It is shown that the method has substantial advantages over other diffusion methods and over conventional use of dialysis, particularly when nucleopore or other membranes with small internal surface area are employed. These advantages include rather short experimental time, not exceeding tens of minutes, lower adsorption losses and lower shift of equilibria among various forms of the trace element studied. A new method for the continuous measurement of and for the evaluation of diffusion is suggested, which enables calculation of the abundance of colloidal forms of the element. Verification of the method is carried out for a particular case using trace radiocerium.     

Microwave assisted extraction for trace element analysis of plant materials by ICP-AES

Application of microwave assisted extraction for the decomposition and dissolution of plant samples for trace metal determination by ICP-AES was examined. Dried onion, leaves of spinach beet and three reference materials CTA-OTL-1, CTA-VTL-2 and CL-1 were analyzed. Water, EDTA and hydrochloric acid (0.01, 0.10 and 1.0 M, respectively) were used as leaching solutions. The extraction efficiency was investigated by comparison of the results with those obtained after microwave wet digestion. HCl was found to be very suitable for quantitative extraction of B, Ba, Cd, Cu, Mn, Ni, Pb, Sr and Zn from the samples. For reference materials, the measured concentrations are well consistent with the certified values. The use of EDTA led to a complete extraction of B, Cd, Ni, Pb, Sr and Zn. Water was found to be a good leaching solution for boron. For extraction with HCl and EDTA, the RSD values for the concentrations measured were below 8% for most of the elements.     

Microwave assisted extraction for trace element analysis of plant materials by ICP-AES

Application of microwave assisted extraction for the decomposition and dissolution of plant samples for trace metal determination by ICP-AES was examined. Dried onion, leaves of spinach beet and three reference materials CTA-OTL-1, CTA-VTL-2 and CL-1 were analyzed. Water, EDTA and hydrochloric acid (0.01, 0.10 and 1.0 M, respectively) were used as leaching solutions. The extraction efficiency was investigated by comparison of the results with those obtained after microwave wet digestion. HCl was found to be very suitable for quantitative extraction of B, Ba, Cd, Cu, Mn, Ni, Pb, Sr and Zn from the samples. For reference materials, the measured concentrations are well consistent with the certified values. The use of EDTA led to a complete extraction of B, Cd, Ni, Pb, Sr and Zn. Water was found to be a good leaching solution for boron. For extraction with HCl and EDTA, the RSD values for the concentrations measured were below 8% for most of the elements. Received: 4 May 2000 / Revised: 20 June 2000 / Accepted: 22 June 2000     

An evaluation of trace element analysis in the forensic investigation of fibre samples

The use of trace element analysis in the forensic examination of fibres has been investigated. Samples of both natural and synthetic fibres have been analysed to show that it is possible to both identify and discriminate between samples that would, by present methods, be considered indistinguishable. A number of wool garments of predetermined trace element composition were sent for wear for a period of nine months. The conditions and frequency of wear and cleaning were reported to enable their effect upon the trace element composition of these garments to be determined. The wool samples were analysed by both short (30 min) and long (50 hrs) irradiations in a reactor flux of about 10¹² n·cm⁻²·sec⁻¹. This permitted the concentrations of the elements such as sodium, chlorine, iodine, manganese, cobalt and chromium to be determined. Both sodium iodide and lithium drifted germanium detectors were used to measure the induced activity of the wool samples. The composition of a range of acrylic fibres from a variety of sources has also been examined using a sodium iodide detector. The concentrations of sodium chlorine, bromine, managese, copper, aluminium, titanium, indium and barium were determined in these samples.     

Database for trace element concentrations in biological samples

Summary Numerous methods have been published for the determination of the concentration of elements such as arsenic, cadmium, chromium, mercury and nickel in biological samples as blood, tissues and urine. It is not easy but highly desirable to assess the reliability of such methods. Several publications present values of trace element levels in samples from apparently healthy subjects as well as from persons with different diseases and after various exposures. Very often published normal values for unexposed subjects differ much — even up to one order of magnitude. There are major problems related to sampling, definition of the reference groups and analysis. Values for such groups can be called reference values rather than normal values.Therefore it is difficult even for experts to find such accurate and typical values to be used for comparative purposes e.g. in toxicology and occupational medicine. Knowledge is desirable of an average value and also of the respective frequency distribution. In this paper factors are discussed influencing the values such as selection of the reference groups and how to get typical reference intervals. We have worked for several years with developing methods for trace element determination and with evaluating data for use in e.g. occupational health. Therefore we felt a need for systematic evaluation accessible through a database.The original publications are retrieved by careful literature data search in e.g. Medline and Chemical Abstracts. We plan to offer discettes with evaluated typical concentrations of elements, specified details of sampling and analysis, reliability as well as references to the original publications. These discettes are very easy to use. A frequently updated and easily accessible database system should be very useful. Cooperation is planned with e.g. International Commission on Occupational Health, International Atomic Energy Agency (IAEA), International Labour Organization (ILO), International Union of Pure and Applied Chemistry (IUPAC), National Institute of Occupational Safety and Health (NIOSH in USA) and the World Health Organization (WHO).

