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.     

Mercury in certain boletus mushrooms from Poland and Belarus

This paper reports the results of the study of Hg contents of four species of Boletus mushroom (Boletus reticulatus Schaeff. 1763, B. pinophilus Pilát & Dermek 1973, B. impolitus Fr. 1838 and B. luridus Schaeff. 1774) and the surface soils (0–10 cm layer, ～100 g) samples beneath the mushrooms from ten forested areas in Poland and Belarus by cold-vapour atomic absorption spectroscopy. The ability of the species to bioconcentrate Hg was calculated (as the BCF) while Hg intakes from consumption of these mushroom species were also estimated. The median Hg content of the caps of the species varied between 0.38 and 4.7 mg kg^?1 dm; in stipes between 0.13 and 2.5 mg kg^?1 dm and in the mean Hg contents of soils varied from 0.020 ± 0.01 mg kg^?1 dm to 0.17 ± 0.10 mg kg^?1 dm which is considered as “background” Hg level. The median Hg content of caps of B. reticulatus and B. pinophilus were up to 4.7 and 3.6 mg kg^?1 dm, respectively, and they very efficiently bioaccumulate Hg with median BCF values of up to 130 for caps and 58 for stipes. The caps and stipes of these mushrooms if eaten will expose consumer to elevated dose of total Hg estimated at 1.4 mg for caps of Boletus reticulatus from the Kacze ??gi site, which is a nature reserve area. Nevertheless, the occasional consumption of the valued B. reticulatus and B. pinophilus mushrooms maybe safe.     

Polychlorinated biphenyls and -naphthalenes in pine needles and soil from Poland--concentrations and patterns in view of long-term environmental monitoring

Pine needles were selected as cost effective and easy collectable matrices suitable for long-term monitoring of the lower troposphere pollution with polychlorinated biphenyls and polychlorinated naphthalenes. The fingerprints of PCNs and PCBs in the top layers of agricultural soils were used for determination of point sources of pollution for terrestrial ecosystems. The new idea based on the use of nona- and decachlorinated isomers fingerprint as an additional tool suitable for the identification of potential point sources of pollution with PCBs, seemed to be a capable tool to identify contamination of soil and ambient air related to former manufacturing and the use of highly chlorinated technical PCB preparations.     

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 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).     

Polychlorinated biphenyl and organochlorine insecticide residues in human adipose tissue in Poland

Concentrations of PCBs (polychlorinated biphenyls) and organochlorine insecticides such as DDT, HCHs (hexachlorocyclohexanes), HCB (hexachlorobenzene) and chlordanes were determined in human adipose fat from the provinces of Skierniewice and Gdańsk in Poland collected during 1979 and 1990, respectively. The mean levels (microg g(-1) lipid weight basis) in Skierniewice and Gdańsk were found to be 1.2+/-0.44 and 1.5+/-1.3 for PCBs, 25+/-16 and 15+/-13 for DDT, 0.53+/-0.17 and 0.25+/-0.09 for HCHs, 0.36+/-0.22 and 0.26+/-0.23 for HCB, and 0.11+/-0.08 and 0.07+/-0.04 for chlordanes, respectively. Very high concentrations of DDT were detected, with the maximum value as high as 52 microg g(-1) lipid weight in Skierniewice and 47 microg g(-1) lipid weight in Gdańsk. PCB residues contained in the human fat from Polish cadavers are comparable to those of the levels reported for industrialized nations. It is appraised from the levels of DDT and PCBs in Poles' fat that the Polish environment is still experiencing both types of contamination, arising from agricultural and industrial activities. Contamination of humans by other organochlorine insecticides was relatively lower.     

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.