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.     

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.     

Hydrological and environmental conditions as key drivers for spatial and seasonal changes in PCDD/PCDF concentrations, transport and deposition along urban cascade reservoirs

To investigate the drivers for transport and deposition of 17 2,3,7,8-substituted PCDDs/PCDFs along an urban river, water samples from five reservoirs located along the river course were collected in January and July 2008. The concentrations of 17 congeners of PCDD/PCDF were determined and compared to environmental - physical, chemical and biological - conditions. The obtained data revealed that the concentration of the sum of toxic PCDDs/PCDFs in water samples differ between reservoirs as well as between seasons, ranging from 12.04 pg L(-1) in UP (first in the cascade) to 1327.94 pg L(-1) in PR (last in the cascade) during winter of 2008; and from 34.94 pg L(-1) in UP to 1352.50 pg L(-1) in TR (next to last) in summer 2008. In comparison, water samples collected from the river had a concentration several times lower at the first two sites (sites no. 1 and 4) and no detectable values at the last three stations (sites no. 7, 8, 10). The obtained data demonstrated strong or moderate correlations between the sum of 17 PCDDs/PCDFs and TEQ in reservoir water samples and physical, chemical and biological conditions, such as: Mg(2+) (R=0.82; R=0.80, respectively), SO(4)(2-) (R=0.80; R=0.80, respectively), K(+) (R=0.80; R=0.80, respectively), Ca(2+) (R=0.67, R=0.70, respectively), OSM (R=0.63, R=0.70, respectively). In addition, the positive strong correlation between TEQ concentrations and the water temperature (R=0.63) and chlorophyll a content (R=0.90) was noted. The violent weather conditions occurred during the research season with periods of intensive storm events (up to 32 mm in mid July), and thus the increased river flow velocity (up to 0.45 m(3)s(-1)) could have a direct and indirect influence on PCDDs/PCDFs concentration through changes in the sedimentation/resuspension ratio and consequently in transport, deposition and degradation processes along the river/reservoirs.     

Sulfadimethoxine and sulfaguanidine: their sorption potential on natural soils

Sulfonamides (SAs) are one of the oldest groups of veterinary chemotherapeutic agents. As these compounds are not completely metabolized in animals, a high proportion of the native form is excreted in feces and urine. They are therefore released either directly to the environment in aquacultures and by grazing animals, or indirectly during the application of manure or slurry. Once released into the environment, SAs become distributed among various environmental compartments and may be transported to surface or ground waters. The physicochemical properties of SAs, dosage and nature of the matrix are the factors mainly responsible for their distribution in the natural environment. Although these rather polar compounds have been in use for over half a century, knowledge of their fate and behavior in soil ecosystems is still limited. Therefore, in this work we have determined the sorption potential of sulfadimethoxine and sulfaguanidine on various natural soils. The influence on sorption of external factors, such as ionic strength and pH, were also determined. The sorption coefficients (K_d) obtained for the sulfonamides investigated were quite low (from 0.20 to 381.17 mL g⁻¹ for sulfadimethoxine and from 0.39 to 35.09 mL g⁻¹ for sulfaguanidine), which indicated that these substances are highly mobile and have the potential to run off into surface waters and/or infiltrate ground water. Moreover, the sorption of these pharmaceuticals was found to be influenced by OC, soil solution pH and ionic strength, with higher K_d values for soils of higher OC and lower K_d values with increasing pH and ionic strength.     

