Most traffic-related antimony air pollutants are derived from brake dust. Brake dust contains Sb2S3, used as a friction material in brake pads, and its high-temperature oxidation products, Sb2O3 or Sb2O4. Systematic investigations were carried out to find the most selective leaching conditions for these substances. First, solubility experiments of the pure potential compounds mentioned above were carried out. Then, the leaching of these compounds from home-made artificial dusts previously spiked with these compounds at the trace level was investigated. A 0.5molL−1 citric acid solution proved to leach the whole Sb2O3 content while extracting less than 10% Sb2S3 and no Sb2O4 at all. It was found that Sb2O3 and Sb2S3 traces were soluble in a 6molL−1 HCl solution, quantitatively and selectively. Graphite furnace atomic absorption spectrometry and hydride generation graphite furnace atomic absorption spectrometry methods were developed to determine the Sb content of the extracts. The proposed method proved to be applicable to settled dust containing traffic-related Sb compounds. The detection limits were 1.2 and 0.3μgg−1 for leaching by citric acid and HCl solution, respectively, which were adequate for Sb content determination in the urban dust studied. The reproducibility of the method expressed as relative standard deviation was about 7%. The results showed that the concentration of leachable Sb was 40μgg−1 in the settled dust of Budapest, about half of which corresponded to Sb2O3. The Sb2O4 content calculated as the difference of total and leachable fraction was about 10% with high uncertainty.

Trace lead impurities of drugs in 1-5% solutions can be preconcentrated on imino diacetic acid-ethyl cellulose (IDAEC). The buffered sample was loaded onto a chelating cellulose minicolumn by flow injection followed by the nitric acid elution and graphite furnace atomic absorption spectrometry (GFAAS) determination. The detection limit of the procedure depending on the concentration of drug solution is in the range 210 ng g(-1). The bonding of lead to various pharmaceutical compounds appeared in reduced rate during preconcentration according to the competition between ligands. The first step was focused on the determination of the stability constants of the lead-chelating cellulose species. In the second step, the sorption was estimated from different pharmaceutical matrices considering the lead-drug interaction. In the third experimental step estimated sorption was compared with the determined values for some medicines like aspartic acid, penicillamine, captopril, N-acetyl-cysteine and its pharmaceutical product, ACC 200. (c) 2006 Elsevier B.V All rights reserved.

Tanulmanyoztuk Pt (II)-Pt(IV), Sb(III)-Sb(V), Te(IV)-Te(VI) megkotődeset imonodiecetsav-etil-celluloz (IDAEC), diamino-dietil-amin (DEN)- es oxim-celluloz kelatcserelőkon es ezek alapjan on-line aramlasos elvalasztasi es dusitasi modszert dolgoztunk ki gyogyszer hatoanyagok GFAAS elemzesehez. Platinafemek, Sr, alkalifemek, Mo, Sb es Te kozvetlen ICP-MS analiziset oldottuk meg gyogyszeralapanyagokban ill. biologiai matrixban. Vizsgaltuk IDAEC cserelőn Pb, Mn es V aramlasos rendszerben tortenő megkotesenek hatekonysagat gyogyszeralapanyagok oldatabol es osszevethetőnek talaltuk a homogen egyensulyra szamolt megoszlasi ertekekkel. Meghataroztuk az IDAEC Pb-, Mn- es V-ionokkal kepzett specieszeinek a szamitasokhoz szukseges stabilitasi allandoit. Karsztvizek terepi frakcionalasat oldottuk meg kulonboző fizikai-kemiai allapotu Mn-, V-, Ti-, Mo- es U-formak GFAAS es ICP-MS meghatarozasahoz membranszűres, valamint dinamikus es batch IDAEC- megkotes segitsegevel. | The sorption of Pt(II,IV), Sb(III,V), Te(IV,VI) was studied on iminodiaceticacid ethyl ?cellulose (IDAEC), 2,2?-diaminodiethylamine (DEN)-, oxime and sulphoxine cellulose and based on these results on-line flow-injection separation and preconcentration method was worked out for GFAAS determination of metal impurities in pharmaceutical substances. Direct ICP-MS analysis was optimized for Pt metals, Sr, alkali metals, Mo, Sb and Te in drug substances and/ or in human biological materials. The efficiency of dynamic sorption concerning Pb, Mn and V on IDAEC microcolumn from solution of pharmaceuticals was investigated and these results was agreed with calculated distribution values in homogeneous media The stability constants of different chelate species formed by IDAEC with Pb, Mn and V were determined for distribution calculations. In situ fractionation of different physico-chemical forms of Mn, V, Ti and U in karstic groundwaters was developed by means of membrane filtration and dynamic and batch sorption on IDAEC for GFAAS and ICP-MS determination.

