Validation of an electrothermal atomization atomic absorption spectrometry method for quantification of total chromium and chromium(VI) in wild mushrooms and underlying soils

An ETAAS method was validated to quantify total Cr and Cr(VI) in mushrooms and the underlying soils. The method includes a sample pretreatment for total Cr dissolution using a wet acid digestion procedure and a selective alkaline extraction for Cr(VI). The limits of detection were, expressed in microg/L, 0.15 and 0.17 for total Cr and Cr(VI), respectively. The linearity ranges under the optimized conditions were 0.15-25.0 and 0.17-20.0 microg/L for total Cr and Cr(VI), respectively. The limits of quantification were, expressed in microg/g of dry weight, 0.0163 and 0.0085 for total and hexavalent chromium, respectively. The precision of the instrumental method for total Cr and Cr(VI) was lower than 1.6%, and for the analytical method, it was lower than 10%. The accuracy of the method for Cr(VI) quantification was evaluated by the standard additions method, with the recoveries being higher than 90% for all of the added concentrations. For total Cr, certified reference materials (lichen CRM 482 and soil sample NCS ZC73001) were used. An interference study was also carried out in a mushroom simulated matrix, and it was verified that the deviations of the expected values were lower than 4.0% for both total Cr and Cr(VI). The validated method was applied to the evaluation of total Cr and Cr(VI) in 34 wild mushrooms and 34 respective underlying soil samples collected in two different regions of Portugal (Beira Interior and TrAs-os-Montes), with different locations regarded as noncontaminated or contaminated areas. The species were identified by a mycologist and subdivided into 10 genera and 15 species: Amanita (rubescens, muscaria, and ponderosa), Boletus (regius), Lactarius (deliciosus, vellereus, and piperatus), Suillus (granulatus and luteus), Tricholoma (acerbum), Agaricus (sylvicola), Volvariella (gloiocephala), Lecopaxillus (giganteus), Macrolepiota (procera), and Psilocybe (fascicularis). The mean values found for total Cr were 1.14 and 1.11 microg/g of dry weight, and for Cr(VI), the mean values were 0.103 and 0.143 microg/g of dry weight for cap and stalk, respectively. For soils, the mean concentrations found were, for total Cr, 84.0 microg/g and, for Cr(VI), 0.483 microg/g. The bioconcentration factors (BCFs) based on dry weight for cap and stalk were determined, and the values found, for both total Cr and Cr(VI), were always <1, although for hexavalent chromium, the BCFs were 10 times higher than for total chromium.     

Screening method for determination of high levels of cadmium, lead, and copper in foods by polarized Zeeman atomic absorption spectrometry using discrete nebulization technique

A screening method for determination of cadmium, lead, and copper in foods was developed. The sample (1-3 g) is digested with HNO3-H2SO4-HClO4 in a centrifuge tube attached to a straight glass tube that prevents loss of HNO3 by volatilization. After digestion, potassium iodide, H2SO4, and MIBK (4-methyl 2-pentanone) are added, and the metals are extracted with MIBK as metal iodides. The MIBK solution is injected and the metals are determined by flame polarized Zeeman atomic absorption spectrometry using a discrete nebulization technique. Recoveries of metals from fortified milk powder, unpolished rice, fish, beef, peanut butter, apple, and cabbage were satisfactory. The analytical results for NBS Oyster Tissue and NIES Pepperbush, Chlorella, and Mussel agreed with certified or reference values except lead in Pepperbush. The limits of quantitation for cadmium, lead, and copper were 0.01, 0.09, and 0.02 ppm, respectively. This method is simple and safe for routine analysis of high levels of cadmium, lead, and copper in foods.     

Determination of copper, cobalt, nickel, and manganese in baby food slurries using electrothermal atomic absorption spectrometry

The analytical conditions for the electrothermal atomic absorption spectrometric determination of copper, manganese, nickel, and cobalt in different types of baby foods using slurried samples are presented. Suspensions were prepared in a medium containing 0.1% w/v Triton X-100, 30% v/v concentrated hydrogen peroxide, 1% v/v concentrated nitric acid, 1% w/v ammonium dihydrogenphosphate (only for copper atomization), and one drop of silicon antifoam.The slurries were homogenized by using a potter and were introduced directly into the furnace. The amount of analyte extracted to the liquid phase was investigated. The graphite furnace conditions were optimized for each element. No matrix effect was observed, and calibration could be carried out using aqueous standard solutions. The detection limits were 3.4, 2.1, 5.4, and 3.7 pg for copper, manganese, nickel, and cobalt, respectively. The reliability of the procedures was checked by statistically comparing the results obtained with those found by using a previous microwave-oven mineralization stage and by analyzing several certified reference materials.     

