Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

Effect of steam hydration on performance of lime sorbent for CO2 capture

Lime is considered a feasible sorbent for the capture of CO₂ from large stationary sources. The positive attributes of a natural source material, low cost and lack of harmful by-products are offset by rapid deterioration in performance and high regeneration temperature. Performance can be improved by hydrating the lime using steam. We investigate a steam hydration process wherein lime is hydrated for 5 min at 300 °C and atmospheric pressure in a mixture of steam and CO₂. The experiments consisted of 10 capture cycles with 60% of the lime active at the end. Extrapolation using a decay model suggests a residual carbonation level of 48%, significantly higher than the 8% achieved by dry lime cycles. The cost of replacement sorbent under these conditions is less than $1/t of CO₂ captured. The hydrated lime process also reduces the thermal load, for heating and cooling, by half as well as the inventory, and therefore solids handling, by a factor 5 over dry lime. The introduction of the hydration reaction provides another exothermic reaction for heat management.     

Phytoremediation of Selected Explosives

The phytoremediation of trinitrotoluene (TNT), nitroglycerine (NG) and pentaerytritoltetranitrate (PETN) using in vitrocultures of Rheum palmatum, Saponaria officinalisand Populus simonii were studied. All above mentioned explosives were degradated to less toxic products and finally probably bound to the cell wall or further involved in the metabolism. The formation of trinitrobenzene (TNB) during degradation of TNT which is a product of alternative degradation pathway was found too.     

Association of minor and trace elements with mineralogical constituents of urinary stones: A hard nut to crack in existing studies of urolithiasis

The role of metals in urinary stone formation has already been studied in several publications. Moreover, urinary calculi can also be used for assessing exposure of humans to minor and trace elements in addition to other biological matrices, for example, blood, urine, or hair. However, using urinary calculi for biomonitoring of trace elements is limited by the association of elements with certain types of minerals. In this work, 614 samples of urinary calculi were subjected to mineralogical and elemental analysis. Inductively coupled plasma mass spectrometry and thermo-oxidation cold vapor atomic absorption spectrometry were used for the determination of major, minor, and trace elements. Infrared spectroscopy was used for mineralogical analysis, and additionally, it was also employed in the calculation of mineralogical composition, based on quantification of major elements and stoichiometry. Results demonstrate the applicability of such an approach in investigating associations of minor and trace elements with mineralogical constituents of stones, especially in low concentrations, where traditional methods of mineralogical analysis are not capable of quantifying mineral content reliably. The main result of this study is the confirmation of association of several elements with struvite (K, Rb) and with calcium phosphate minerals, here calculated as hydroxylapatite (Na, Zn, Sr, Ba, Pb). Phosphates were proved as the most important metal-bearing minerals in urinary calculi. Moreover, a significantly different content was also observed for Fe, Zr, Mo, Cu, Cd, Se, Sn, and Hg in investigated groups of minerals. Examination of such associations is essential, and critical analysis of mineral constituents should precede any comparison of element content among various groups of samples.     

Individual sensitivity distribution evaluation from survival data using a mechanistic model: implications for ecotoxicological risk assessment

Two main alternatives are typically used to model mechanistically dose-survival relationship in ecotoxicity tests. Effects are related to a concentration of concern, for instance body concentration, and, to account for their differences relative to time-to-death, individuals have either different concentration thresholds for death (“individual tolerance approach”), or equal probability to die, with death occurring randomly (“stochastic death approach”). A general framework to unify both approaches has recently been proposed. We derived a model from this framework to analyse five datasets (daphnids exposed to selenium, guppies exposed to dieldrin and second, third and fourth instars chironomids exposed to copper), by extending the standard stochastic death approach. We showed the possibility to estimate properly the toxicity parameters together with inter-organisms differences of sensitivity for at least one of these parameters (here the threshold for effect). For the daphnids, there was no improvement of using the extended model, which confirms the expected low variability among genetically identical individuals. For all the other datasets, our model outperformed the standard approach without accounting for differences of sensitivity. We estimated coefficients of variations in the distribution of the logarithm of the threshold from 44% to 4% and showed, for chironomids, a decrease of inter-individual differences of sensitivity with the age of the larvae. All standard threshold estimates were close but above the medium value of the distribution in the new approach, which means that a concentration equal to the standard threshold would ultimately result in the death of more than half of the exposed organisms. A more relevant parameter, such as the concentration protecting 95% of the population, would be 2-4 times inferior to the standard threshold.     

The influence of temperature and hydration on the sorption properties of bentonite

The effects of exposure to synthetic groundwater at elevated temperature gradients on the sorption properties of bentonite were investigated using the Mock-Up-Cz experiment. This experiment simulated the vertical placement of a container of radioactive waste according to the Swedish KBS-3 system for a period of more than 3 years. The mineralogical composition, as well as its chemical and physico-chemical properties, including the uptake of (99)TcO(4)(-) and (134)Cs(+), was used to evaluate the chemical changes caused by the long-term exposure of bentonite buffer to thermal and hydration gradients. It was found that the bentonite material was predominantly stable. No more than 2% of the montmorillonite was transformed due to thermal and moisture gradients. It was concluded that the new-formed mineral phases have no significant influence on the ion exchange and sorption properties of bulk bentonite samples.