Prediction of environmental partition coefficients and the Henry's law constants for 135 congeners of chlorodibenzothiophene

Polychlorinated dibenzothiophenes (PCDTs) could be classified as persistent organic pollutants (POPs) in the environment and are particularly interesting due to their structural resemblance to highly toxic dioxins. We show here some basic environmental properties such as n-octanol water (K_OW), n-octanol/air (K_OA) and air/water (K_AW) partition coefficients as well as Henry’s law constants (K_H) for all 135 congeners of chlorodibenzothiophene. Predictions were made by regression of principal components (PCR) and with aid of a set of standard chemicals, for which physical–chemical properties are well featured. Computed K_OW, K_OA, K_AW and K_H values for mono-CDTs ranged, respectively, between 4.66 and 4.71, 7.48 and 7.55, −2.84 and −2.82, 3.56 and 3.74; for di-CDTs between 5.02 and 5.28, 8.03 and 8.29, −3.01 and −2.95, 2.42 and 2.75; for tri-CDTs between 5.53 and 5.70, 8.65 and 8.87, −3.2 and −3.11, 1.58 and 1.92; for tetra-CDTs between 5.95 and 6.13, 9.27 and 9.50, −3.39 and −3.27, 1.02 and 1.33; for penta-CDTs between 6.38 and 6.51, 9.88 and 10.05, −3.54 and −3.45, 0.72 and 0.88; for hexa-CDTs between 6.83 and 6.97, 10.54 and 10.66, −3.72 and −3.64, 0.47 and 0.56; for hepta-CDTs between 7.28 and 7.35, 11.12 and 11.20, −3.81 and −3.87, 0.33 and 0.38; for octa-CDT 7.74, 11.78, −4.04 and 0.23. An estimated value of the three types of partition coefficient and Henry’s law constants suggest that polychlorinated dibenzothiophenes are lipophilic and semi-volatile persistent organic pollutants. Their mobility in the environment seems to be very similar to that of some well-known POPs such as polychlorinated dibenzofurans, -dibenzo-p-dioxins, and -biphenyls or organochlorine pesticides.     

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.     

Sediment Quality Assessment in the Gulf of Gdańsk (Baltic Sea) Using Complementary Lines of Evidence

Sediments from Polish coastal environments were classified by a quality assessment approach that took into account trace metal and organic micropollutant concentrations, grain-size distribution, and organic carbon content. Generally, no benthic organisms were found at sites where sediments were classified as heavily polluted. However, areas characterized by a moderate contamination showed a variable composition of the benthic community and changing bioaccumulation patterns; therefore, no single species found in the Gulf of Gdańsk could be considered representative of the whole benthic environment. Although sediment monitoring must be considered a suitable tool to detect hot-spot pollution areas in coastal and inland waters, it should be complemented by bioaccumulation measurements to evaluate the actual risk posed by contaminants to benthic organisms. This “biological information” allows a better appreciation of the real benthic infaunal community exposure to chemicals and can usefully complement the existing sediment quality guidelines.     

Mercury in wild mushrooms and underlying soil substrate from the great lakes land in Poland

Fifteen species of wild mushrooms and underlying soil samples collected in a virgin landscape of Augustowska Forest in northeastern Poland in 1997-98 were analyzed for total mercury to evaluate the status of contamination and usefulness of higher mushrooms as possible bioindicators of mercury pollution. Among the 15 species analyzed, Pinewood King Bolete, Scaly Tooth and King Bolete showed relatively high bioconcentration factors (BCF: dry-weight normalized concentrations of mercury in mushrooms relative to concentrations in soil) for mercury, which varied between 69 and 110. These three species were also characterized by great concentrations of total mercury in caps (between 2,000 +/- 800 and 2,300 +/- 1,100 ng g-1 dry wt) and stalks (between 850 +/- 390 and 1,000 +/- 500 ng g-1 dry wt.). Species such as Red-hot Milk Cap, Poison Pax and Common Chantherelle had mercury BCFs of less than 1, while Gipsy Bolete, Orange Birch Bolete, Brown Scaber Stalk, Variegated Bolete, Sandy Knight-cap and Yellow-cracking Bolete were weak or moderate mercury accumulators with BCFs between 1 and 40. Concentrations of mercury in mushrooms were greater than the tolerance limits suggested for mercury in plant foods.     

