Hyphenated techniques in speciation analysis of polyoxometalates: identification of individual [PMo12-xVxO40]-3-x (x = 1-3) in the reaction mixtures by high performance liquid chromatography and atomic emission spectrometry with inductively coupled plasma.

Unambiguous identification of polyoxometalate (POM) species generated in self-assembly reactions in solution is rather problematic due to close similarity of their properties such as solubility and spectral characteristics. The situation is made more complex by protonation equilibria (which can change their analytical signals) and the lack of individual compounds to serve as standards for individual members of these mixtures. In the present work a new approach to the study of such POMs has been suggested, taking molybdovanadates [PMo12-xVxO40]-3-x as a model. The key feature of this approach consists of generation of so-called "conditional model systems" that include most of the expected components of a mixture formed by self-assembly, tracked down by reliable detection techniques, e.g., 51V NMR-spectroscopy in this particular case. Then the proposed composition of the mixture is verified and corrected by means of high-performance liquid chromatography coupled with inductively coupled plasma atomic emission spectrometry (HPLC-ICP-AES).

Redistribution of elements between wastes and organic-bearing material in the dispersion train of gold-bearing sulfide tailings: Part I. Geochemistry and mineralogy.

Migration and redistribution of elements during prolonged interaction of cyanide wastes with the underlying natural organic-bearing material have been studied in two ~40cm deep cores that sample primary ores and their weathering profile (wastes I and II, respectively) in the dispersion train of gold-bearing sulfide tailings in Siberia. Analytical results of SR-XRF, whole-rock XRF, AAS, CHNS, and SEM measurements of core samples show high K, Sr, Ti, and Fe enrichments and correlation of P2O5 and Mn with LOI and Corg. Organic material interlayered or mixed with the wastes accumulates Cu, Zn, Se, Cd, Ag, Au, and Hg. The peat that contacts wastes II bears up to 3wt.% Zn, 1000g/t Se, 100g/t Cd, and 8000g/t Hg. New phases of Zn and Hg sulfides and Hg selenides occur as abundant sheaths over bacterial cells suggesting microbial mediation in sorption of elements. Organic-bearing material in the cores contains 10-30g/t Au in 2-5cm thick intervals, both within and outside the intervals rich in sulfides and selenides. Most of gold is invisible but reaches 345g/t and forms 50nm to 1.5µm Au0 particles in a thin 2-3cm interval of organic remnants mixed with wastes I. Vertical and lateral infiltration of AMD waters in peat and oxidative dissolution of wastes within the dispersion train of the Ursk tailings lead to redistribution of elements and their accumulation by combined physical (material's permeability, direction AMD), chemical (complexing, sorption by organic matter and Fe(III) hydroxides) and biochemical (metabolism of sulfate-reducing bacteria) processes. The accumulated elements form secondary sulfates, and Hg and Zn selenides. The results provide insights into accumulation of elements in the early history of coal and black shale deposits and have implications for remediation of polluted areas and for secondary enrichment technologies.

Coordination-induced condensation of [Ta6O19](8-): synthesis and structure of [{(C6H6)Ru}2Ta6O19](4-) and [{(C6H6)RuTa6O18}2(µ-O)](10-).

Reaction of [(C6H6)RuCl2]2 and Na8[Ta6O19] gives two new hybrid organometallic POM complexes, Na10[{(C6H6)RuTa6O18}2(µ-O)]·39.4H2O (Na10-1) and Na4(trans-[{(C6H6)Ru}2Ta6O19]·20H2O (Na4-2). In both cases the half-sandwich fragments {(C6H6)Ru}(2+) are coordinated as additional vertices to the {Ta3(µ2-O)3} triangles of the hexatantalate. According to NMR and ESI-MS data, the dimeric complex [{(C6H6)RuTa6O18}2(µ-O)](10-) dissociates in water with the formation of monomeric [(C6H6)RuTa6O19](6-) species (1a). X-ray structural characterization and aqueous speciation of the complexes by (13)C, (1)H, and DOSY NMR; ESI-MS; and capillary electrophoresis (CE) have been carried out.

Trace metal bioaccumulation by soft-bottom polychaetes (Annelida) of Sundarban Mangrove Wetland, India and their potential use as contamination indicator.

Bioaccumulation of trace metals in four soft-bottom polychaetes along with the host sediments was recorded from the intertidal regions of Indian Sundarban mangrove wetland. The enrichment of Mn (maximum 730 mg kg⁻¹) and Zn (maximum 320 mg kg⁻¹) was recorded for all the polychaetes followed by Cr, Cu, As, Co, Ni and Pb, showing sharp variations between the species. However, concentrations of Sn and Hg were very low with small variations between the species. An overall high bioconcentration factor (BCF) was recorded in the capitellid worm Mastobranchus indicus. The results of the investigation indicate the possibility of developing a standard test protocol for bioaccumulation by polychaetous annelids.