Alteration of cholinesterase activity as possible mechanism of silver nanoparticle toxicity

Due to their broad-spectrum antimicrobial activity, silver nanoparticles (AgNPs) have been used in a large number of commercial and medical products. Such proliferated AgNP production poses toxicological and environmental issues which need to be addressed. The present study aimed to investigate the effects of AgNPs on acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), important enzymes in areas of neurobiology, toxicology and pharmacology. Three different AgNPs, prepared by the chemical reduction using trisodium citrate, hydroxylamine hydrochloride (Cl-AgNPs), and borohydride following stabilization with poly(vinyl alcohol), were purified and characterised with respect to their sizes, shapes and optical properties. Their inhibition potential on AChE and BChE was evaluated in vitro using an enzyme assay with o-nitrophenyl acetate or o-nitrophenyl butyrate as substrates, respectively. All three studied AgNPs were reversible inhibitors of ChEs. Among tested nanoparticles, Cl-AgNP was found to be the most potent inhibitor of both AChE and BChE. Although the detailed mechanism by which the AgNPs inhibit esterase activities remains unknown, structural perturbation of the enzyme may be the common mode of ChE inhibition by AgNPs.     

Direct electrothermal atomic spectrometric determination of Ag in aqua regia extracts of soils, sediments, and sewage sludge with matrix modification

Silver is subject to significant interferences caused by high chloride concentrations in electrothermal atomic absorption spectrometry, thus its direct determination in aqua regia leaches from soils, sediments, and sludges is very difficult, especially when using instrumentation equipped with deuterium-lamp background correction (D₂). In this study, the interference of the aqua regia medium was successfully eliminated using Pd–citric acid chemical modifier. This chemical modifier was found to be the most advantageous in comparison with Pd mixture with ascorbic acid, tartaric acid, or citric acid–Li based on its ability to suppress the interference originating from different chloride matrix. Palladium increases the analyte stability; citric acid serves as a reducing reagent, and furthermore, it helps to remove the interfering chlorides by forming HCl, in the drying step of the electrothermal program. In the presence of the modifier, the pyrolysis temperature can be adjusted up to 1,000 °C with no loss of the analyte. The obtained limit of detection and characteristic mass were 5 ng g^?1 and 1.7 pg, respectively. The accuracy of the method was verified by means of six different reference samples and by comparing the results of the analysis of real samples with those obtained by inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometer. The proposed method was applied to the Ag determination in soils, sediments, and sewage sludge samples from the Pardubice region in Czech Republic.     

Assessment of flood-induced changes of phytoplankton along a river–floodplain system using the morpho-functional approach

In this research, we aimed to find out how the differences in hydrological connectivity between the main river channel and adjacent floodplain influence the changes in phytoplankton community structure along a river–floodplain system. The research was performed in the River Danube floodplain (Croatian river section) in the period 2008–2009 characterised by different flooding pattern on an annual time scale. By utilising the morpho-functional approach and multivariate analyses, the flood-derived structural changes of phytoplankton were analysed. The lake stability during the isolation phase triggered the specific pattern of morpho-functional groups (MFG) which were characterised by cyanobacterial species achieving very high biomass. Adversely, the high water turbulence in the lake during the frequent and extreme flooding led to evident similarity between lake and river assemblages. Besides different diatom species (groups of small and large centrics and pennates), which are the most abundant representatives in the river phytoplankton, many other groups such as cryptophytes and colonial phytomonads appeared to indicate altered conditions in the floodplain driven by flooding. Having different functional properties, small centric diatom taxa sorted to only one MFG cannot clearly reflect environmental changes that are shown by the species-level pattern. Disadvantages in using the MFG approach highlight that it is still necessary to combine it with taxonomical approach in monitoring of phytoplankton in the river–floodplain ecosystems.     

Long-term investigations of post-Chernobyl radiocaesium in fallout and air in North Croatia

