Analysis of uranium in the insoluble residues after decomposition of soil samples by various techniques.

A comparison of different dissolution techniques for determination of uranium in soil samples was made. Conventional wet dissolution with mixtures of HNO3, HClO4 and HF acids, microwave dissolution using HNO3 and HF, and alkaline fusion with Na2CO3 and Na2O2 were evaluated. For testing the effectiveness of the dissolution procedures, two reference materials and six soil samples from the surroundings of a former uranium mine were investigated. It was observed that the content of uranium in the residues determined by INAA represents a significant contribution to its total concentration in the sample, especially in the case of microwave dissolution.

Investigation of factors affecting the quality of americium electroplating.

Four different electrolyte solutions were used in the electrodeposition of americium and their influences on the quality of the thin layer of deposited americium isotopes in combination with three different cathode disc materials were investigated. The relations between alpha spectral resolution and disc surface properties were established.

Development and characterization of methacrylate-based hydrazide monoliths for oriented immobilization of antibodies.

Convective interaction media (CIM; BIA Separations) monoliths are attractive stationary phases for use in affinity chromatography because they enable fast affinity binding, which is a consequence of convectively enhanced mass transport. This work focuses on the development of novel CIM hydrazide (HZ) monoliths for the oriented immobilization of antibodies. Adipic acid dihydrazide (AADH) was covalently bound to CIM epoxy monoliths to gain hydrazide groups on the monolith surface. Two different antibodies were afterwards immobilized to hydrazide functionalized monolithic columns and prepared columns were tested for their selectivity. One column was further tested for the dynamic binding capacity.

A new method for determination of hydroperoxides in cellulose.

A new chromatographic method for determination of hydroperoxides in cellulose is described, whereby the sample is dispersed in phosphate buffer solution (pH 7) of FeCl(3), EDTA and the hydroxyl radical scavenger, N,N'-(5-nitro,1,3-phenylene)bisglutaramide. The reaction time, concentration of reagents and chromatographic conditions for subsequent separation and quantification of hydroxylated products are optimised. The limit of detection is 0.14 micro mol L(-1) H(2)O(2) which corresponds to 2.1 micro mol hydroperoxides per kg of cellulose (mass of sample: 0.4 g). It was shown that in the concentration range of H(2)O(2) up to 15 micro mol L(-1) the method gives linear response and that adsorption of reaction products on fibres is negligible. For cellulose samples, this corresponds to a linear range of 2.1-225 micro mol of hydroperoxides per kg. Due to possible side reactions of hydroxyl radicals in the suspension of analyte, it is recommended that the standard addition technique is used. In purified cotton cellulose, the steady state concentration of hydroperoxides at room conditions was found to be 15.1+/-1.5 micro mol kg(-1).

Potentiometric determination of antimony in metal(II) hexafluoroantimonates(V).

The purpose of this study was to develop an accurate and precise analytical procedure for the determination of the content of antimony in coordination compounds of metal(II) hexafluoroantimonates(V) (M(SbF(6))(2) compounds, where M=Mg, Ca, Sr or Ba) synthesized in our laboratory. The major problem was to find an appropriate reagent for reductive decomposition of SbF(6)(-) to Sb(3+) required for the determination of antimony by redox titration. Effective reduction of Sb(5+) regardless of the metal M bound to SbF(6)(-) species was achieved using metallic aluminium powder in acidic medium. Precipitated Sb(0) was quantitatively reoxidized to Sb(3+) and determined potentiometrically with KBrO(3) or KMnO(4). Other metals were determined complexometrically with disodium ethylenediaminetetraacetic acid (EDTA). Highly accurate and reproducible results were obtained in the concentration range 5-25 mg Sb with an RSD smaller than 0.6%. Antimony-fluoro-hydroxo species and fluoride did not interfere with the complexometric determinations of other metals with EDTA. The developed method enabled, for the first time, complete elemental chemical analysis of M(SbF(6))(2) compounds in the bulk form.

Potential for the speciation of Zn using fast protein liquid chromatography (FPLC) and convective interaction media (CIM) fast monolithic chromatography with FAAS and electrospray (ES)-MS-MS detection.

