Determination of Heavy Metals in Soil Extracts and Plant Tissues at Around of a Zinc Smelter

Abstract

Extractable contents of heavy metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb and Bi in soil and plant tissue samples (fruit, leaf, twig and root) collected, along a distance of 1100 m to the West, from the surroundings of a metallurgical factory producing mainly zinc, cadmium and lead were determined by flame atomic absorption spectrometry (FAAS). In addition, the determinations of Ca and Mg, macro nutrient elements for plants, were also performed. Three extractant solutions were used for dissolution of soil samples, namely aqua regia (1 HNO₃₊ 3 HCl) for total metal analysis, 1 mol L^?1 ammonium acetate for exchangeable metal contents, and a dilute acid mixture (0.1 M HCl in 0.025 M H₂SO₄) for acid soluble metal contents. A mixture of HNO₃ and HClO₄ was used to analyze the fruit samples. The analyses of the leaf, the twig, and the root tissue samples were made by dry ashing method. The detection limits of the metals were in the range of 0.04 to 0.45 μg/mL for all soil extracts and 0.01 to 1.50 μg/mL for the fruit samples. The recovery values for all the determinations were higher than 95%. The results obtained from the analyses of plant tissue and soil samples were evaluated using linear correlation analysis and concentration factors to identify the effect of the factory near the grape-vine area.     

Statistical Evaluation of Bioavailability of Metals to Grapes Growing in Contaminated Vineyard Soils using Single Extractants

This article describes the statistical evaluation of concentrations of Cd, Co, Cr, Cu, Fe, Mn. Ni, Pb. Zn, Ca. and Mg metals determined in twenty-two grape and corresponding soil samples from around a zinc smelter in Kayseri. Turkey. In the analyses of soil samples. three different extraetants. 0.1 M HCl in 0.025 M H₂SO₄, 1 M NH₄OAc, and aqua regia (1HNO₃ + 3HCl), were used to extract and determine the leachable metal contents which are acid soluble, exchangeable, and total. respectively. A mixture of HNO₃ and HCIO₄ was used to dissolve grape samples. The determinations of metals were performed by flame atomic absorption spectrometry (FAAS). The analytical data were evaluated by using principal component analysis (PCA). hierarchial cluster analysis (HCA), correlation analysis (CA), and enrichment factors (EF). The relationship between the grapemetal and soil-extractable-metal concentrations was examined to evaluate the bioavailability of metals in soil to grape samples. As a consequence of statistical evaluations. Cd, Pb, Zn. Mn. and Fe labile levels in soil were related to total grape-metal contents indicating the method’s suitability for bioavailability studies in polluted soil–plant systems.     

Human Enamel and Dentin: Effect of Gender,Geographic Location and Smoking Upon Metal Concentrations

Abstract

The goal of this study was to determine the content of 12 metals in 23 samples of teeth from two cities in Bosnia and Herzegovina (B&H): Sarajevo, a capital city with heavy traffic, industrial facilities, and long periods of smog during winter and Bihac, a picturesque small city, with no industrialization, settled among vivid national park and rivers. The teeth were separated into enamel and dentin. Dissolution of samples was performed in concentrated HNO₃ with the addition of H₂O₂ followed by flame atomic absorption spectroscopy (FAAS) analysis. The results showed expected high contents of Ca, Na, Mg, and K, while elevated contents of Cu, Fe, and Zn were present in some samples. K and Na showed uniform distributions throughout enamel and dentin. Alkaline and earth-alkaline metals showed significant positive correlations. Zinc and manganese exhibited differences in the dentin content based on the place of residence. Zinc also displayed statistically significant differences between smokers’ and nonsmokers’ dentin samples. The differences were more pronounced between intra groups (within one sample) than for inter groups (within different groups, such as location, gender, and smoking).     

Liquid-liquid extraction with 2-acetylpyridinebenzoylhydrazone in the determination of traces of copper,nickel, cobalt and zinc by atomic absorption spectrometry

Trace amounts of Cu, Ni, Co and Zn in aqueous solutions are determined by their simultaneous extraction with 2-acetylpyridinebenzoylhydrazone followed by flame atomic absorption spectrometry. Isoamyl alcohol is the preferred solvent. Calibration graphs are linear, usually over the range 0–0.2 mg 1^?1 of aqueous phase. There are few interferences from other ions present in 500–1000-fold amounts.     