The long-term behaviour of (137)Cs activity concentrations in air and fallout has been studied in the city of Zagreb for the post-Chernobyl period (1986-2006) as a part of an extended monitoring program of radioactive contamination of human environment in Croatia. Annual mean (137)Cs activity concentrations in air and annual total deposition fluxes (wet plus dry) decreased from 2.8 x 10(-4) Bq m(-3) in September 1986 to 3.0 x 10(-6) Bq m(-3) in last quarter of 2006 and from 6,410 Bq m(-2) year(-1) in 1986 to 2 Bq m(-2) year(-1) in 2006 respectively. By fitting the measured (137)Cs activity concentrations to the theoretical curve the ecological half-lives of (137)Cs in air and fallout were estimated with respective values of 0.46 and 0.54 years for immediate post-Chernobyl period, increasing to 5.52 and 3.97 years afterwards. Using the data on (137)Cs activity concentrations in air and fallout total caesium deposition velocity of (3.34 +/- 3.13) x 10(-2) ms(-1) was estimated with median value being 2.13 x 10(-2) ms(-1). Such relatively high (137)Cs deposition velocities compared with pre-Chernobyl ones, are characteristic for the post-Chernobyl period and, according to Stokes' settling law, indicate that the diameters of aerosol particles associated with (137)Cs originated from the Chernobyl accident are pretty large, i.e. >1 microm. (134)Cs/(137)Cs activity ratio in fallout and in air has been found to be similar to the theoretically predicted values, initial value being about 0.5 and decreasing according to differential radioactive decay. The similar ratio has been observed in most of the other environmental samples.     

Fluxes and Loading of Heavy Metals, Benzo[a]pyrene and Oil Products in Vilnius City

The concentrations of heavy metals Pb, Cd, Cu, Zn and Hg, benzo[a]pyrene and oil products (C₁₅–C₂₈) in bulk (wet and dry) atmospheric deposition in Vilnius city in 2005–2006 were analysed. The highest flux to the ground surface of the city residential area, reaching 1,680 mg m^?2 year^?1, was determined for oil products, which in atmospheric bulk deposition was estimated to be mainly in the form of solid sediments. Among heavy metals, the highest flux was determined for Zn (113.5 mg m^?2 year^?1), while the lowest flux was determined for Hg (0.06 mg m^?2 year^?1). The flux of investigated pollutants ranges from a few times, or for some pollutants, up to one order of magnitude higher at the urban sampling site in comparison to residential or background sites. Some hundred tons of oil products, approximately 52 tons of zinc and a considerably lower amount of mercury, benzo[a]pyrene and cadmium deposit yearly to the ground and water surface of Vilnius city. Metallic constructions related to transport and buildings, automobile exhausts, spills of fuel and lubricants are suggested to be the factors which result in the accumulation of high amounts of heavy metals, oil products and other pollutants on the ground surface of the city.     

Evaluation of the Impact of Long-range Transport and Aerosol Concentration Temporal Variations at the Eastern Coast of the Baltic Sea

Ambient particles vary greatly in their ability to affect visibility, climate and human health. The fine fraction of aerosol is responsible for greater and wider effects on human health; thus, investigation of this fraction is very important. Continuous measurements of PM2.5 (particulate matter below 2.5 μm in size) concentrations at the Preila monitoring station started in 2003. During a period of 2 years, the episodes of high daily and semi-hourly concentrations of PM2.5 were measured. These episodes did not depend on the season or time of day. The substantial role of long-range transport of pollutants to these increases in concentration was shown using chemical and statistical analysis. It was found that most of the severe episodes occurred when air masses came from a specific site besides it was established that air masses of different origin were characterized by different mixing layer depth. Lower mixing depth was observed in air masses characterized by higher observed concentrations at the measuring site and vice versa. PM2.5 concentrations showed diurnal and seasonal variations whose pattern reflected the regional origin of the aerosol. The regional pollution level was evaluated by the statistical analysis of PM2.5 concentrations. The background annual average of PM2.5 mass concentration for the eastern coast of the Baltic Sea was 15.1 ± 0.8 μg m⁻³.     

Using historical ecology to reassess the conservation status of coniferous forests in Central Europe

Forests cover approximately one‐third of Central Europe. Oak (Quercus) and European beech (Fagus sylvatica) are considered the natural dominants at low and middle elevations, respectively. Many coniferous forests (especially of Picea abies) occur primarily at midelevations, but these are thought to have resulted from forestry plantations planted over the past 200 years. Nature conservation and forestry policy seek to promote broadleaved trees over conifers. However, there are discrepancies between conservation guidelines (included in Natura 2000) and historical and palaeoecological data with regard to the distribution of conifers. Our aim was to bring new evidence to the debate on the conservation of conifers versus broadleaved trees at midelevations in Central Europe. We created a vegetation and land‐cover model based on pollen data for a highland area of 11,300 km² in the Czech Republic and assessed tree species composition in the forests before the onset of modern forestry based on 18th‐century archival sources. Conifers dominated the study region throughout the entire Holocene (approximately 40–60% of the area). Broadleaved trees were present in a much smaller area than envisaged by current ideas of natural vegetation. Rather than casting doubt on the principles of Central European nature conservation in general, our results highlight the necessity of detailed regional investigations and the importance of historical data in challenging established notions on the natural distribution of tree species.