Phyllite/bentonite mixture-an alternative effective buffer material for a geological disposal of radioactive waste.

The use of phyllite (Phy) instead of quartz in mixtures with bentonite (B) is recommended as a buffer material for engineering barriers in a geological repository of nuclear waste. The recommendation is based on experimentally determined sorption properties of various Phy/B mixtures. The adsorption capacity of Phy/B mixtures (Phy/B: 75/25, 50/50, and 25/75), the removal efficacy of Eu(III) ions (an analog for fissiongenic lanthanides and actinides), and the rate of their binding reaction were studied using the batch adsorption equilibrium and kinetic experiments at different Eu(III) initial concentrations, solution pH, and solution to adsorbent (L/S) ratio. The adsorption capacity of the Phy/B mixtures increased with the increased bentonite content in the mixture depending on the L/S ratio and solution pH. The highest increase in the adsorption capacity of the Phy/B mixtures compared to phyllite was observed for the Phy/B proportions of 25/75 and 50/50. The rate of the Eu(III) adsorption was the best fitted by the pseudo-second-order kinetic model indicating that the adsorption rate was controlled by chemisorption. The Sips model provided the best correlation of the adsorption experimental data, indicative of more than one adsorption site. The results of this study show the advantage of the Phy/B mixtures in immobilizing Eu and certain fission products by combining adsorption properties of the materials.

The role of authigenic sulfides in immobilization of potentially toxic metals in the Bagno Bory wetland, southern Poland.

The supply of Cd, Cu, Fe, Pb, Zn, and Tl into a wetland in the industrial area of Upper Silesia, southern Poland via atmospheric precipitation and dust deposition has been counterbalanced by the biogenic metal sulfide crystallization in microsites of the thin (<30 cm) peat layer, despite the overall oxidative conditions in the wetland. Disequilibrium of the redox reactions in the peat pore water (pH 5.4-6.2) caused by sulfate-reducing microorganisms has resulted in the localized decrease in Eh and subsequent precipitation of micron- and submicron-sized framboidal pyrite, spheroidal ZnS and (Zn,Cd)S, and galena as revealed by high-resolution scanning electron microscopy (SEM)/energy dispersive spectrometer (EDS). Saturation index for each sulfide is at a maximum within the calculated Eh range of -80 and -146 mV. Lead was also immobilized in galena deposited in fungal filaments, possibly at a higher Eh. Thallium (up to 3 mg kg(-1)) in the peat strongly correlates with Zn, whereas Cu (up to 55 mg kg(-1)) co-precipitated with Pb. The metal sulfides occur within microbial exudates, which protect them from oxidation and mechanical displacement. Vertical distribution of toxic metals in the peat layer reflects differences in pollution loads from atmospheric deposition, which has been much reduced recently.

Pseudomorphs of barite and biogenic ZnS after phyto-crystals of calcium oxalate (whewellite) in the peat layer of a poor fen.

Pseudomorphs of barite (BaSO4) and Cd-rich ZnS after whewellite (CaC2O4·H2O) occur within remnants of Scots pine bark tissues in the peat layer of a poor fen located near a zinc smelter in south Poland. A two-step formation of the pseudomorphs is postulated based on SEM observations: (1) complete dissolution of whewellite, possibly caused by oxalotrophic bacteria, and (2) subsequent bacterially induced precipitation of barite and spheroidal aggregates of ZnS together with galena (PbS) in voids left by the dissolved whewellite crystals. Local increase in pH due to microbial degradation of whewellite, elevated concentrations of Zn(II) and Ba(II) in pore water due to the decomposition of atmospheric particles of sphalerite and barite in the acidic (pH 3.5-3.8) environment, oxidation of S species during drying and rewetting of the peat layer, and subsequent partial reduction of sulfate anions by sulfur-reducing bacteria were all factors likely involved in the crystallization of ZnS and barite in the microenvironment of the post-whewellite voids.