A separation procedure for antimony(III) and antimony(V) was developed with the use of chelating celluloses. Sb(III) was separately preconcentrated on imino diacetic acid-ethyl cellulose in the acidic pH range, in which the uptake of Sb(V) was negligible in the mu g L-1 concentration range. On the other hand, both Sb species Sb(V) and Sb(III) were pre-concentrated on a chloride form of 2,2'-diaminodiethylaminecellulose. These solid phase extraction procedures were combined with graphite furnace atomic absorption spectrometry (SPE-GFAAS) for Sb detection. Pharmaceutical compounds of organic and inorganic types (ten compounds), as well as mineral water samples (twelve types) were analyzed. Detection limits of 0. 18 mu g L-1 Sb(III) and 0.25 mu g L-1 Sb(V) were found in aqueous sample solutions and water samples, respectively, considering a 25-fold pre-concentration. The total Sb, mostly in the form of Sb(V), could be determined in phosphate-containing pharmaceuticals, while in phosphoric acid, Sb(III) was the dominant form. In all other types of samples the Sb content was below the detection threshold, and therefore, the potential suitability of the SPE-GFAAS method for the determination of Sb(III) species was proven by recovery tests of spiked samples. This method ensures the required detection power with regard to the allowable Sb limits established by international organizations. (c) 2007 Elsevier B.V. All rights reserved.

The possibility of chemical speciation of manganese was studied to explain the behavior and fate of trace metals in the aquatic environment. An operationally defined on-site preconcentration and fractionation scheme was developed that was based on the difference in the thermodynamic and kinetic behavior of manganese species. This scheme was used to distinguish between the different manganese forms in river and karstic groundwater. According to the elaborated “in field” procedure, the water sample was pressed through a membrane filter (0.22 μm) coupled to an imino diacetic acid–ethyl cellulose (IDAEC) chelating exchanger minicolumn by means of a syringe, followed by a batch enrichment. The fractions were analyzed by graphite furnace atomic absorption spectrometry. The dissolved manganese part was in the range of 0.5–1.5 μg l−1 and the on-site spike addition resulted in a satisfactory recovery. The binding behavior of manganese in different classes was characterized by means of stability constants of the Mn-IDAEC complexes.

Strontium content of five brain regions of five control and five Alzheimer's diseased (AD) patients and eight brain regions of three Hungarian control patients was determined. Microwave-assisted and high-pressure Parr-bomb digestions were used for sample dissolution. Strontium content of the digested samples was measured by ETAAS. The optimized parameters for digested human brain samples are: Tpyrolysis, max: 1500 °C, Tatomization: 2500 °C, 0.4% La(NO3)3 as a chemical modifier. The detection limit is 0.057 ng/ml and the characteristic mass is 1.0 pg. Calcium and magnesium content of the same digested samples were measured by ICP-OES. Accuracy of the applied methods was tested by analyzing NBS SRM1577 Bovine liver reference material, digested and measured with the samples together. Recovery measurements were done to eliminate the disturbing effect of the matrix. Strontium concentrations show great individual differences (20–450 ng/g, dry weight) independent of being either control or AD values, in contrast to the Mg (ccontrol,Hungarian: 590–675 μg/g, ccontrol,German: 620–675 μg/g, cAD,German: 640–695 μg/g) and Ca (ccontrol,Hungarian: 270–390 μg/g, ccontrol,German: 310–400 μg/g, cAD,German: 435–515 μg/g) concentrations.