Flame Atomic Absorption Spectrometry Assay for Copper Determination in Pharmaceutical Products for Veterinary Use

Abstract

The scope of the present study is to quantify copper in pharmaceutical products of veterinary use, using flame atomic absorption spectometry (f_AAS). The determination is carried out after samples' mineralization in a HCl:HNO₃ (20∶1, v:v) mixture followed by the instrument quantification and the validation of the result. The validation indicates that the interferences from the whole analytical system and their measurement do not influence the results and ensure that there are no other effects which have not been considered.     

Ion-Selective Electrode Determination of Calcium and Potassium in Bovine Skim-Milk Powder

Abstract

Ion-selective electrode determinations of potassium and calcium have been carried out on skim milk powder and the results compared with data obtained by flame emission spectroscopy for potassium and by atomic absorption spectroscopy for calcium. The data indicate that ion-selective electrodes can be used as an alternative to spectroscopic methods for determining these metals by using a dry-ashing pretreatment procedure. Acid digestion pretreatment is not recommended because of the ensuing high ionic strength and possible interferences. Sodium and magnesium contents obtained by spectroscopy are also quoted for interest. The various percentage metal contents are: potassium: 1.96 ± 0.155 (ISE direct) 1.81 ± 0.144 (ISE Gran) and 1.82 ± 0.076 (flame emission), sodium: 0.511 ± 0.017 (flame emission), calcium: 1.37 ± 0.095 (ISE direct), 1.36 + 0.079 (ISE Gran) and 1.41 ± 0.082 (flame aas), and magnesium 0.119 ± 0.003 (flame aas).     

Demetalization of oils resulting from recycled tires by liquid-liquid extraction using modified superheated water An environmentally friendly approach

An approach based on continuous pressurized liquid-liquid extraction with 20% HNO₃/1 M KCl/10⁻³ M EDTA as extractant has been developed for the extraction of metals from the oil resulting from recycled tires. A multivariate optimization of the main variables affecting the extraction process has been performed. The method has been applied to three oil samples with different contents in V, Ni, Zn, Fe and Cu. The target metals have been determined in both untreated and treated oil by flame atomic absorption spectrometry (FAAS) in order to obtain the extraction efficiency. Under the optimum conditions, recoveries higher than 90% have been obtained with a repeatability and within-laboratory reproducibility, expressed as relative standard deviations, ranging from 2.75 to 6.91 and 2.97 to 8.16%, respectively. For applications where the demetalization does not require being complete, a study of the demetalization degree achieved depending on the extraction temperature and extractant composition has also been performed. This study provides useful data about the cheapest working conditions to be used in order to obtain a given demetalization level.     

New Application of Chemically Modified Multiwalled Carbon Nanotubes with Thiosemicarbazide as a Sorbent for Separation and Preconcentration of Trace Amounts of Co(II), Cd(II), Cu(II), and Zn(II) in Environmental and Biological Samples Prior to Determination by Flame Atomic Absorption Spectrometry

The present article reports the application of Thiosemicarbazide‐modified multiwalled carbon nanotubes (MWCNTs‐TSC) as a new, easily prepared selective and stable solid sorbent for the preconcentration of trace Co(II), Cd(II), Cu(II) and Zn(II) ions in aqueous solution prior to the determination by flame atomic absorption spectrometry. The studied metal ions can be adsorbed quantitatively on MMWNTs at pH 5.0 and then eluted completely with HNO₃ (1.5 mol L^?1) prior to their determination by flame atomic absorption spectrometry. The separation/preconcentration conditions of analytes were investigated, including the pH, the sample flow rate and volume, the elution condition and the interfering ions. The maximum adsorption capacity of the adsorbent at optimum conditions were found to be 32.5, 27.3, 44.5 and 34.1 mg g^?1 for Co(II), Cd(II), Cu(II) and Zn(II), and the detection limits of the method were found to be 0.28, 0.13, 0.21 and 0.17 μg L^?1, respectively. The proposed method was successfully applied for extraction and determination of the analytes in well water, sea water, wastewater, soil, and blood samples.     