Analytical procedures were developed for the speciation of Zn using fast protein liquid chromatography (FPLC), flame atomic absorption spectrometry (FAAS) and convective interaction media (CIM) fast monolithic chromatography with FAAS and electrospray (ES)-MS-MS detection. The investigation was performed on synthetic solutions (2 microg cm-3 Zn) of hydrated Zn2+ species and Zn complexes with citrate, oxalate and EDTA (ligand-to-Zn molar ratio 100:1) over a pH range from 5.4 to 7.4. It was found that Zn interacts with various buffers and the careful adjustment of the pH with diluted solutions of KOH is, therefore, required. FPLC separations were carried out on a Mono Q HR 5/5 strong anion-exchange column, applying an aqueous 1 mol dm(-3) NH4NO3 linear gradient elution over 15 min, at a flow rate of 1.0 cm3 min(-1). The separated Zn species were determined in 1.0 cm3 eluate fractions "off line" by FAAS. Speciation of Zn was also performed on a weak anion-exchange CIM DEAE fast monolithic disc by applying an aqueous 0.4 mol dm(-3) NH4NO3 linear gradient elution over 7.5 min, at a flow rate of 2.0 cm3 min(-1) and determination of the separated Zn species in 1.0 cm3 eluate fractions "off line" by FAAS. Zn-binding ligands in separated fractions were also characterized by electrospray (ES)-MS-MS analysis. The CIM DEAE disc was found to be more efficient in the separation of negatively charged Zn complexes than the Mono Q FPLC column. On the CIM DEAE disc Zn-citrate was separated from both Zn-oxalate and from Zn-EDTA. All these species were also separated from hydrated Zn2+, which was eluted with the solvent front. This method has an advantage over commonly used analytical techniques for the speciation of Zn which are only able to distinguish between labile and strong Zn complexes. Good repeatability of the measurements (RSD 2-4%), tested for six parallel determinations (2 microg cm(-3) Zn) of Zn-EDTA, Zn-citrate and Zn-oxalate was found at a pH of 6.4 on a CIM DAEA disc. The limit of detection (3s) for the separated Zn species was 10 ng cm(-3). The proposed analytical procedure was applied to the speciation of Zn in aqueous soil extracts and industrial waste water from a lead and zinc mining area.

The uptake and speciation of various Al species in the Brassica rapa pekinensis.

An investigation was carried out on the uptake and speciation of Al species in Al tolerant Chinese cabbage (Brassica rapa L. ssp. pekinensis). Plants were exposed to 10 microg cm(-3) of Al in the chemical forms of Al3+, Al-citrate and Al-malate in a time span from 1 up to 24 h. In each experiment the nutrient solution and stem sap were analysed by a combination of FPLC ICP AES and ES MS MS techniques. Speciation analysis enabled determination of particular chemical forms of Al present in the nutrient solution or in stem sap. The results indicate that Al3+ added to the nutrient solution remained as Al3+ in the solution during the experiments, but in the roots transformation to Al-malate occurred. Al was transported from roots to the upper parts of the plant as Al-malate (70%) and Al3+ (30%). Al-citrate or Al-malate added to the nutrient solution were transferred to the upper parts of the plant without transformation of their chemical forms.

Partitioning of Zn, Pb and Cd in river sediments from a lead and zinc mining area using the BCR three-step sequential extraction procedure.

The extent of pollution was investigated in sediments collected along the course of the river Meza and its tributaries in the lead and zinc mining area of the Mezica valley (Slovenia). In order to evaluate the heavy metal burden, total concentrations of Zn, Pb and Cd were determined and the partitioning of these metals between the easily and sparingly soluble sediment fractions was performed by the use of the slightly modified BCR sequential extraction procedure. The quality of analytical data was checked with Certified Reference Material CRM 601. Good agreement between the determined and certified or indicative metal concentrations was obtained. In order to estimate the natural and anthropogenic inputs of Zn, Pb and Cd in the sediments, normalisation to Al was applied. The results of the partitioning study indicate that Zn prevails in the most sparingly soluble fraction and is distributed between organic matter and sulfides, while a smaller proportion is found in the easily soluble fraction. Pb is distributed mainly between organic matter and sulfides, whereas Cd is predominantly associated with the most sparingly soluble fraction. Data from the normalisation procedure indicate that the anthropogenic inputs of Zn, Pb and Cd correlate with the very high total metal concentrations determined in sediments. The highest total Zn, Pb and Cd concentrations (16.3. 9.3 and 0.13 g kg(-1), respectively) were found in the sediment of the Helena rivulet, arising from former mining activities. In spite of the relatively low easily soluble metal fractions in the sediment, the concentrations of metals in these fractions are high, owing to the extremely high total metal concentrations. These data indicate severe pollution of the terrestrial and aquatic environment.