---

Datenbasis für Spurenelementkonzentrationen in biologischen Proben

     

Target preparation of biological samples for trace element analysis using nuclear techniques

An easy and rapid method for preparing biological targets for trace element analysis using nuclear techniques involving charged particle beams is described. The targets are thin, homogeneous and uniform. They withstand 100 nA of 1–2 MeV proton beams and of 5–10 MeV alpha beams for about 10 hrs.     

Determination of Pt from coke samples by ICP-MS after microwave assisted digestion and microwave assisted cloud point extraction

Platinum in coke samples was determined by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted sample digestion and temperature controlled microwave assisted cloud point extraction (MW-CPE). Interferences due to hafnium (¹⁷⁹Hf¹⁶O) were successfully eliminated using MW-CPE with 2-MBT prior to the determination of platinum by ICP-MS. The validity of the method was studied by spike recovery tests and by analyzing certified reference material (BCR-723 street dust). The results obtained for platinum in the BCR-723 were generally in good agreement with the certified values. Furthermore, the preliminary platinum results obtained for coke sample by ICP-MS after MW-CPE were compared to those obtained by a reference method (NiS-Fire Assay preconcentration/Te coprecipitation and ICP-MS determination).     

Rapid analysis of trace organics in aqueous solutions by enrichment in uncoated capillary columns

Summary A novel technique has been developed for the analysis of trace organics in aqueous solutions. Concentration of organics is effected by passage of the solution being analysed through uncoated plastic or metal capillaries as reported. The concentrated organics are then desorbed from the capillary using an organic solvent, and the desorbed solution is subsequently analysed by gas chromatography. Organics trapped inside a variety of columns have been recovered by solvent desorption in this manner using a number of different solvents, mixed solvents, different solvent volumes, different solvent flow rates through the capillary column and at different desorption temperatures, and the effects of these variables on the efficiency of desorption are discussed.     

Assessment of ICP-MS for routine multielement analysis of soil samples in environmental trace element studies

Summary The suitability of inductively coupled plasma mass spectrometry (ICP-MS) following acid digestion of samples was evaluated for the routine determination of trace elements in contaminated and control soil samples. The contaminated samples were collected near an expressway and two secondary lead smelters in Toronto. All samples were acid digested in pressure vessels using a combination of reagents including hydrofluoric and perchloric acids. Consequently, the total amount of the elements (Pb, Sb, Cd, As, Mn, Mo and Cr) were being determined. In the case of lead direct comparison and isotope dilutional MS procedures were compared. Standard Reference Materials (SRM's) were run to allow an assessment of precision and accuracy. Isotope ratios were determined in the contaminated samples to evaluate whether this approach could be used, routinely, to determine the source of the lead. National Bureau of standards (NBS) 981 isotope ratio reference sample was used to evaluate the accuracy of the lead isotopic ratio data.Generally, the results obtained for the total amounts of the elements in the SRM's were in satisfactory agreement with the certified values. The measured isotopic ratios had a small positive bias compared to the NBS certified values. Isotope dilution MS values for Pb were superior in accuracy and precision to those obtained by direct comparison calibration. At the present state-of-the-art, routine isotope ratio measurements are not good enough for source typing in a study such as this. Values obtained in the present investigation compared well with those reported in a 1974 study of same areas.     