Catalytic destruction of 1,2-dichlorobenzene on V2O5-WO3/Al2O3-TiO2 catalyst

Studies on the catalytic destruction of 1,2-dichlorobenzene were carried out on a specially constructed semi-technical equipment whose most important element was a catalytic reactor with a monolithic catalyst in the form of 150 x 150 x 100 mm cubes. A catalyst made from cordierite with an active layer composed of Al2O3 - 64 wt%, TiO2 - 26 wt%, V2O5 - 6.6 wt% and WO3 - 3.4 wt% was used. The reactor made it possible to carry out the process in the temperature range 150-350 degrees C, at variable catalyst loading and different velocities of gas flow through the reactor. The content of 1,2-dichlorobenzene in the air was analysed by a chromatographic method. A significant effect of catalyst loading and temperature on 1,2-dichlorobenzene destruction efficiency was observed and no effect of the linear flow velocity through the catalyst on o-dichlorobenzene destruction efficiency was reported. The applied vanadium-tungsten catalyst on a monolithic carrier made from TiO2/gamma-Al2O3 revealed very good activity that resulted in an over 80% efficiency of 1,2-dichlorobenzene destruction at the temperature around 250 degrees C at a very high catalyst loading reaching ca. 8200 h(-1). Additionally, in this study the kinetics of 1,2-dichlorobenzene decomposition was determined, specifying the order of reaction and dependence of the decomposition rate constant on temperature, using a simple power-rate law model.     

The redox state and activity of superoxide dismutase classes in Arabidopsis thaliana under cadmium or copper stress

The redox state of glutathione and ascorbate as well as the activity of superoxide dismutase classes were determined in leaves of Arabidopsis thaliana grown for seven days in the nutrient solution containing 0, 5 and 50 microM Cd or Cu excess. A decrease in GSH/GSSG ratio was found in plants under Cd and Cu stress. In the plants exposed to Cu stress the activity of all SOD classes increased. However, in the plants treated with Cd the activity of FeSOD and MnSOD was elevated, but CuZnSOD activity was diminished in comparison with control. In these plants the activity of SOD classes was dependent on both the GSH/GSSG and AA/DHA ratios, while in those exposed to Cu excess - on the GSH/GSSG ratio. Differences were shown in the changes both in redox state and activity of SOD classes caused by the metals differing in physiochemical properties. Moreover, relationships between changes in SOD class activities and ROS levels were discussed.     

Atmospheric nitrogen fluxes at the Belgian coast: 2004–2006

Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel).The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m^?2 d^?1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m^?2 d^?1, respectively.Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.9–1.4 mg N m^?2 d^?1. Generally, the contribution of aerosol NH₄⁺ was more significant in the medium and fine particulate fractions than that of aerosol NO₃^?, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (～15%) to the total N-budget.Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m^?2 d^?1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH₄⁺ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 2–2.5-times higher than in other campaigns.     

The effects of cadmium or zinc multigenerational exposure on metal tolerance of Spodoptera exigua (Lepidoptera: Noctuidae)

The effects of ten generational zinc or cadmium pre-exposure on metal tolerance among beet armyworm Spodoptera exigua individuals were compared. These effects were assessed in animals from the 11th generation, reared on a diet either uncontaminated or contaminated with metal (cadmium or zinc). The survival rate of larvae and the degree of metal accumulation (in larvae, pupae and moths; among larval organs: gut and fat body) were analysed. Catalase, superoxide dismutase and glutathione transferase activity in larval organs of individuals subjected to different metal treatments were also measured. Animals transferred from control rearing to metals (cadmium or zinc) in the 11th generation, as well as those from multigenerational zinc treatment, but not from multigenerational cadmium treatment, had a significantly lower survival rate than control animals. Insects from the groups with the high metal treatment had high bioaccumulation factors (above 3.7 and 2.3 following cadmium and zinc, respectively). Cadmium (but not zinc) pre-exposure had a significant effect on metal accumulation in larvae. Multigenerational metal pre-exposure seemed to have mainly a negative effect on glutathione transferase activity in the gut of larvae from the 11th generation, in the case of the individuals exposed to metal other than that used in pre-exposure treatment or kept in control conditions. However, in the case of zinc pre-exposure, such effect was only apparent when zinc was replaced by cadmium. The long-term effect of cadmium on catalase activity in larvae was found.