The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

Assessment of aluminum bioavailability in alum sludge for agricultural utilization

Inorganic aluminum ions, [Al(H₂O)₆]³⁺, [Al(OH)(H₂O)₅]²⁺, and [Al(OH)₂(H₂O)₄]⁺, are toxic to a number of crops. The aim of this study was to estimate the danger of soil contamination of bioavailable aluminum and heavy metals forms because of alum sludge which was a by-product of water, and wastewater treatment technology using aluminum coagulant is introduced into the soil. Aluminum and selected heavy metal fractionation was carried out in the post-coagulation sludge collected at a water treatment plant (where aluminum was used as a coagulant), fermented sewage sludge at a municipal wastewater treatment plant (which did not apply aluminum coagulant), and soil from water treatment plant as well as the mixtures of sludge and soil. It has been found that post-coagulation sludge used as natural fertilizer is a secondary source of bioavailable aluminum, especially when aluminum coagulants are used during water and wastewater treatment. The evaluation of applicability of the sludge to very weak acidic and acidic agricultural soils was carried out. The authors shall debate the question whether, in this case, the Regulation of EU and Polish Government on sewage sludge should also take the bioavailable aluminum into account and add to the list of the elements whose allowable contents are limited.     

Mercury in European Blushers,Amanita rubescens,mushrooms and topsoils: Bioconcentration potential and intake assessment

Total mercury content has been determined in fruiting bodies of European Blushers and topsoils collected from 11 sites across Poland in 2006-2008. Mercury analysis was carried out using a validated analytical method and cold-vapour atomic absorption (CV-AAS). The European Blusher effectively accumulated mercury in fruiting bodies. The mean values of total mercury in caps of European Blushers from background (uncontaminated) areas were from 0.22 to 1.0 (0.067-3.2) and in stipes from 0.16 to 0.65 (0.071-2.7) μg/g dry weight. In topsoil beneath to fruiting bodies, the median Hg concentration at 10 sites in Northern Poland varied between 0.030 and 0.072 (0.0096–0.19) μg/g dw, and in one site in Southern Poland was 0.20 (0.079–0.34) μg/g dw. Data on Hg in European Blushers from different countries were reviewed. The mean concentrations of total Hg in caps of European Blushers from two “pristine” sites in northern part of Poland were ～1.0 μg/g dw. A meal made with 300–500 g of fresh caps of European Blushers collected at such sites (assuming 90% water content in caps) can result in Hg intake of 0.0003–0.0005 mg Hg/kg bm (assuming a 60 kg bm), which is a dose equipotent to a new provisional tolerable weekly intake (PTWI) value set for inorganic Hg.     

Novel application of the CORAL software to model cytotoxicity of metal oxide nanoparticles to bacteria Escherichia coli

Convenient to apply and available on the Internet software CORAL (http://www.insilico.eu/CORAL) has been used to build up quantitative structure-activity relationships (QSAR) for prediction of cytotoxicity of metal oxide nanoparticles to bacteria Escherichia coli (minus logarithm of concentration for 50% effect pEC50). In this study six random splits of the data into the training and test set were examined. It has been shown that the CORAL provides a reliable tool that could be used to build up a QSAR of the pEC50.     

Temporal variability in 20 chemical elements content of Parasol Mushroom (Macrolepiota procera) collected from two sites over a few years

Mature specimens of Parasol Mushroom were collected annually in the outskirts of the Siemiany (2000-2003) and Rafa (2001-2003) sites in the northern part of Poland to examine temporal variations and similarities in the composition of 20 chemical elements. Analysis was done under the same condition and using well-validated analytical methods. Elements were determined by inductively coupled plasma-atomic emission spectroscopy and cold vapour-atomic absorption spectroscopy (Hg). The ranges of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn concentrations in the caps of fruiting bodies were similar (p > 0.05; Mann-Whitney U test) for both geographically distant sites, and these specimens from Rafa were more contaminated with Pb (p < 0.05; Mann-Whitney U test). The annual collections of caps in the Siemiany site varied in Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, Na, Rb and Sr and contents (0.05 < p < 0.001), while they were similar in Cr, K, Mg, Mn, Ni, P, Pb and Zn (p > 0.05; Mann-Whitney U test). The annual collections of specimens from the Rafa site varied in contents of Ag, Al, Ba, Ca, Fe, Hg, K, Mg, Mn, P, Rb and Zn (p > 0.05), while they were similar in Cd, Co, Cr, Cu, Na, Ni, Pb and Sr (p < 0.05). The results of this study imply that metallic elements content of Parasol Mushroom collected at the same undisrupted sites, and hence keeping the same geochemical condition for mushroom development and fructification (the same stands and probably the same mycelia), can fluctuate over the years or the life-span of mycelium. Hence, when assessing the nutritional value of essential metallic elements and status of non-essential or toxic metallic elements in Parasol's Mushroom caps (and probably also of other mushrooms species) to man, the possible fluctuation in contents over time have to be taken into account.     