A study was undertaken to determine Mo and Mn concentrations in 5 different brain regions of 5 control and 5 Alzheimer's diseased (AD) patients. The main purpose of this work was to evaluate the performance of our analytical methods including sample preparation. Microwave-assisted digestion was used for sample dissolution. The digested samples were analyzed for Mo by ETAAS and ICP-MS. Low levels of Mo in the digested solutions (ng ml(-1)) preclude the direct ETAAS analysis (LOD 0.75 ng ml(-1)). This problem could be solved by preconcentration of Mo on an iminodiacetic acid ethyl-cellulose (IDAEC) chelating microcolumn. The optimal pH range of sorption is between 1.5 and 4. Our ICP-MS method is adequate for Mo determination in human brain samples using Mo-98 for the evaluation (LOD 0.05 ng ml(-1)). The Mn content was determined applying ETAAS, ICP-MS, ICP-AES and NAA. The results of the different techniques were in good agreement. The techniques are compared in terms of accuracy, precision, detection limits, time and sample requirement. The accuracy of the measured data is investigated by the analysis of biological certified reference materials. The mean concentration of Mn in human brain samples is in the range 1.1-2.9 ppm, while for Mo it is between 90 and 330 ppb, for dry weight. Significantly higher values were found in the putamen and a difference in these concentrations between AD (c(Mo) = 330 +/- 42 ppb, c(Mn) = 2.90 +/- 0.07 ppm) and control patients (c(Mo) = 219 +/- 16 ppb, c(Mn) = 2.40 +/- 0.08 ppm).

Flow-injection graphite furnace atomic absorption spectrometric (GFAAS) methods were worked out using oxime, sulphoxine and 2,2′-diamino-diethylamine (DEN) cellulose microcolumns for preconcentration of platinum after reduction by iodide or sulphite ions. The detection limits were, at 20-fold enrichment, 0.21, 0.18 and 0.30 μg l−1, respectively. The total reflection X-ray fluorescence spectrometry (TXRF) was also used for the determination of platinum in eluates. The method was applied for the determination of platinum in salmeterol xinafoate and Ca-folinate pharmaceutical compounds. Decomposition of organic matrix of Ca-folinate was necessary before the preconcentration.

Palladium, platinum and rhodium impurities were determined in pharmaceuticals by ICP-MS. The detection limits were 15, 2.8, 2.5 ng/g for palladium in enalapril maleate, platinum in calcium folinate and rhodium in levodopa, respectively. The rhodium impurity was also determined by the GFAAS method as well. ICP-MS and TXRF methods were applied for screening of other metal impurities of pharmaceuticals.

An on-line separation preconcentration system coupled to electrothermal (graphite furnace) atomic absorption spectrometry was developed. A miniature column packed with iminodiacetic acid ethyl cellulose (IDAEC) was inserted into the loop. A peristaltic pump was used to deliver solutions. A flow of air was driven into the packed column, evacuating it between sample loading, washing and elution. The retained analyte was introduced on-line to graphite furnace using countercurrent elution with HNO3. The system was applied for the determination of V, Co and Pb in medicinal mineral water samples, and nickel in sea water samples. The detection limits (3σ) were 0.058, 0.022, 0.067, 0.062 μg/l for Co, Pb, V, and Ni, respectively. The R.S.D. (n=5) was <5% at 0.4–1.0 μg/l concentration range.

Atomspectrometric techniques are selective, sensitive methods for the quantitative determination of metals. They are commonly used for the detection and determination of metals applied as catalysts (e.g. Pd, Ni, Pt, Rh) in the synthesis of pharmaceuticals or metal impurities—for example, Fe and Cr—that might arise from stainless steel reaction vessels. There are stringent requirements for maximum allowable quantities of impurities in drug substances or products. The sensitivity and selectivity of heavy metal tests of pharmacopoeias in many cases do not meet the recent requirements. The species-selective information in the biomedical field is becoming increasingly important. The atom-spectrometric methods determine the total metal content of the sample but provide no information on its chemical identity. There is a need for determination of concentrations of different forms of elements because of the different toxicities of the different species. Separation techniques coupled with atom-spectrometric methods are applied for speciation analysis.