Preconcentration of quinolones by dialysis on-line coupled to high-performance liquid chromatography.

The parameters influencing dialytic separation of ciprofloxacin (CF) fluoroquinolone were investigated. Dialysis with a porous cellulose acetate membrane was on-line coupled with HPLC and the analysis of dialysate was made by isocratic ion-pairing liquid chromatography using a reversed-phase analytical column and fluorescence detection. Optimisation of the experimental conditions for selective dialytic enrichment are described and explanations of some phenomena affecting dialysis efficiency discussed. By the use of a neutral donor (pH approximately 7) and acidic acceptor solution (pH < 4) a substantial enrichment of quinolones was achieved. Accumulation of CF in the acidic acceptor phase is based on the protonation of the analyte in the acceptor compartment. Continuous-flow of donor solution and a stagnant acceptor solution gave high dialysis efficiency in 5-15 min. Effects of interfering substances present in real samples on the variation of dialysis efficiency can be minimised by successive dialysis runs of the original and spiked samples.

Possibilities for speciation of Al-citrate and other negatively charged Al complexes by anion-exchange FPLC-ICP-AES.

An anion-exchange fast protein liquid chromatographic-inductively coupled plasma atomic emission spectrometric procedure (FPLC-ICP-AES) was developed for speciation of Al-citrate and other negatively charged Al complexes. FPLC separations were carried out on a Mono Q HR 5/5 strong anion-exchange FPLC column over a pH range from 3.5 to 11.0. An aqueous-NaNO(3) (4 mol dm(-3)) linear gradient elution was applied over 10 min for separation of a particular Al species. The separated Al species were determined in 0.5 cm(3) eluate fractions ;off line' by ICP-AES. Under optimal analytical procedures Al-citrate was separated from Al-oxalate and Al-EDTA in a neutral pH range. Good reproducibility of the FPLC-ICP-AES procedure was obtained for determination of a particular Al species at optimal measurement conditions (RSD +/-2%). Al(3+) and neutral Al-citrate species were strongly adsorbed on the column resin and did not interfere with the separation of negatively charged Al complexes. Al(OH)(4)(-) species were separated from Al-citrate in an alkaline pH region, but quantitatively determined only at a pH of 11.0. The distribution of Al species over a pH range from 3.5 to 11.0 agreed with the reported calculated data. The limit of detection (3sigma basis) for separated Al species was 0.1 mug cm(-3).

Quantitative determination of trace amounts of Al-citrate by anion-exchange FPLC-ETAAS.