Resolving Chernobyl vs. global fallout contributions in soils from Poland using Plutonium atom ratios measured by inductively coupled plasma mass spectrometry

Plutonium in Polish forest soils and the Bór za Lasem peat bog is resolved between Chernobyl and global fallout contributions via inductively coupled plasma mass spectrometric measurements of 240Pu/230Pu and 241Pu/239Pu atom ratios in previously prepared NdF3 alpha spectrometric sources. Compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/230Pu and 241Pu/239Pu co-vary and range from 0.186 to 0.348 and 0.0029 to 0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407 x [240Pu/239Pu] - 0.0413; r2 = 0.9924). Two-component mixing models are developed to apportion 239+240Pu and 241Pu activities; various estimates of the percentage of Chernobyl-derived 239+240Pu activity in forest soils range from < 10% to > 90% for the sample set. The 240Pu/230Pu - 241Pu/239Pu atom ratio mixing line extrapolates to estimate 241Pu/239Pu and the 241Pu/239+240Pu activity ratio for the Chernobyl source term (0.123 +/- 0.0007; 83 +/- 5; 1 May 1986). Sample 241Pu activities, calculated using existing alpha spectrometric 239+240Pu activities, and the 240Pu/230Pu and 241Pu/239Pu atom ratios, agree relatively well with previous liquid scintillation spectrometry measurements. Chernobyl Pu is most evident in locations from northeastern Poland. The 241Pu activities and/or the 241Pu/239Pu atom ratios are more sensitive than 240Pu/239Pu or 238Pu/239+240Pu activity ratios at detecting small Chernobyl 239+240Pu inputs, found in southern Poland. The mass spectrometric data show that the 241Pu activity is 40-62% Chernobyl-derived in southern Poland, and 58-96% Chernobyl in northeastern Poland. The Bór za Lasem peat bog (49.42 degrees N, 19.75 degrees E), located in the Orawsko-Nowotarska valley of southern Poland, consists of global fallout Pu.     

Radon concentrations in groundwaters of the Polish part of the Sudety Mountains (SW Poland)

In the course of researches into radon occurrence in the groundwaters of the Polish part of the Sudety Mountains, conducted in various research centres in Poland, almost 1000 radon concentration determinations have been collected. These results have given the basis for an attempt to characterise the groundwaters of this region with respect to radon content. Radon concentrations oscillated within the range of 0.2-1645 Bq/dm3, with the arithmetic mean at 240.0 Bq/dm3 and the geometric mean at 106.7 Bq/dm3. The largest number of radon concentrations found in the Sudetic groundwaters ranged between ca. 3-6 and 1000 Bq/dm3. The values over 1000 Bq/dm3 can be considered anomalously high. They constitute 3.9% of all the results and occur around six localities within different geological units of the Sudety Mountains. These are shallow circulation, low mineralised groundwaters, which outflow from gneisses and granites. In the face of the fact that from 12.8% to 72.7% (depending on the adopted norm of maximum radon concentration for drinking waters) of the examined waters cannot be drunk directly without removing at least part of the radon, and in the face of the possibility of recognizing as many as 63.5% of the waters as potentially medicinal, extensive research of radon geochemistry in the Sudety Mountains area should be urgently undertaken.     

Treatment of 2,4-dichlorophenol polluted soil with free and immobilized laccase

Enzyme treatment is currently considered for remediation of terrestrial systems polluted with organic compounds. In this study, two soils from Pennsylvania with 2.8 or 7.4% organic matter contents (Soils 1 and 2, respectively) were amended with 14C-labeled 2,4-dichlorophenol (2,4-DCP) and incubated with a laccase from Trametes villosa (free or immobilized on montmorillonite). 2,4-DCP was either transformed to methanol-soluble polymeric products (11-32%) or covalently bound to soil organic matter (53-85%); unaltered 2,4-DCP could be recovered from soil by methanol extraction (0-38%) at the completion of a 14-d incubation period. In Soil 1, both free and immobilized laccase removed 100% of 2,4-DCP without regard for moisture conditions. In Soil 2, immobilized laccase removed more 2,4-DCP (about 95%, regardless of moisture conditions) than free enzyme (55, 75, and 90% at 30, 55, and 100% of maximum water-holding capacity, respectively). Binding of 2,4-DCP in the humin fraction was nearly the same for free and immobilized laccase. More 2,4-DCP, however, was bound to humic and fulvic acids in the presence of immobilized laccase than in the presence of free laccase. In general, immobilized laccase performed better than free laccase. However, for practical applications, the higher activity of immobilized laccase is offset by a 23% loss in enzyme activity during immobilization, which approximates the 30% increase in free laccase needed to achieve the same level of remediation. Furthermore, immobilized laccase is more costly than free T. villosa laccase.