Combination of three analytical techniques for speciation of Al in environmental samples

An analytical scheme is proposed which combines three speciation techniques for determination of particular Al species in soil extracts and percolating waters. A cation-exchange fast protein liquid chromatography — inductively coupled plasma atomic emission spectrometry (FPLC-ICP-AES) procedure, a microcolumn chelating ion-exchange chromatography- atomic absorption spectrometry (MCC-ETAAS) technique and the 8-hydroxyquinoline spectrophotometric method (8HQ-spectrophotometry) were employed. The FPLC-ICP-AES procedure offers determination of Al³⁺ (retention time 4.5 min) and Al(OH)²⁺ species (retention time 4.0 min) which are separated from Al(OH)⁺ ₂ (retention time 1.5min). AlF²⁺ coelutes with Al(OH)²⁺ species, while Al(SO₄)⁺, AlF⁺ ₂ and negatively charged Al organic complexes coelute with Al(OH)⁺ ₂ species. The MCC-ETAAS technique enables determination of the sum of positively charged monomeric aqua- and hydroxy-Al species plus sulphate- and fluoro-Al complexes. Employing the 8HQ-spectrophotometry the sum of positively charged monomeric aqua- and hydroxy-Al species plus sulphato- and most of the labile organic Al species are determined. The sensitivities of these selected techniques were adequate for speciation of Al in the samples analyzed. On the basis of the specific selectivity of a particular technique various groups of Al species may be determined. Thus, the comparison of analytical data from complementary procedures provides more comprehensive information on Al species present in soil extracts and percolating waters.     

Bis(tetramethylammonium) hexaaquadodeca‐μ‐bromo‐octahedro‐hexatantalum tetrabromide dihydrate

The novel title compound, [(CH₃)₄N]₂[Ta₆Br₁₂(H₂O)₆]Br₄·2H₂O, with a [Ta₆Br₁₂]²⁺ cluster unit, has been prepared and structurally characterized. The compound crystallizes in space group C2/c, with a twofold axis passing through the cluster and the centre of symmetry located between the clusters. The nearest neighbouring cluster units are aligned along the crystallographic c axis, forming a one‐dimensional chain pattern.     

Hexa­aqua­dodeca‐μ‐bromo‐octahedro‐hexatantalum bromide chloride octahydrate

The title compound, [Ta₆Br₁₂(H₂O)₆](Br_0.4Cl_1.6)·8H₂O, crystallizes in space group P. The structure contains two crystallographically independent [Ta₆Br₁₂(H₂O)₆]²⁺ cluster cations forming distinct layers parallel to the ab plane. The compound is isoconfigurational with the double salts [Ta₆Br₁₂(H₂O)₆]X₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O (X = Cl, Br).     

First measurements of 238Pu and 238Pu/137Cs activity ratio in Montenegro soil

Plutonium-238 (²³⁸Pu) activity concentrations in soil samples from Montenegro (six samples from three localities) have been measured for the first time. The ²³⁸Pu/¹³⁷Cs activity ratio was determined on the basis of alpha and gamma-spectrometric measurements, and found to be with an average of 0.0006 and standard deviation of 0.0003. By using the activity ratios determined in the present study, ²³⁸Pu activity concentrations were estimated for three localities in the central: one in the northern, and two in the eastern part of Montenegro.     

The formation of oxide nanoparticles on the surface of natural clinoptilolite

Nanoparticles of NiO, ZnO and Cu₂O crystallize when the Ni-, Zn- and Cu-exchanged natural clinoptilolite, respectively, are dehydrated by heating in air at 550 °C. The dehydration of Mn-exchanged clinoptilolite does not lead to the crystallization of manganese oxide but affects the crystallinity of the host clinoptilolite lattice, which becomes amorphous. The NiO, ZnO and Cu₂O nanoparticles are found to be randomly dispersed in the clinoptilolite matrix. The particle size varies from 2 to 5 nm and exceeds the aperture of the clinoptilolite channel (approximately 0.4 nm), suggesting that the crystallization of the oxide phases takes place on the surfaces of clinoptilolite microcrystals.     

Circular Dichroism of Some 2-(Phenylmethyl)pyridine Derivatives

The absolute configuration of the 2-(phenylmethyl)pyridine derivatives 1 – 9 had been established by X-ray diffraction and chemical correlation. Their CD spectra have been studied in different solvents for the free and protonated forms. It has now been found that, from the sign of the strong CD couplet between 270 and 220 nm, which was observable for all these compounds besides 7 and 9 , their absolute configuration can be determined much quicker.     