Accumulation factors of mercury in mushrooms from Zaborski Landscape Park, Poland

Total mercury concentrations were determined by cold-vapour atomic absorption spectroscopy (CV-AAS) in 117 samples of caps, 117 of stalks and 47 of whole fruiting bodies of 13 species of wild mushrooms and in 164 underlying soil substrate collected from Zaborski Landscape Park during 1997 and 1998. The study area is a background, forested site with rural landscape and no known local sources of mercury emission. Mean mercury concentrations in mushrooms varied widely (range: 50 +/- 20 to 3700 +/- 1700 ng/g, dry matter) depending on the site and mushroom species investigated. However, mercury concentrations in soil samples varied less (range: 3.0 +/- 3.0 to 43 +/- 17 ng/g dry matter). Fruiting bodies of Common Puffball (Lycoperdon perlatum) and King Bolete (Boletus edulis) contained the greatest concentrations of mercury of 3700 +/- 1700 and 2600 +/- 1200 ng/g dry matter, respectively. A positive correlation existed between mercury concentrations in the caps of Slippery Jack (Suillus luteus) and Fly Agaric (Amanita muscaria) (p < 0.01) and mercury concentrations in corresponding soils. However, concentrations of mercury in The Sickener (Russula emetica) was negatively correlated with its soil substrate (p < 0.01). Bioconcentration factors (BCFs: concentrations ratios of mercury in mushroom to soil) of total mercury in whole fruiting bodies or caps were greatest for Common Puffball (L. perlatum), Larch Bolete (Suillus grevillei) and King Bolete (B. edulis) and varied between 130 +/- 78 and 160 +/- 120, while for the other species BCFs were between 4.0 +/- 6.0 and 61 +/- 20 in caps, and 4.4 +/- 3.1 and 70 +/- 68 in stalks. The concentration ratios of Hg in cap to stalk were from 1.1 +/- 0.5 for Poison Pax (Paxillus involutus) to 2.7 +/- 1.7 in Larch Bolete (S. grevillei).     

Hydrogenolysis of chlorobenzene,dichlorobenzenes and chlorotoluenes by in situ generated and gaseous hydrogen in alkaline media and the presence of Pd/C catalyst

A method for dechlorination of chloroaromatic compounds at room temperature and atmospheric pressure by an in situ generated––in reaction of Al particles with water––or gaseous hydrogen in alkaline media and the presence of Pd/C catalyst was thoroughly investigated, having in mind its possible application in utilization of organochlorine waste. Conversion degree to dechlorinated compounds depended on the constitution of substrates and ranged between 88% and 96% when in situ hydrogen was used (at substrate (chlorine) to catalyst molar ratio 550:1 and over twofold stoichiometric excess of Al relative to substrate (chlorine); the process lasted ca. 26 h until all Al was consumed), or 90–97% if gaseous hydrogen was purged. Effectiveness of dechlorination was markedly affected by stirring, i.e. size of the stirrer and speed of revolution. Prospects for application of the method described were briefly outlined.     

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.     

Methyl-triclosan binding to human serum albumin: Multi-spectroscopic study and visualized molecular simulation

Methyl-triclosan (MTCS), a transformation product and metabolite of triclosan, has been widely spread in environment through the daily use of triclosan which is a commonly used anti-bacterial and anti-fungal substance in consumer products. Once entering human body, MTCS could affect the conformation of human serum albumin (HSA) by forming MTCS–HSA complex and alter function of protein and endocrine in human body. To evaluate the potential toxicity of MTCS, the binding mechanism of HSA with MTCS was investigated by UV–vis absorption, circular dichroism and Fourier transform infrared spectroscopy. Binding constants, thermodynamic parameters, the binding forces and the specific binding site were studied in detail. Binding constant at room tempreture (T = 298 K) is 6.32 × 10³ L mol⁻¹; ΔH⁰, ΔS⁰ and ΔG⁰ were 22.48 kJ mol⁻¹, 148.16 J mol⁻¹ K⁻¹ and −21.68 kJ mol⁻¹, respectively. The results showed that the interactions between MTCS and HSA are mainly hydrophobic forces. The effects of MTCS on HSA conformation were also discussed. The binding distance (r = 1.2 nm) for MTCS–HSA system was calculated by the efficiency of fluorescence resonance energy transfer. The visualized binding details were also exhibited by molecular modeling method and the results could agree well with that from the experimental study.     

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.     

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.