Application of quantum-chemical approximations to environmental problems: Prediction of physical and chemical properties of TNT and related species

This paper presents accurate predictions of ecologically important properties of nitroaromatic compounds and their derivatives, including vapor pressure, Henry's law constants, water solubility, octanol/water partition coefficients, heats of formation and ionization potentials. The proposed technique of calculations was based on quantum-chemical methods. The relationship between the chemical structure and mentioned physico-chemical parameters of such widespread military produced contaminants as trinitrotoluene and its derivatives was considered. We revealed that the DFT level of theory combined with the COSMO-RS technique is able to predict the studied parameters with an accuracy that results in error bars of less then one logarithmic unit.     

Tributyltin (TBT) induces oxidative stress and modifies lipid profile in the filamentous fungus Cunninghamella elegans

To investigate the response of the tributyltin-degrading fungal strain Cunninghamella elegans to the organotin, a comparative lipidomics strategy was employed using an LC/MS-MS technique. A total of 49 lipid species were identified. Individual phospholipids were then quantified using a multiple reaction monitoring method. Tributyltin (TBT) caused a decline in the amounts of many molecular species of phosphatidylethanolamine or phosphatidylserine and an increase in the levels of phosphatidic acid, phosphatidylinositol and phosphatidylcholine. In the presence of TBT, it was observed that overall unsaturation was lower than in the control. Lipidome data were analyzed using principal component analysis, which confirmed the compositional changes in membrane lipids in response to TBT. Additionally, treatment of fungal biomass with butyltin led to a significant increase in lipid peroxidation. It is suggested that modification of the phospholipids profile and lipids peroxidation may reflect damage to mycelium caused by TBT.     

QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P(L)) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P(L) predicted by models used varied between -3.94 to -2.66 for Mono-; -4.85 to -2.97 for Di-; -5.18 to -3.17 for Tri-; -6.02 to -3.77 for Tetra-; -6.64 to -4.64 for Penta-; -7.36 to -4.76 for Hexa-; -7.54 to -5.79 for Hepta-; -7.75 to -6.64 for Octa-; -7.89 to -7.44 for Nona-Ct-Abs; and -8.09 and -8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P(L) -4 to -2) and low (log P(L) < -4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.     

基于QSAR模型的蒙特卡洛方法分析有机化学物质对大型蚤(Daphnia magna)的毒性

本文建立一系列758种有机化合物对大型蚤(Daphnia magna)毒性的定量结构-活性关系(QSARs)。用简化的分子线性输入系统(SMILES)代表分子结构。用CORAL(关联和逻辑)软件作为工具来开发QSAR模型。这些模型使用蒙特卡罗方法建立,依据的原理是QSAR是一个“随机事件”,假设检验一组随机数据分布在可见的训练集和不可见的验证集。检验了三组分布于可见的训练、校准、测试集中的数据以及不可见的验证集。最佳模型的预测潜能,也就是其不可见的验证集的统计特征如下:n = 87,r² = 0.8377,RMSE = 0.564。建议和讨论了所构建模型的机械解释和适用领域。
精选自Alla P. Toropova, Andrey A. Toropov, Aleksandar M. Veselinovi?, Jovana B. Veselinovi?, Danuta Leszczynska, Jerzy Leszczynski. Monte Carlo based QSAR models for toxicity of organic chemicals to Daphnia magna. Environmental Toxicology and Chemistry: Volume 35, Issue 11, pages 2691–2697, November 2016. DOI: 10.1002/etc.3466
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3466/full
     

Comparison of methods for leaching heavy metals from composts

This paper presents the determination of total iron, copper, zinc, chromium, nickel, lead, cadmium and mercury contents in the compost obtained from sorted municipal organic solid waste applying the following methods of sample mineralization: 40% hydrofluoric acid with preliminary incineration of a sample, a mixture of concentrated nitric(V) and chloric(VII) acids with preliminary incineration of organic matter and a mixture of nitric(V) and chloric(VII) acids without sample incineration. The speciation analysis of Tessier was used to estimate the bioavailability of the metals. Elution degrees of the mobile forms of the metals from the compost with 10% nitric(V) acid and 1 mol/dm(3) hydrochloric acid were compared. The contents of the elements in the eluates were determined applying atomic absorption spectrometry.     

The effect of the corticosteroid hormone cortexolone on the metabolites produced during phenanthrene biotransformation in Cunninghamella elegans

The metabolism of phenanthrene and the mammalian corticosteroid hormone cortexolone by the fungus Cunninghamella elegans was studied. The amounts of the cortexolone transformation products, cortisol and epicortisol, were affected by the presence of phenanthrene. Approximately 40% more cortisol was produced by C. elegans in cultures with phenanthrene. In contrast, epicortisol formation decreased. C. elegans transformed phenanthrene to phenanthrene trans-1,2-,3,4-, and 9,10-dihydrodiols, phenols, diphenols (diols) and glucoside conjugates of 1-, 2-, 3-, 4-, and 9-phenanthrols. Almost all of the phenanthrene initially added was metabolized to ethyl acetate extractable metabolites. In the mycelia and culture medium extracts, phenanthrol glucosides represented 80% and 94% of the total metabolites, respectively. The major metabolite was the glucoside conjugate of 1-phenanthrol. The presence of cortexolone affected the biodegradation of phenanthrene by decreasing the amounts of phenanthrene metabolites compared to control cultures.     

Source determination of highly chlorinated biphenyl isomers in pine needles - comparison to several PCB preparations

The isomer specific composition of 13 technical PCB formulations of different origin and of pine needles was analyzed using GC/MS and HRGC/HRMS. Nonachlorinated biphenyls were identified in 11 among 13 formulations analyzed, with the highest abundance found for highly chlorinated ones (Aroclors 1268 and 1260, Chlorofen, Sovol, Kanechlors 600 and 500, Delor 106, Clophen A60). Decachlorobiphenyl was identified only in Aroclor 1268, Clophen A60, Aroclor 1260 and Chlorofen, comprising, respectively, 8.9, 2.8, 1.3 and 0.82% of the total bulk of nona- and decaCBs detected. Nona- and decaCB were detected in pine needles in Poland with the highest concentrations found at the sites neighboring to a former production sites of the Polish PCB formulations, while in pine needles collected around the Tokyo Bay nona- and decacCB were detected only in four of 10 sites and the concentrations corresponded to those found at the rural areas of Poland.     

Structural and technological changes of greenhouse gas emissions during the transition period in Polish industry

We analyzed the patterns of energy use and greenhouse gas (GHG) emissions in Polish industry arising during the transition from a centrally planned economy to a market economy. A method of analyzing industry energy use and GHG emissions is discussed. Using this method, the impact of changes in industrial production value, the share of specific industry branches in the total industrial production, energy intensity, and the mix of the energy carriers in the 1989–1993 period has been analyzed. The last year of the analyzed period shows favorable trends in efficiency and signs of production structure shift to a less energy-intensive one. Economic reform implemented after 1989, which released energy carriers' prices from government control, had important effects on the industrial sector. Energy efficiency and emission intensity trends of 1992–1994 were favorable; if they continue, production will return to 1989 levels with much lower energy consumption and significantly decreased GHG emissions.