Systematic investigation of aluminium interferences with the alkaline earths in flame atomic absorption spectrometry

Summary Aluminium interferes with the absorption of Mg and Ca in the air-acetylene flame to such an extent that the corresponding absorbances may fall even to zero. This well-known chemical interference can be overcome with the nitrous oxide-acetylene flame, completely in the case of Mg, however only to a restricted extent in the case of Ca. Mg and Ca with concentrations of the AAS-working range in aqueous solutions and Cl^– or NO ₃ ^– as anions (in an aqueous HCl or HNO₃ matrix, respectively), were determined in the air-acetylene flame with continuously rising Al portions and with (or without) 0.25% Cs as radiation buffer, in order to quantify the degree of these interferences. The same was done to evaluate the extent of the suppression of those interference when using a releaser or protector reagent in both the air-acetylene and the nitrous oxide-acetylene flame. After the decrease of absorption in the air-acetylene flame by forming thermally stable Mg or Ca aluminates, a rapid increase (positive interference) occurs unexpectedly in the presence of Cl^–±Cs and with further rising Al contents. This effect still appears for Ca also in the hotter nitrous oxideacetylene flame, however, only in a restricted extent. In the air-acetylene flame the undisturbed absorptions for Mg and Ca (i.e. the starting data without Al) are nearly reached again within the range of the positive interference. This supports the assumption that in consequence of a continuous equilibrium change in the flame because of the rising Al content and in the presence of Cl^– and ±Cs the formation of only pure Al oxides now generates the release of Mg and Ca (instead of the thermally stable aluminates in the beginning). In the air-acetylene flame interferences of 1000 mg/l Al are completely removed by an addition of 1% releaser-La, when measuring up to 0.2 mg/l Mg and up to 4 mg/l Ca. The extent of releasing Mg and Ca is effective only up to that Al concentration range which leads to the absorption maximum of Mg and Ca. In the nitrous oxideacetylene flame 5000 mg/l Al are compensated when determining up to 1 mg/l Mg. In the case of Ca, which is detected up to 4 mg/l, interferences of 1000 mg/l Al are only avoided by using the nitrous oxide acetylene flame together with 1% releaser-La. The excellent sensitivity of Ca in this flame (in contrast to the air-acetylene flame) permits a strong dilution, lowering thereby the interfering Al concentration, too. For Mg the same option is valid because of its high sensitivity in the air-acetylene flame.     

Determination of Trace Elements in Aerosol Samples Collected on Polycarbonate Filters by Atomic Absorption Spectrometry

Abstract

The multi-element analysis of aerosol samples collected on polycarbonate filters and the wet digestion procedure in open vessel were investigated. The concentrations of Na, K, Ca, Mg and Zn were determined by flame atomic absorption spectrometry with a micro injection system while Cd, Pb, Cu, Ni and V were determined by graphite furnace atomic absorption spectrometry (AAS).

NIES N[ddot] 8 “Vehicle Exhaust Particulate” Certified Reference Material from the Japan Environment Agency was used to study the decomposition of the samples. Different treatments were applied in order to completely dissolve the aerosol samples. It was found that, from all the methods tested, attack with micro-quantities of HNO₃ and HCIO₄ in an air pressure digestion system was the best procedure for the determination of the elements by AAS.

The recommended method was appropriate for all elements and it was applied to real samples. Two nondestructive analytical techniques for the determination of Na, K, Ca, Mg, Zn and Pb have been compared with the proposed method: proton induced X-ray emission (PIXE) and neutron activation analysis (NAA). Results obtained by the application of these three techniques were similar.     

Anreicherung von elementspuren aus hochreinem gallium durch partielles lösen der matrix : Analyse des spurenkonzentrats durch flammen-atomabsorptions-spektrometrie mit der “injektionsmethode”

Trace elements can be preconcentrated from high-purity gallium by simple dissolution of the sample in HCl—HNO₃, until a residue of less than 5 mg remains. Traces of metals which are nobler electrochemically than the matrix (Ag, Au, Bi, Co, Cu, Fe, Hg, Ni, Pb, Pd and Sn) are enriched in the residue (recovery > 95 %), a concentration factor of about 10³ being obtained. Traces of Cd, Co, Fe, Tl and Zn can be extracted from gallium without dissolving the matrix by treatment with a mixture of HI and I₂. Most of the preconcentrated elements are determined by flame atomic absorption spectrometry with the “injection method”. The limit of detection (3σ) for different elements was found to be between 0.06 and 0.004 p.p.m. The relative standard deviation is generally about 5 %.     