An anion-exchange fast protein liquid chromatographic-electrothermal atomic absorption spectrometric procedure (FPLC-ETAAS) was developed for determination of trace amounts of negatively charged Al-citrate in the pH range 3.5-8.0. Aqueous-4 mol dm(-3) NH(4)NO(3) linear gradient elution at a flow rate of 1 cm(3) min(-1) was applied for 10 min to separate Al-citrate on a FPLC Mono Q HR 5/5 column. The separated aluminium species were determined 'off line' by ETAAS in 0.5 cm(3) fractions. After separation the column was regenerated for 5 min with 4 mol dm(-3) NH(4)NO(3) and equilibrated with water. All reagents used in the separation procedure were cleaned with a silica based LiChrosorb RP-18 HPLC column to remove traces of aluminium. The main advantage of NH(4)NO(3) as eluent lies in its ability to decompose quantitatively in the graphite tube during the ashing step, which enables reproducible analysis of aluminium in the separated fractions. Using the procedure developed reproducible (RSD+/-2.0%) and quantitative determination of negatively charged Al-citrate at a retention time of 4.5 min was obtained. The LOD was found to be 2.0 ng cm(-3) of Al-citrate. The technique was successfully applied for the determination of Al-citrate in human serum. Spiked samples (50-150 ng Al(3+) cm(-3)) were microultrafiltered through a membrane filter (cut-off 30 000 Da) to separate aluminium bound to transferrin from low molecular weight aluminium complexes. It was found that 15-19% of aluminium in spiked samples from healthy volunteers passed through the membrane. By applying FPLC separation it was proved that all the aluminium in the filtrate corresponded to Al-citrate. The analytical technique developed enabled quantitative and reproducible determination (RSD+/-3.0%) of Al-citrate in spiked human serum at levels which could be found in patients undergoing long term haemodialysis.

Carbonate interferences by ion chromatographic determination of anions in mineral waters.

The high content of hydrogen carbonate anions and dissolved CO2 in some mineral waters interfere with the determination of anions in such samples by ion chromatography. It was found that the irreproducibility of retention times of all anions present in the samples was caused by on-column neutralisation of CO(3)2- to HCO3- by CO2. Microbubbles of CO2 released downstream by the suppressor inhibited exchange of Na+ with H3O+ resulting in lower conductivity and consequently in the decrease of chloride peak. To avoid peak deformation and overlapping caused by carbonate species, they should be removed by acidification followed by CO2 elimination in a gas separation unit. To prevent sample contamination by the anion of the added acid, the electrodialytic clean-up procedure was applied. The liberated CO2 was removed in a microporous Gore-Tex semipermeable tubing connected in series with the dialytic cell. The developed dialytic clean-up procedure was applied to the analysis of some typical mineral waters.

Surface examination of electrodes of removed implants.

The influence of the corrosive environment in human tissue on implantable platinum electrodes during long term electrical stimulation with monophasic voltage stimulation pulses was studied. Various anomalies caused by electrochemical reactions and/or mechanical deformations produced on the surface of the electrodes owing to electrical stimulation were identified and investigated by means of scanning electron microscopy. Since the corrosion reactions of the electrodes depend mostly on the composition of the electrode-electrolyte system, the potentials of anode and cathode during pulsing were measured in 0.9% NaCl solution and in vivo.

Amperometric determination of cyanide by use of a flow-through electrode.

A new approach to cyanide determination based on the measurement of the diffusion current arising from the oxidation of silver to dicyanoargentate(I) is described. Parameters defining the effect of the electrode geometry and the hydrodynamic characteristics of the system on the response of the electrode have been evaluated so that the performance can be optimized. Response is fast and linear for levels from one microgram to several grams per litre of solution. By use of the flow injection principle and a manifold arrangement, absolute amounts of less than one nanogram of cyanide can be determined precisely in volumes as small as 10 mul and at a rate exceeding 100 samples per hour. The method is easily adapted to automated routine analytical control and continuous monitoring of industrial processes depending on the use of cyanide, such as galvanizing plants and certain organic synthetic industries, and also to control of effluents.

Amperometric study of some effects in the precipitation of lead and barium chromates.

Amperometric titration has been applied to study parameters determining the extent of mutual co-precipitation of lead and barium in the formation of their chromates. The anomalous behaviour of dichromate due to repulsion at the dropping mercury electrode, which severely affects the precision of the measurements, has been eliminated by addition of tetrabutylammonium hydroxide. By this modification the amperometric end-point detection has been extended to higher concentrations of the reagent and a wider pH range of the medium as required for this study. Shifts in the distribution of chromium species, slow evolution of the precipitate and, in the case of lead, its varying composition, all depend on pH and ionic strength. They have been identified as limiting factors in the amperometric titration of lead and barium and optimum conditions found for their determination. The applicability of the technique to practical analysis is limited, but in the absence of ions which precipitate at the required pH, it permits precise and accurate titration of lead in the presence of barium at pH 2-3 and of their sum at pH 5-6.