The impact of pesticides on oxidative stress level in human organism and their activity as an endocrine disruptor

Pesticides cause serious environmental and health problems both to humans and animals. The aim of this review is to discuss selected herbicides and fungicides regarding their mode of action and their influence on basic oxidative stress parameters and endocrine disruption properties tested in selected cell cultures in vitro. Because of numerous difficulties which animal studies are subject to, cell cultures are an excellent experimental model reflecting human exposure to different pesticides through all relevant routes. This experimental model can be used to monitor aggregate and cumulative pesticide exposures.     

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.     

Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

Efficacy of supplementation of selected medicinal mushrooms with inorganic selenium salts

The aim of the study was to evaluate the possibility of supplementation with inorganic forms of selenium (Na₂SeO₄ and Na₂SeO₃) in concentrations of 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5 mM of three medicinal mushroom species: Agrocybe aegerita, Hericium erinaceus and Ganoderma lucidum. Tested mushroom species grew in Se additions of 0–0.6 mM (A. aegerita and H. erinaceus), while growth of G. lucidum bodies was observed for 0–0.8 mM. For the latter mushroom species, the total Se content was the highest. Content of Se_org was diverse; for control bodies it was the highest for G. lucidum (only organic forms were present), lower for A. aegerita (84% organic forms) and the lowest for H. erinaceus (56% organic forms). Accumulation of Se(IV) was generally significantly higher than Se(VI) for all tested mushroom species. There was no significant decrease of A. aegerita or G. lucidum biomass with the exception of G. lucidum bodies growing under 0.8 mM of Se species addition (15.51 ± 6.53 g). Biomass of H. erinaceus bodies was the highest under 0.2 (197.04 ± 8.73 g), control (191.80 ± 6.06 g) and 0.1 mM (185.04 ± 8.73 g) of both inorganic salts. The addition to the medium of Se salts brought about macroscopic changes in the fruiting bodies of the examined mushrooms. Concentrations exceeding 0.4 mM caused diminution of carpophores or even their total absence. In addition, colour changes of fruiting bodies were also recorded. At Se concentrations of 0.4 and 0.6 mM, A. aegerita fruiting bodies were distinctly lighter and those of H. erinaceus changed colour from purely white to white-pink.     

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

Adaptive alterations in the fatty acids composition under induced oxidative stress in heavy metal-tolerant filamentous fungus Paecilomyces marquandii cultured in ascorbic acid presence

The ability of the heavy metal-tolerant fungus Paecilomyces marquandii to modulate whole cells fatty acid composition and saturation in response to IC₅₀ of Cd, Pb, Zn, Ni, and Cu was studied. Cadmium and nickel caused the most significant growth reduction. In the mycelia cultured with all tested metals, with the exception of nickel, a rise in the fatty acid unsaturation was noted. The fungus exposure to Pb, Cu, and Ni led to significantly higher lipid peroxidation. P. marquandii incubated in the presence of the tested metals responded with an increase in the level of linoleic acid and escalation of electrolyte leakage. The highest efflux of electrolytes was caused by lead. In these conditions, the fungus was able to bind up to 100 mg?g^?1 of lead, whereas the content of the other metals in the mycelium was significantly lower and reached from 3.18 mg?g^?1 (Cu) to 15.21 mg?g^?1 (Zn). Additionally, it was shown that ascorbic acid at the concentration of 1 mM protected fungal growth and prevented the changes in the fatty acid composition and saturation but did not alleviate lipid peroxidation or affect the increased permeability of membranes after lead exposure. Pro-oxidant properties of ascorbic acid in the copper-stressed cells manifested strong growth inhibition and enhanced metal accumulation as a result of membrane damage. Toxic metals action caused cellular modulations, which might contributed to P. marquandii tolerance to the studied metals. Moreover, these changes can enhance metal removal from contaminated environment.     

The evolution of December 2004 tsunami deposits: Temporal and spatial distribution of potentially toxic metalloids

The article presents the results of research into the content of metalloid fractions in the tsunami deposits from southern Thailand. The following fractions, which are potentially most easily released from deposits to the environment, have been distinguished: the water soluble fraction, the exchangeable fraction extracted with the phosphate buffer and the fraction eluted with the solution of hydrochloric acid. The analytical technique atomic absorption spectrometry with hydride generation was applied. Spatial variability of the metalloid fractions in deposits and changes occurring in deposits over a period of several years of observation were determined. Based on the statistical analysis of the results, an attempt was made to determine the post-depositional release of deposits components to the environment. Based on the conducted research, the 4 years forming process of the arsenic, antimony and selenium occurrence after the deposition of sediments on land were described, as well as the balance in the amount of deposit components released to the environment.     

NMR study of the humification process during sewage sludge treatment

Humic acids, extracted from sludge at the biologic-mechanical sewage treatment plant in Jastrzebie Zdroj, have been investigated by means of (1)H, (13)C and (31)P NMR spectroscopy. Sludge samples for studies were taken from the primary settling tank, the nitrification chamber, the digestion chamber and the sludge drying beds. The (1)H NMR analysis of humic acid extracted from sludge at various stages of sewage treatment confirmed the presence of the functional groups that are characteristic for humic substances, and the analysis showed changes in their relative intensities. The (13)C NMR indicated that the aromatisation of the humic acid increased during sewage treatment. Moreover, the analysis of the (31)P NMR spectra allowed us to observe the changes in the phosphorus groups of the studied humic acids.     

Co-combustion of dried sewage sludge and coal in a pulverized coal boiler

More than 1.1 million tons of municipal and industrial sewage sludge is produced annually in Poland. Most of this sewage sludge is landfilled or used for recultivation and fertilization of soil. After accession of Poland to the EU, large investments are planned for wastewater treatment, so it is expected that the amount of sewage sludge produced in Poland will grow in the near future. It is well known that the combustion of sewage sludge is becoming a more and more popular utilization method of such waste. Unfortunately, the current situation in Poland makes it impossible to incinerate the sewage sludge because of a lack of incinerators. One possible solution for Poland is the co-firing of dried sewage sludge in existing coal-fired utility boilers. This article presents results of initial Polish industrial trials of dried municipal sewage sludge and hard coal co-combustion in an OP-230 pulverized coal boiler. Such a solution was shown to be technically viable and not to require changes to the existing technological system. Cocombustion of sewage sludge with coal in power plants seems to be the best solution for sludge utilization in the near future in Poland.     

Differences in the Spatial Distribution and Chemical Composition of PM10 Between the UK and Poland

The Fine Resolution Atmospheric Multi-pollutant Exchange Model was used to calculate the spatial distribution and chemical composition of PM₁₀ concentrations for two geographically remote countries in Europe—the UK and Poland—for the year 2007. These countries are diverse in terms of pollutant emissions as well as climate conditions. Information on the contribution of natural and anthropogenic as well as national and imported particles in total PM₁₀ concentrations in both countries is presented. The paper shows that the modelled national annual average PM₁₀ concentrations, calculated for the entire country area, are similar for the UK and Poland and close to 12 μg m^?3. Secondary inorganic aerosols dominate the total PM₁₀ concentrations in Poland. Primary particulate matter has the greatest contribution to total PM₁₀ in the UK, with large contribution of base cations. Anthropogenic sources predominate (81 %) in total PM₁₀ concentrations in Poland, whereas natural prevail in the UK—hence, the future reduction of PM₁₀ air concentrations by emissions reduction could be more difficult in the UK than in Poland.