Schnellbestimmung von Cu, Ag und Pd in PbSn-Verzinnungsb?dern durch Atomabsorptions-Spektroskopie

Zusammenfassung Eine Absorptionsmethode zur direkten Bestimmung von Cu, Ag und Pd in Pb-Sn-Legierungen wurde erarbeitet. Für die Bestimmung vorteilhafte Absorptionslinien (Cu 324,7 nm, Ag 338,3 nm und Pd 276,3 nm) wurden ermittelt und auf diesen intermetallische Interferenzen von 0–500 ppm Cu, Ag und Pd sowie von 10000ppm Pb und Sn gemessen. 1g der Legierung wird in 10 ml HNO₃ (D 1,52) und 2 ml 50 % HF gelöst. Die Lösung wird in einer Acetylen-Luft-Flamme analysiert. Die Methode erlaubt Gehalte bis zu 3·10^–4 % Cu, 5·10^–4 % Ag und 8·10^–4% Pd (zweifache Blindwerthöhe) mit ausreichender Genauigkeit zu bestimmen.

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Rapid determination of Cu, Ag and Pd in PbSn-tinning baths by atomic-absorption spectroscopy

An atomic absorption method for direct determination of Cu, Ag and Pd in Pb-Sn-alloys has been developed. For the determination favourable absorption lines (Cu 324.7 nm, Ag 338.3 nm and Pd 276.3 nm) were found out. Intermetallic interferences of 0–500 ppm of Cu, Ag and Pd as also 10000 ppm of Pb and Sn were measured on these lines. 1 g of the alloy is dissolved in 10 ml HNO₃ (d 1.52) and 2 ml of 50 % HF. The solution is analyzed in an acetylene-air flame. This method allows the analyzing of contents up to 3×10^–4 % Cu, 5·10^–4% Ag and 8×10^–4% Pd (twofold blank) with sufficient precision.

     

AAS multielement analysis of strontium and barium salts after preconcentration by precipitation of the matrix as nitrates

A method is described for the preconcentration and AAS-determination of trace elements such as Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, In, K, Mg, Mn, Na, Ni, Pd, Tl and Zn in high-purity strontium and barium nitrate and chloride. For that purpose the main constituents Sr or Ba are precipitated as nitrates by simple evaporation of the diluted nitric acid sample solutions. The solubility of Sr and Ba nitrate in the resulting concentrated HNO₃ is so small that the preconcentrated traces can be determined without interference from the matrix using the “injection method” in the flame AAS determination. For most of the investigated elements the recovery is about 95% (Hg ～ 50%, Cr ～ 80%); the relative standard deviation (N = 10, trace contents of the sample 0.2…5 ppm) in general is about 0.05. The detection limits (3σ, N = 25) were found to be between 1 and 0.01 ppm depending on the AAS sensitivity of the elements.     

Determination of Cd, Co, Cu, Mn, Ni, Pb, and Zn by Inductively Coupled Plasma Mass Spectroscopy or Flame Atomic Absorption Spectrometry after On-line Preconcentration and Solvent Extraction by Flow Injection System

The concentrations of Cd, Co, Cu, Mn, Ni, Pb, and Zn in natural and sea waters are too low to be directly determined with by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GFAAS). Specific sample preparations are requested that make possible the determination of these analytes by preconcentration or extraction. These techniques are affected by severe problems of sample contamination. In this work Cd, Co, Cu, Mn, Ni, Pb, and Zn were determined by inductively coupled plasma mass spectroscopy (ICP-MS) or by atomic absorption spectrometry, in fresh and seawater samples, after on-line preconcentration and following solvent elution with a flow injection system. Bonded silica with octadecyl functional group C₁₈, packed in a microcolumn of 100-μl capacity, was used to collect diethyldithiocarbamate complexes of the heavy metals in aqueous solutions. The metals are complexed with a chelating agent, adsorbed on the C₁₈column, and eluted with methanol directly in the flow injection system. The methanolic stream can be addressed to FAAS for direct determination of Cu, Ni, and Zn, or collected in a vial for successive analysis by GFAAS. The eluted samples can be also dried in a vacuum container and restored to a little volume with concentrated HNO₃and Milli-Q water for analysis by ICP-MS or GFAAS.     

Developed Method for Spectroscopic Studies of Viscous Samples

Abstract

In this work, the trace elements in phosphoric acid, which has been considered an example of the proposed viscous sample, were measured accurately by a developed method. Samples were diluted to decrease matrix and background interferences. Quantitative analysis of As, Ca, Cd, Cu, Fe, Hg, K, Mg, Na, Pb, and Zn were carried out using flame atomic absorption spectrometry (FAAS). A comparison with inductively coupled plasma-atomic emission spectroscopy (ICP-AES) proves the validity of the developed method. The change of the electronic transition due to diluted of the viscous samples was demonstrated using UV-VIS spectroscopy.     