Direct and combined methods for the determination of chromium, copper, and nickel in honey by electrothermal atomic absorption spectroscopy

In the present work, direct methods for the determination of chromium, copper, and nickel in honey by electrothermal atomic absorption spectroscopy were developed using experimental design as an optimization tool. Once the optimum conditions for the individual methods were established, a direct method for the combined determination of the three elements was optimized using the response surface tool. Palladium was used as chemical modifier in all cases. Honey was diluted in water, hydrogen peroxide, and nitric acid. Triton X-100 was added to minimize the matrix effect and the viscosity of the sample. The RSD (better than 10%) and the analytical recovery (98-103%) were acceptable for all of the developed methods. Calibration graphs were used in the four methods to determine the concentration of the analytes in the sample. The detection limits of the combined method (0.21, 0.35, and 0.37 microg L(-)(1) for Cr, Cu, and Ni, respectively) were similar to those obtained for the individual methods (LOD = 0.17, 0.21, 0.33 microg L(-)(1) for Cr, Cu, and Ni, respectively). The direct-combined proposed method has been applied to the determination of chromium, copper, and nickel content in representative honey samples from Galicia (northwestern Spain). The concentrations found in the analyzed samples were in the range of (5.75 +/- 0.64)-(26.4 +/- 0.38) ng g(-)(1) of Cr, (79 +/- 7.8)-(2049 +/- 80) ng g(-)(1) of Cu, and (12.6 +/- 1.36)-(172 +/- 6.88) ng g(-)(1) of Ni.     

Rapid determination of mercury in food colorants using electrothermal atomic absorption spectrometry with slurry sample introduction

The determination of mercury in different types of color food additives using electrothermal atomic absorption spectrometry is proposed. The procedure involves direct introduction of the additive samples as suspensions, and fast-program methodology is used to avoid mercury volatilization losses. Suspensions are prepared in a medium containing 0.1% w/v Triton X-100, 1% v/v concentrated nitric acid, 2% w/v potassium permanganate, and 3% w/v silver nitrate before being directly introduced into the furnace. Calibration uses aqueous standards, and compensation of the background is carried out using the Zeeman device. The characteristic mass is 61 pg and the detection limit is 59 pg. The reliability of the procedure is checked by comparing the results obtained with other results based on microwave-oven sample digestion, and by analyzing a certified reference material.     

Validation of a method for the analysis of iron and manganese in table olives by flame atomic absorption spectrometry

There is no generally accepted method for determination of the amounts of iron and manganese in table olives. Application of flame atomic absorption spectrometry to the analysis of both elements has been examined to validate a method that may be used by the industry's quality control laboratory as well as by the laboratories of regulatory agencies. The method has detection limits of 0.106 and 0.022 mg/L and quantification limits of 0.271 and 0.057 mg/L, for Fe and Mn, respectively, referred to the solution to be measured. There was no significant effect due to the matrix, but a slight bias due to the presence of Ca has been detected. Recoveries were excellent, and the method was robust. Influence of operator, HCl and Mg salt compounds, calcination equipment, or dates on results was not found. Relative errors were, in general, below 4% for both cations, and repeatability was below 3.43 and 0.38 mg/kg of olive paste for Fe and Mn, respectively. The method is proposed for the analysis of Fe and Mn in ripe olives and table olives in general.     

The determination of total lead in soil by atomic absorption spectrophotometry

A method is described for the determination of total lead in soil by atomic absorption spectrophotometry. The sample is digested with hot nitric acid. The dry residue is taken up in hydrochloric acid and excess iron is removed by extraction with acetylacetone‐chloroform. Lead is then extracted using the system DDC‐MIBK. The organic phase can be sprayed directly into the flame.

The method is not affected by elements occurring in contaminated soils. Iron is removed because a slow‐forming precipitate of the Fe‐DDC‐complex blocks the nebuliser system. The method is an improvement on other methods because no sulfuric acid is used for digestion, and therefore losses of lead by precipitation or occlusion are avoided. Tests confirm that the recommended method gives complete recovery of lead.

Lead can be determined in the range from 4 to 240 ppm in the soil. A standard soil sample has been analyzed, yielding a mean value of 125 μg Pb/g soil with a relative standard deviation of 2.4%.     