Flow injection iminodiacetic acid ethyl cellulose (IDAEC) microcolumn preconcentration and graphite furnace atomic absorption spectrometry determination of trace metals (Cd, Co, Ni, Ph) were carried out without decomposition of the drug matrix. The two forms of chromium Cr(III) and Cr(VI) were separated using IDAEC and anion exchanger diethylaminoethyl (DE)-cellulose, respectively. The detection limits of trace elements in pharmaceutical substances (sugars, sorbitol, mannitol, paracetamol, amidopyrine, chloral hydrate) after a 10-fold preconcentration in 1-5% m/v solution of pharmaceuticals were in the 0.3-29 ng g(-1) range. The measured concentration of trace elements in substances investigated was below 100 ng g(-1). The spike recovery was close to 100%. The capability of total reflection X-ray fluorescence technique for the determination of trace elements in pharmaceuticals with and without preconcentation was explored. (C) 1999 Elsevier Science B.V. All rights reserved.

Sulphoxine cellulose microcolumn was used in an FI-GFAAS system for the preconcentration of trace metals, Cd, Co, Ni, Pb and V from water and from highly mineralised water and also in the presence of complexing agent, e.g. citrate. The recovery was quantitative at pH 5 for all of the elements from NIST 1643c trace elements in water SRM and from highly mineralised water samples. No significant difference was found in the sorption of V(IV) and V(V) during preconcentration. The preparation of the 8-hydroxyquinoline-5-sulphonic acid cellulose (sulphoxine-cellulose) by Mannich reaction from aminoethyl cellulose or via chlorodeoxy and ethylenediamine cellulose is also described.

Sulphoxine cellulose microcolumn was used in an FI-GFAAS system for the preconcentration of trace metals, Cd, Co, Ni, Pb and V from water and from highly mineralised water and also in the presence of complexing agent, e.g. citrate. The recovery was quantitative at pH 5 for all of the elements from NIST 1643c trace elements in water SRM and from highly mineralised water samples. No significant difference was found in the sorption of V(IV) and V(V) during preconcentration. The preparation of the 8-hydroxyquinoline-5-sulphonic acid cellulose (sulphoxine-cellulose) by Mannich reaction from aminoethyl cellulose or via chlorodeoxy and ethylenediamine cellulose is also described. (C) 1998 Elsevier Science B.V. All rights reserved.

Palladium was determined in pharmaceuticals by direct graphite furnace atomic absorption spectrometry (GFAAS) method. The detection limit was 0.1 μg/g in 5% solution; the recovery of 0.5–2.0 μg/g Pd spike was close to 100%. The flow injection GFAAS method was worked out using oxime and iminodiacetic acid ethyl cellulose (IDAEC) microcolumns for preconcentration of Pd in aqueous and 50% methanol solutions. The optimal pH range for preconcentration was 2–5. At 20-fold enrichment the detection limits for Pd were 0.39 μg/liter for oxime cellulose and 0.42 μg/liter for IDAEC.

Semiquantitative analysis with accuracy of ±30 to 50% is a valuable tool for rapid screening of samples prior to quantitative determination of trace metals. In this study semiquantitative analysis software available with commercial inductively coupled plasma–mass spectrometry (ICP-MS) instrumentation is applied for rapid multielemental analysis, and the accuracy and precision of this semiquantitative analysis approach is evaluated with biological certified reference materials. Samples were prepared by high-pressure, high-temperature nitric acid vapor-phase digestion. For most elements the measured semiquantitative results are in the range of the certified values. With appropriate analyte solution dilution, the measured concentrations of the major elements (e.g., Ca) also agree with certified values. The accuracy is within ±10% for 28 element determinations that include 16 individual elements (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Rb, Sb, Sr, Tl, and Zn) and ±20% for 54 element determinations that include three more elements (Mg, V, and U) in eight certified reference materials including water. The method precision is 11 ± 11% (relative standard deviation,n= 65).