Synthetic inorganic ion exchanger. IX. Thorium antimonate. Synthesis,properties and ion exchange separations

Summary Thorium antimonate has been synthesised by mixing 0.1 M Th(NO₃)₄ solution in 0.1 N HNO₃ and 0.05 M potassium pyroantimonate and by mixing 0.1 M Th(NO₃)₄ solution in 0.1 N HNO₃ with 0.1 M SbCl₅ in 4N HCl at controlled pH. The preparative procedure, composition, I.R. spectra, chemical and thermal stability, physico-chemical properties and distribution coefficients of metal ions on thorium antimonate have been determined at pH 5.5–6.5. On the basis of distribution co-efficient values separations of Cu(II) from Mg(II), Ni(II), Mn(II), Mg(II), from Zn(II) and Cd(II) and Zn(II) from Cd(II) have been achieved. Part VIII: Reference [1]     

Some observations on the determination of total heavy metals in sewage sludge by atomic absorption spectrophotometry after a pressurized acid digestion

An economical and simple method for the flame atomic absorption spectrometric determination of Cd, Pb, Ni, Cu, Fe, and Zn in sewage sludges is described. Samples are treated with concentrated HNO₃ in a thermal oven using Pyrex glass tubes hermetically sealed with Bakelite screw caps. The effect of the digestion parameters, such as digestion time, acid volume, sample mass, and temperature, were studied. The precision and accuracy of this procedure were evaluated by the analysis of two BCR (Community Bureau of Reference, European Communities) certified sewage sludge samples (CRM 146 and 144).     

Microsampling and Determination of Metals in Iron Gall Ink

Abstract

Iron gall ink contains transition metals such as Fe, Cu, and Mn which are known to catalyze chemical reactions in support materials such as paper and parchment, which eventually leads to their deterioration over time. Identification of metals in ink can be an important step prior to the conservation treatment of a written document. In this work, syringe needles (16G–23G) were used to sample micro-cores (～0.7 mm in diameter) of ink and paper prior to analysis. Metals were extracted from the micro-core with HNO₃, prior to analysis using graphite furnace atomic absorption spectroscopy (GFAAS).     

An Ion Exchange Separation-Atomic Absorption Spectrophotometric Method for the Determination of Microgram Quantities of Copper,Iron and Zinc in Infant Milk Formula: Powder Form.

Abstract

An atomic absorption spectrophotometric method is described for the determination of microgram quantities of copper, iron and zinc in infant formula powdered milks. After sample digestion in concentrated nitric acid in a pressure vessel, the solution is evaporated till dryness, and then a solution of 6M HCl is added, in order to form the chlorocomplexes of the metals. This acid solution is passed through an ion-exchange column (anion exchange resin, chloride form). The metals are eluted from the column with diluted acid mixture of 0.005M HCl + 0.5% (v/v) HNO₃, and then the eluate is evaporated till dryness. The residue is dissolved in 1% (v/v) HNO₃, and then atomized into an air-acetylene flame. A standard addition procedure was employed as a back-up technique. The results obtained by this proposed method and those obtained by the standard addition technique were statistically treated, compared and discussed in this paper.     

Preconcentration of trace metal ions by combined complexation-anion exchange : Part I. Cobalt,zinc and cadmium with 2-(3′-sulfobenzoyl)-pyridine-2-pyridylhydrazone

The ligand 2-(3′-sulfobenzoyl)pyridine-2-pyridylhydrazone forms anionic complexes with Fe, Co, Ni, Cu, Zn, Cd, Hg and Pd which demonstrate high affinities for anion-exchange resins. The behavior of Co, Zn and Cd was studied in detail, with respect to pH, flow rate, ligand/metal ratio, volume, concentration and percentage retention of the anionic complex on the Bio-Rad AG1-X2 resin. At optimal conditions, Co, Zn and Cd are quantitatively retained; Zn and Cd are removed completely by 2 M HNO₃ or 1 M H₂SO₄, and Co by 12 M HCl and 1 M HNO₃. Concentration enhancements up to 300-fold can be easily achieved. The complexes can be left on the columns for 48–96 h and still be quantitatively recovered. A ligand-loaded resin column can also be used to remove Co, Zn and Cd from solution. Batch experiments were used to determine distribution coefficients for the metal complexes.