Determination of polycyclic aromatic hydrocarbons in aqueous samples by microwave assisted headspace solid-phase microextraction and gas chromatography/flame ionization detection

The novel pretreatment technique, microwave-assisted heating coupled to headspace solid-phase microextraction (MA-HS-SPME) has been studied for one-step in situ sample preparation for polycyclic aromatic hydrocarbons (PAHs) in aqueous samples before gas chromatography/flame ionization detection (GC/FID). The PAHs evaporated into headspace with the water by microwave irradiation, and absorbed directly on a SPME fiber in the headspace. After being desorbed from the SPME fiber in the GC injection port, PAHs were analyzed by GC/FID. Parameters affecting extraction efficiency, such as SPME fiber coating, adsorption temperature, microwave power and irradiation time, and desorption conditions were investigated.Experimental results indicated that extraction of 20 mL aqueous sample containing PAHs at optional pH, by microwave irradiation with effective power 145 W for 30 min (the same as the extraction time), and collection with a 65 μm PDMS/DVB fiber at 20 °C circular cooling water to control sampling temperature, resulted in the best extraction efficiency. Optimum desorption of PAHs from the SPME fiber in the GC hot injection port was achieved at 290 °C for 5 min. The method was developed using spiked water sample such as field water with a range of 0.1-200 μg/L PAHs. Detection limits varied from 0.03 to 1.0 μg/L for different PAHs based on S/N = 3 and the relative standard deviations for repeatability were <13%. A real sample was collected from the scrubber water of an incineration system. PAHs of two to three rings were measured with concentrations varied from 0.35 to 7.53 μg/L. Recovery was more than 88% and R.S.D. was less than 17%. The proposed method is a simple, rapid, and organic solvent-free procedure for determination of PAHs in wastewater.     

Concentration and determination of trace amounts of chlorinated pesticides in aqueous samples

Summary A method for the quantitative analysis of the organochloro-pesticides heptachlor, dieldrin, DDT and aldrin in water, using the HPLC technique of on-line trace enrichment, has been developed. A standard HPLC isocratic analytical system was employed the principle modification being the incorporation of a short pre-column across the sample loop connections of a Rheodyne 7125 valve to serve as the trace enrichment column. Pesticide recoveries of >95% were achieved at sample flow rate of 5–15 ml/min by employing stainless steel fittings throughout the system and with 5% methanol included in the pesticide sample reservoir. The pesticides were concentrated onto a 50 mm, 10 m Spherisorb ODS column; analysis was performed on a 25 cm, 5 m Spherisorb ODS column with methanol-water (7525) elution; detection was by UV absorption measurement at 220 mm and 0.64 AUFS.Resolution achieved was >=1.16 and selectivity >=1.14. 100 ml aqueous samples allow ppb detection of the named pesticides in real samples. Total analysis time including concentration and chromatography was less than 30 minutes.     

Radiotracer analysis of the physico-chemical state of trace elements in aqueous solutions III. Lead

The physico-chemical state of trace lead in aqueous nitrate solutions (I=0.01) was studied using equilibrium calculation, free-liquid electrophoresis, dialysis and centrifugation methods and^{210, 212}Pb. It has been found that lead is present exclusively as nonhydrolyzed cations in solutions of pH 2–3.5. Colloidal or larger particulate forms of lead exist in solutions of lower acidity (pH>4). They are of pseudocolloidal nature, i.e. they are formed by adsorption of lead on solid impurities in the studied solutions. The pseudocolloids are negatively charged at pH>5 and reversible at pH 4–7. Reversibility of the adsorption of lead on impurities decreases at pH>7. Experiments have indicated that a significant hydrolysis of bivalent lead takes place already at pH>4. Anionic hydroxo-complexes of lead predominate in alkaline solutions of pH>12.     

Spectrophotometric determination of trace amounts of acetylacetone in aqueous solutions

A sensitive spectrophotometric method for the determination of trace amounts of acetylacetone in aqueous solution is carried out. In the presence of bicarbonate solution, diazotized anthranilic acid reagent reacts rapidly with acetylacetone to form a yellow-colored compound with maximum absorption at 330 nm, which is water-soluble and reasonably stable. Adherence to Beer's law is observed in the range 20–200 μg of acetylacetone/25 ml, with a molar absorptivity of 19.5 × 10³ liters mol⁻¹ cm⁻¹, a sensitivity index of 0.0051 μg cm⁻², relative to + 0.3 to −0.9%, and a relative standard deviation of 0.5–1.4%, depending on the concentration level.     

ICP and DCP emission spectrometry for trace element analysis in biomedical and environmental samples. A review

The capabilities of ICP (inductively coupled plasma and DCP (direct current plasma) emission spectrometry for the analysis of trace elements in biomedical (tissues, body fluids, etc.) and environmental samples (plants, soils, sludges, etc.) are discussed with the use of practical examples. In particular, possible matrix influences, physical interferences (overlapping), choice of instrumental parameters and other considerations are described.