The preconcentration of some elements such as Cd, Co, Ni, and V(IV) was modeled in the presence of complexing agents such as citrate and oxalate at high Ca, Mg, and sulfate concentrations on iminodiacetic acid/ethyl cellulose (IDAEC), a chelating cellulose. The effect of the species present in the solution was studied after construction of the species distribution curves using critical, estimated, and measured stability constants. The stability constants of the IDAEC chelates were determined potentiometrically. The constants were calculated or estimated using computer programs. The diagrams calculated in homogeneous media were used for optimization of the flow injection on-line preconcentration for analysis of ultratrace metals in the highly mineralized water “Hunyadi.”

Water soluble tertiary amines enhance signals and decrease polyatomic chloride interferences in the direct inductively coupled plasma – mass spectrometric (ICP-MS) determination of As and Se in biological samples. Preliminary experiments with amine concentrations and nebulizer flow rates produced element and interference signal intensity changes. Arsenic and Se ICP-MS determination parameters have been optimized by a simplex procedure with amines in an argon plasma or without amines but with addition of N2 to the Ar. Variables include RF (radio frequency) power, nebulizer gas flow rate, intermediate gas flow rate, and amine concentration or nitrogen gas flow rate. Detection limit, minimization of polyatomic ion intensities, and reproducibility have been evaluated as reponse factors. The signal enhancement and element-to-molecular interference ratios differ to some extent with analyte intensity optimum operating conditions. The detection limits with addition of nitrogen (16 pg mL–1 for As and 180 pg mL–1 for Se) or of amines (8 pg mL–1 for As and 120 pg mL–1 for Se) and the extent of chloride interference minimization were compared. Amines addition was more beneficial. Biological standard reference materials and food and fecal samples were analyzed following different sample dissolution procedures.

A semiquantitative inductively coupled plasma mass spectrometric (ICP-MS) analysis protocol for biological materials was developed to include water-soluble tertiary amines with microwave heated sample preparation. Certified reference materials digested with HNO3, H2O2 and HF required addition of H3BO3 and a solution of tertiary amines (CFA-C reagent) to dissolve insoluble fluorides and neutralize free fluorides. Commercial semiquantitative analysis software that evaluates the entire mit range and includes preprogrammed corrections for spectroscopic interferences was applied to investigate matrix interferences resulting from 10% tertiary amines and-chlorides (added as 1% HCl). Measurement parameters including m/z range, spectrometer sensitivity and number of elements in the external calibration were evaluated The accuracy of the semiquantitative analysis improved when the standard solution was matrix matched; interference-free isotopes were selected for some elements instead of scanning the whole mit range, and additional elements with m/z values of under 80 were included for updating the instrument pre-calibration response factor. This semiquantitative analysis approach can be applied successfully for the multi-element analysis of biological materials when optimum instrumental conditions are employed. Thirty-eight elements were determined in six certified reference materials and food samples with a precision of 1-20% and accuracy of 1-50%. The determinations of Al, K, Na and Si were unreliable.

Methodology developed with inductively coupled plasma mass spectrometry (ICP-MS) for the determination of total arsenic in soil, house dust, and children's daily diet and faecal samples is described. Microwave oven dissolution, high temperature, pressure vapour phase acid digestion, and dry ashing with conventional thermal and microwave furnace heating and Mg(NO3)2 ashing aid are compared for sample preparation. Arsenic recovery from reference materials and spiked samples is between 94.8 and 109%. The ICP-MS Elan 5000a As detection limits (3sb) were 2.0 ng g–1 in freeze-dried human faeces prepared by closed-vessel, microwave-heated digestion and 1.1 ng g–1 in freeze-dried children's diets prepared by furnace ashing with an ashing aid.