Concentration factors for 226Ra in the mullet (Mugilidae) species Mugil cephalus from the South Adriatic Sea

²²⁶Ra activity concentration in the mullet (Mugilidae) species Mugil cephalus whole individuals, and some organs (gills, gastrointestinal system, fins, muscle and bones), was measured by the γ-coincidence spectrometer PRIPYAT-2M. ²²⁶Ra transfer parameters [concentration factors (CFs)] from seawater, sediment and mud with detritus to fish tissues, and annual intake by humans consuming this fish species, have been estimated. Minimum detected radium activity concentration in whole M. cephalus individuals was found to be 0.89 ± 0.42 to 3.09 ± 0.41 Bq kg⁻¹, with arithmetic mean of 1.65 ± 0.39 Bq kg⁻¹. An average concentration in muscles is found to be 2.28 ± 0.84 Bq kg⁻¹, in gills—5.02 ± 1.85 Bq kg⁻¹, in gastrointestinal system—12.88 ± 1.71 Bq kg⁻¹, and in bones—14.72 ± 3.75 Bq kg⁻¹. No one fins showed radium activity above minimum detectable one. Annual intake of ²²⁶Ra by human consumers of this fish species is estimated to provide an effective dose of 0.006 mSv year⁻¹. CFs for ²²⁶Ra indicating transfer from seawater to whole individuals ranged from 8.9 to 30.9, and those indicating transfer from the sediment and mud with detritus—from 0.11 to 0.39 and from 0.08 to 0.3, respectively. The seawater to bones CFs varied from 97.9 to 197.3, to gastrointestinal system—from 59 to 178.8, to gills—from 22.5 to 68.3, to muscles—from 17 to 30.8.     

Removal of nickel(II) ions from aqueous solutions using the natural clinoptilolite and preparation of nano-NiO on the exhausted clinoptilolite

The natural zeolite tuff (clinoptilolite) from a Serbian deposit has been studied as adsorbent for Ni(II) ions from aqueous solutions. Its sorption capacity at 298 K varies from 1.9 mg Ni g⁻¹ (for the initial solution concentration of 100 mg Ni dm⁻³) to 3.8 mg Ni g⁻¹ (for C₀ = 600 mg Ni dm⁻³) and it increases 3 times at 338 K. The sorption is best described by the Sips isotherm model. The sorption kinetics follows the pseudo-second-order model, the activation energies being 7.44, 5.86, 6.62 and 6.63 kJ mol⁻¹ for C₀ = 100, 200, 300 and 400 mg Ni dm⁻³, respectively. The sorption involves a film diffusion, an intra-particle diffusion, and a chemical cation-exchange between the Na⁺ ions of clinoptilolite and the Ni²⁺ ions. The sorption is endothermic (ΔH° being 37.9, 33.4, 30.0, 27.7 and 24.3 kJ mol⁻¹ for C₀ = 100, 200, 300, 400 and 600 mg Ni dm⁻³, respectively) and spontaneous in the 298-338 K temperature range. Thermal treatment of the Ni(II)-loaded clinoptilolite results in the formation of spherical nano-NiO particles of approx. 5 nm in diameter which are randomly dispersed in the clinoptilolite lattice.     

Development of electrochemistry in Serbia-challenges and perspectives

In this review, the development of electrochemistry in Serbia is presented, with an accent on historical moments from the beginning up to contemporary research directions. The pioneer in the establishment of electrochemical science was Professor Panta S. Tutundzic, who was elected Assistant Professor in Physical Chemistry and Electrochemistry in 1925, when the Department of Technology, previously integrated within the Technical Faculty in Belgrade, was established as a separate department. From the time of Professor Tutundzic′s group to today, a community of many eminent researchers has been involved in electrochemistry development, creating the world-renowned Belgrade School of Electrochemistry. It was not actually a formal school of electrochemistry but rather a variety of research directions, and first of all people doing excellent electrochemical science recognized at the international level. As one of the members of the contemporary active electrochemistry community from Serbia, and successors of the Belgrade School of Electrochemistry, I have both the special honor and the responsibility of presenting the historical contribution of such outstanding and internationally recognized scientists in the most appropriate way. Having in mind that any school and research area is predominantly determined by human resources, I will focus on the great contribution of the most prominent electrochemists, from the founders up to those active today. The main research directions were and still are electrodeposition, electrochemical reaction kinetics, electrocatalysis, energy production and storage, and corrosion and corrosion protection.

     

Synthesis, crystal structure, spectroscopic and thermal properties of [Et4N][Ta6Br12(H2O)6]Br4·4H2O (Et=ethyl)—A new compound with the paramagnetic [Ta6Br12] cluster core

A new hexanuclear cluster compound, [Et₄N][Ta₆Br₁₂(H₂O)₆]Br₄·4H₂O (Et=ethyl) (1), with the paramagnetic [Ta₆Br₁₂]³⁺ cluster entity, was synthesized and characterized by elemental and TG/DTA analyses, IR and UV/Vis spectroscopy and by a single-crystal X-ray diffraction study. The presence of the paramagnetic [Ta₆Br₁₂]³⁺ unit was confirmed also by the room-temperature magnetic and EPR measurements. The compound crystallizes in the tetragonal I4₁/a space group, with a=14.299(5), c=21.241(5) Å, Z=4, R₁(F)/wR₂(F²)=0.0296/0.0811. The structure contains discrete [Ta₆Br₁₂(H₂O)₆]³⁺ cations with an octahedron of metal atoms edge-bridged by bromine atoms and with water molecules occupying all six terminal positions. The cluster units are positioned in the vertices of the three-dimensional (pseudo)diamond lattice. The structure shows similarities with literature reported structures of cluster compounds crystallizing in the diamond space group.