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
     

The practical societal problem of pollution and public health as the source of a variety of problems regarding chance mechanisms operating in living organisms

The essence of the societal problem which justifies the expenditure of large sums on studies of pollution and health is illustrated by three figures included in this paper. The first two of these figures illustrate the contemporary publicity favoring the two competing energy-producing technologies, the nuclear and the conventional fossil-burning technologies. The very existence of this costly publicity demonstrates that the decisions affecting public health are now frequently made without due regard to the relevant scientific findings. The third figure illustrates the most laudable effort of the Environmental Protection Agency to establish a relationship between hoped-for decreases in mortality and the dollar cost of removing from the environment any one of the several investigated pollutants, e.g., “particulates”, krypton-85, tritium, etc.The subsequent parts of this presentation tend to document the fact that the reliability of the EPA chart published in 1973 is illusory. The same applies to the large number of other official publications, including those of the National Academy of Sciences. The results of more modern studies brought to the fore a variety of biological chance mechanisms, such as competing risks, dose-rate effects, synergisms, etc., which make the problem attacked by EPA much more difficult than was originally anticipated.The basic research, combining the laboratory experimentation on animals and theoretical considerations, results in a better understanding of a variety of phenomena. However, this better understanding seems to imply that the solution of the practical societal problem requires a large multipollutant and multilocality epidemiological study.     

Human health risk assessment case study: an abandoned metal smelter site in Poland

United States Environmental Protection Agency methodologies for human health risk assessment (HRA) were applied in a Brownfields Demonstration Project on the Warynski smelter site (WSS), an abandoned industrial site at Piekary Slaskie town, Upper Silesia, Poland. The HRA included the baseline risk assessment (BRA) and the development of risk-based preliminary remedial goals (RBPRGs). The HRA focused on surface area covered with waste materials, which were evaluated with regard to the potential risks they may pose to humans. Cadmium, copper, iron, manganese, lead, and zinc were proposed as the contaminants of potential concern (COPCs) at WSS based on archive data on chemical composition of waste located on WSS. For the defined future land use patterns, the industrial (I) and recreational (II) exposure scenarios were assumed and evaluated. The combined hazard index for all COPCs was 3.1E+00 for Scenario I and 3.2E+00 for Scenario II. Regarding potential carcinogenic risks associated with the inhalation route, only cadmium was a contributor, with risks of 1.6E-06 and 2.6E-07 for Scenario I and Scenario II, respectively. The results of the BRA indicated that the potential health risks at WSS were mainly associated with waste material exposure to cadmium (industrial and recreational scenarios) and lead (industrial scenario). RBPRGs calculated under the industrial scenario were 1.17E+03 and 1.62E+03 mg/kg for cadmium and lead, respectively. The RBPRG for cadmium was 1.18E+03 mg/kg under the recreational scenario. The BRA results, as well as RBCs, are comparable for both scenarios, so it is impossible to prioritize land use patterns for WSS based on these results. For choosing a future land use pattern or an appropriate redevelopment option, different factors would be decisive in the decision-making process, e.g., social, market needs, technical feasibility and costs of redevelopment actions or acceptance of local community.     