Flame absorption spectroscopic determination of cadmium, copper, iron, lead, and zinc in mussels

A rapid method is proposed for determination of Cd, Cu, Fe, Pb, and Zn in mussel samples. The elements are extracted with concentrated nitric acid in borosilicate glass tubes at 90 degrees C for 1 h, and determined by flame atomic absorption spectroscopy. Detection limits for a 300 mg sample corresponded to 0.3 microgram Cd/g, 0.7 microgram Cu/g, 33 microgram Fe/g, 0.7 microgram Pb/g, and 6 micrograms Zn/g. The coefficient of variation for 20 independent analyses was 7% for Cd, 7% for Cu, 6% for Fe, 14% for Pb, and 8% for Zn. Recoveries were 107 +/- 3% for Cd, 90 +/- 3% for Cu, 94 +/- 1% for Fe, 90 +/- 5% for Pb, and 96 +/- 3% for Zn. The accuracy of the method was determined by analyzing NBS Oyster Tissues.     

Determination of cadmium, copper, and lead in sodium chloride food salts by flame atomic absorption spectroscopy

A method for determination of Cd, Cu, and Pb in sodium chloride food salt samples has been developed. It consists of extraction in 4-methyl-2-pentanone of the complexes formed with ammonium pyrrolidine dithiocarbamate and further analysis of the extracts by flame atomic absorption spectroscopy. Detection limits in ng/g salt were 0.2 for Cd, 0.7 for Cu, and 10.0 for Pb. The coefficients of variation of 12 independent analyses were 13% for Cd (at a level of 0.4 ppb), 18% for Cu (1.6 ppb), and 5% for Pb (40 ppb). The recoveries were 100 +/- 0% for Cd, 115 +/- 14% for Cu, and 100 +/- 13% for Pb.     

Continuous sorbent preconcentration for the electrothermal atomic absorption spectrometric determination of ultratrace amounts of cobalt in milled wheat fractions

A method for the rapid determination of cobalt at ultratrace levels was applied in flour and flour byproducts (shorts and bran) obtained from various types of wheat that includes on-line preconcentration and electrothermal atomic absorption spectrometry is proposed. Solutions in 0.1 mol/L HNO(3) of milled wheat fractions subjected to wet ashing are preconcentrated in a straightforward flow-injection system by sorption on a RP-C(18) column following chelation. The eluent, ethanol, is carried by an air stream, and the chelate is eluted and collected in a 500 microL PTFE autosampler cup. The determination of cobalt features a precision (RSD) of 6% for a concentration of 0.2 ng/mL and a sensitivity (slope of the calibration graph) of 0.38 +/- 0.03 A s x ng/mL. The cobalt content in each type of wheat was found to be influenced by its geographical origin and texture. Also, it was found to depend on the amount of bran present in the milled wheat fraction. On the other hand, it is not significantly affected by the technological processes involved in wheat milling at a flour-producing factory.     

The determination of extractable plant available selenium from soils by electrothermal atomic absorption spectroscopy

Abstract

Plant available selenate was measured in a soil extract by electrothermal atomic absorption spectroscopy. Selenate in soil was first extracted with potassium sulfate then extracted into toluene fron an iodide‐sulfuric acid media. Aliquots of the toluene were injected into the graphite furnace for selenium determination. Quantities of extractable selenium measured using the electrothermal atomic absorption method compared favorably with the results of determinations using a fluorometric technique on aliquots of the soil extract. The simplicity of the procedure allowed for the precise determination of soil selenate in a brief period of time.     

Extraction of silver from soils and its determination by atomic absorption spectrometry

A simple, sensitive and reliable method for determining silver in soils by atomic absorption spectrometry with a graphite furnace is described which involves direct analysis of acid digests and avoids pre-concentration of the analyte. Chemical extracts have been investigated as a means of fractionating soil silver and results are reported for a range of soils, from areas of differing geology in Wales, U.K. Background concentrations are compared with areas contaminated by spoil from derelict mines. Uncontaminated soils contained silver in the range 0.01–1 μg Ag/g. The proportion of total silver extracted from a soil spiked and equilibrated with 110m AgNO₃ and unspiked field samples gave good agreement for the extractants 0.1 M and 1.0 M nitric acid, 0.005 M DTPA (diethylenetriaminepentaacetic acid), 0.05 M acetic acid, 1 M ammonium acetate and deionised water, although some extractants did not meet their predicted extraction efficiency. In the field samples soluble plus exchangeable silver was present between 0.4–40 ng Ag/g (< 1% of total), whereas biologically-available silver measured in 0.005 M DTPA was in the range 3–540 ng Ag/g (< 5% of total).     

Simultaneous determination of antimony and bismuth in soils by continuous hydride generation—atomic absorption spectrometry

A method for the simultaneous determination of Sb and Bi in soils using an automated hydride generation system with an electrically heated quartz cell atomizer, and an atomic absorption spectrophotometer is described. Five g of the air-dried soil was placed in a 100 mL Erlenmyer flask fitted with a Liebig condenser and boiled gently with 20 mL 6 M HCl for 1 hr on a sand bath. The extract was then filtered into a 100 mL volumetric flask. The two elements in the sample solution (<30 mL) placed in a 50 mL volumetric flask are prereduced by potassium iodide and ascorbic acid solutions. Reduction of Sb and Bi ions to stibine and bismuthine is obtained by sodium tetrahydroborate solution. Detection limits (S/N = 2) are 7 ng g^?1 dry soil for Sb and 0.7 ng g^?1 dry soil for Bi. The effects of 19 diverse ions on the absorbances of Sb and Bi were investigasted, and it was found that the errors by these ions will be within 5% in the ordinary unpolluted or even polluted soils. In order to examine the accuracy of the proposed method, Sb and Bi in the four Canadian reference soils and NBS-4355 from the National Bureau of Standards in the USA were determined. The values obtained in this work are close to the recommended or the not-certified values. The amounts of Sb, Bi and the related elements in the soils near a smelter were also analyzed.     

Influence of phosphorus and calcium on flame atomic absorption spectrophotometric determination of lead in canned fish products

Lead was determined in the presence of whole multiples of the P/Ca ratio found in Portuguese canned fish by flame atomic absorption spectrophotometry with and without using an ashing aid. Under our experimental conditions, use of the ashing aid eliminates P and Ca interference. Results with real samples, spiked with 1, 2, 3, and 4 ppm lead, are presented and statistically treated.     

Determination of copper, iron, and nickel in oils and fats by direct graphite furnace atomic absorption spectrometry: summary of collaborative study

A collaborative study of a method for the determination of copper, iron, and nickel in edible oils and fats by direct graphite furnace atomic absorption spectrometry was recently conducted by the International Union of Pure and Applied Chemistry. The quantitation limits of the method are 5 micrograms/kg for copper and 10 micrograms/kg for iron and nickel. The method has been adopted official first action as an IUPAC-AOAC method.     

Simplified flow injection slurry method for direct flame atomic absorption spectrometric determination of calcium,magnesium, sodium and potassium in fruits

A rapid, direct flow injection slurry atomization flame atomic absorption spectrometric procedure for Ca, Mg, Na and K determination is shown to give reproducible and accurate results for a variety of tropical fruits. The optimized conditions obtained for instrumental, slurry formation and manner of calibration graphs preparation are detailed. Ground fruit is simply suspended by being shaken in a Triton X-100 solution. Statistical evaluation of results from certified and non-certified materials indicate that the flow injection slurry method is both accurate and comparable in precision to a traditional wet acidic sample digestion procedure.     

Determination of silver in soils by atomic absorption spectrometry

A method for the determination of Ag in soils using atomic absorption spectrometry is described. The method involves the extraction of Ag from soil by boiling with 6 M HC1 followed by separation of the extracted Ag into methylisobutylketone (MIBK) using sodium N, N-diethyldithiocarbamate (DDTC) as a complexing agent. Silver is determined in the MIBK by direct aspiration into a flame atomic absorption spectrophotometer. The detection limit (S/N=2) for this method is 0.0001 mg L^?1 for aqueous solution and 0.002 mg kg^?1 for soil. The Ag content of even unpolluted soils can be determined by this method. The determination of Ag using this method was shown to be unaffected by the presence of various ions in the soil. The method was able to recover nearly 100% of Ag added to soil and approximately the same amounts of soil Ag were determined using this method as with HF-H₂SO₄ decomposition. For 3 reference soils of the Canadian Certified Reference Materials Project (CCRMP), the Ag values obtained by this method were the same as the values determined by Ebarvia et al. (1988). The amounts of Ag in the soils sampled in the Ichi River basin and the Ichi River sediments were determined using this method. This area has been polluted by Cd, Cu, Pb, and Zn discharged from the Ikuno Mine and Smelter. The Ag values ranged from 0.27 to 6.89 mg kg^?1 which were much higher than the values of the unpolluted soils.