Studies on reactions of ozone with alkenes

In the last years, a continuous increase of the O3 concentration has been recorded in the lower atmospheric layers. Photochemical reactions with NO(x), CO and organic compounds are the main sources of O3 in the troposphere. In this work, an attempt was made to determine the impact of alkenes on the O3 concentration in the troposphere. A study on the gas-phase reactions of 03 with 1-hexene, 1-heptene and 1-nonene was made. The reactions were carried out at room temperature under atmospheric pressure. Ozone was formed by the ultraviolet radiation emitted by a mercury lamp, in order to simulate the atmospheric conditions. The changes with time in the concentration of O3, 1-alkenes and formed aldehydes were investigated. Qualitative and quantitative analyses were done by means of the gas chromatography and colorimetry. The following products were identified: pentanal from 1-hexene; hexanal from 1-heptene; oktanal from 1-nonene. For each of the reactions, HCHO was also determined as a product. The reaction rate constants were calculated and obtained in units of 10(-17) cm(-3) molecule(-1) s(-1): 1.94-0.99 for 1-hexene, 5.54-4.51 for 1-heptene and 1.54-0.76 for 1-nonene. Based on the results obtained, an explanation of O3 concentration variations in the planetary boundary layer can be given. Last year a considerable increase of O3 concentration on the roads of Western Europe was recorded. This increase could have resulted from the decrease of alkene concentration in the air due to common use of the catalytic converters in cars. The unsaturated hydrocarbons rapidly oxidize on the catalyst. In Eastern Europe, where the amount of cars equipped with catalytic converters is smaller than in Western Europe, the alkene content in the exhaust fumes results in a decrease of the O3 concentration in the troposphere.     

Qualitative structure residue relationship analysis in the determination of the maximum residue limit of veterinary drugs

Aim of the present study was an attempt to find a correlation between physicochemical structure of veterinary drugs and the maximum residue limit (MRL) for muscle tissue of food producing animals. Direct correlation and analysis in quintile groups for 52 physicochemical parameters were performed. An internal validation using leave-one-out cross-validation was performed. In the quintile groups, there were 11 arithmetic expressions created for the limited group of individual parameters (13 from 52 analyzed), which showed a significant linear or quadratic correlation between the number of quintile group and the mean value of MRL within the quintile. The results obtained suggest that there is no direct correlation between individual physicochemical parameters and MRL value in muscle tissue; however, such correlation can be determined for arithmetic expressions created on the basis of several physicochemical parameters, using quintile group analysis.     

Metals in edible fish from Vistula River and Dead Vistula River channel, Baltic Sea

Metals including Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Sr and Zn were determined in muscle tissue of 12 fish species by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and cold vapour-atomic absorption spectroscopy (CV-AAS). Fish were collected from Vistula River at lower course and Dead Vistula River channel in south of Baltic Sea in Poland. The fish species examined include Round Goby (Neogobius melanostomus), Crucian Carp (Carassius carassius), Bull-rout (Myoxocephalus scorpius), Tench (Tinca tinca), Bream (Abramis brama), Burbot (Lota lot), Perch (Perca perca), Roach (Rutilus rutilus), Silver Carp (Hypophthalmichthys molitrix), Pikeperch (Stizostediun lucioperca), Brown salmon (Salmo trutta m. Trutta) and Eel (Anguilla anguilla). The median values of metal concentrations in fresh muscle tissue of 11 fish species varied as follows: Al < 0.5-60; Ba < 0.05-0.31; Ca 120-1800; Cd < 0.05-0.096; Co < 0.10; Cr < 0.10-0.50; Cu < 0.15-0.77; Fe 1.5-21; Hg 0.0058-0.65; K 1800-4200; Mg 130-560; Mn 0.12-0.59; Na 350-840; Ni < 0.2-0.31; Pb < 0.75; Sr 0.079-2.9; Zn 3.3-23 μg/g fresh weight. The Target Hazard Quotient (THQ) values calculated in this study for Cd and Hg from muscles of fish species collected from Vistula River were low in the range of 0.4 for Hg and 0.8 for Cd.     

Estimation of K(OA) values of 209 polychlorinated trans-azobenzenes by PM6 and DFT methods

The octanol-air partition coefficients (K(OA)) of all 209 PCt-ABs were determined computationally to fill gaps on their environmentally relevant physical and chemical properties. These properties have been determined using two computational approaches: the semi-empirical quantum chemistry method for property parameterization (PM6) of the molecular orbital package (MOPAC) and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set in Gaussian 03 software and artificial neural network (ANN) predicting abilities. Both computational methods enabled estimation of log K(OA) partition coefficients of PCt-ABs with a similar accuracy and precision. The PM6 method compared to DFT was highly superior because it requires much less time, manpower and cost of hardware. The determined log K(OA) values of the investigated PCt-ABs for standard condition (25 °C) varied between 8.30 and 8.75 for Mono-; 8.71 and 9.92 for Di-; 9.58 and 10.72 for Tri-; 10.11 and 11.34 for Tetra-, 10.83 and 11.85 for Penta-; 11.24 and 12.36 for Hexa-; 11.87 and 12.66 for Hepta-; 12.31 and 12.97 for Octa-; 12.89 and 13.21 for Nona-Ct-ABs; and 13.17- and 13.49 for Deca-Ct-AB. PCt-ABs, in view of these log K(OA) values, can be classified as compounds of relatively low (Mono-, Di- and some of Tri- Ct-ABs with values of log K(OA) around 8 to 10) environmental mobility (most of Tri- to Nona-Ct-ABs and Deca-Ct-AB homologues with values of log K(OA) >10), and with a potential to be adsorbed by soil particles.     

Multivariate analysis of mineral constituents of edible Parasol Mushroom (Macrolepiota procera) and soils beneath fruiting bodies collected from Northern Poland

Caps and stipes of 141 fruiting bodies of Parasol Mushroom (Macrolepiota procera) and surface layer of soils collected from 11 spatially distant and background (pristine) areas in Northern Poland were analyzed for Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr, and Zn by inductively coupled plasma optical emission spectroscopy and cold vapor atomic absorption spectroscopy. In terms of bioconcentration and bioexclusion concept, K, Ag, Cu, Rb, and P were highly bioconcentrated in caps, and their bioconcentration factor values varied for the 11 sites between 120 and 500—67–420, 70–220, 10–170, and 45–100, respectively. Cd, Zn, Mg, and Na showed bioconcentration factors (BCFs) between 3.3 and 36, 3.7–15, 0.92–6.3, and 1.4–44 while Al, Ba, Ca, Co, Cr, Mn, Ni, Pb, and Sr were excluded (BCF < 1). The Parasol Mushroom is a species harvested in the wild, and its caps are of unique taste and can contain a spectrum of essential and hazardous mineral compounds accumulated at elevated concentrations, even if collected at the background (pristine) areas. These elevated mineral concentrations of the caps are due to the efficient bioconcentration potential of the species (K, Ag, Cu, Rb, P, Cd, Zn, Mg, and Na) and abundance in the soil substrates (Al, Ca, Fe, Mn). The estimated intake rates of Cd, Hg, and Pb contained in Parasol Mushroom’s caps show a cause for concern associated with these metals resulting from the consumption of between 300- and 500-g caps daily, on a frequent basis in the mushrooming season.     

Response of non-enzymatic antioxidative mechanisms to stress caused by infection with Fusarium fungi and chemical protection in different wheat genotypes

The aim of this study was to assess the effect of infection with Fusarium fungi and chemical protection on the contents of phenolic acids and antioxidative potential of extracts from grains of 23 wheat genotypes. Based on chemical analyses including abiotic factors such as weather conditions and the location of the plantation, the authors attempted to clarify non-enzymatic antioxidative response mechanisms to two different stressors in 23 wheat genotypes. Based on chemical analysis, it was found that mass infection with fungi from the genus Fusarium induces defence mechanisms of the plant, which results in an increased production of phenolic acids, mainly those, which are substrates for the production of acids exhibiting antimicrobial action. This mechanism is confirmed by the analyses of antioxidant activity, which also increases significantly during fungal infection, connected with the production of mycotoxins. In the course of chemical plant protection, significant changes were observed in the production of phenolic acids. Even if antioxidant activity was not higher in comparison to the control, an increased production of certain phenolic acids was recorded, which suggests stimulation of the resistance system of the plant, at a simultaneous complete response of antioxidative mechanisms, as it takes place during fungal infection.