Application of chemometric analysis based on physicochemical and chromatographic data for the differentiation origin of plant protection products containing chlorpyrifos

The aim of this study was to investigate the similarities and dissimilarities between the pesticide samples in form of emulsifiable concentrates (EC) formulation containing chlorpyrifos as active ingredient coming from different sources (i.e., shops and wholesales) and also belonging to various series. The results obtained by the Headspace Gas Chromatography–Mass Spectrometry method and also some selected physicochemical properties of examined pesticides including pH, density, stability, active ingredient and water content in pesticides tested were compared using two chemometric methods. Applicability of simple cluster analysis and also principal component analysis of obtained data in differentiation of examined plant protection products coming from different sources was confirmed. It would be advantageous in the routine control of originality and also in the detection of counterfeit pesticides, respectively, among commercially available pesticides containing chlorpyrifos as an active ingredient.     

Mercury in Precipitation at an Urbanized Coastal Zone of the Baltic Sea (Poland)

Wet deposition is an important source of metals to the sea. The temporal variability of Hg concentrations in precipitation, and the impact of air masses of different origins over the Polish coastal zone were assessed. Samples of precipitation were collected (August 2008–May 2009) at an urbanized coastal station in Poland. Hg analyses were conducted using CVAFS. These were the first measurements of Hg concentration in precipitation obtained in the Polish coastal zone. Since Poland was identified as the biggest emitter of Hg to the Baltic, these data are very important. In the heating and non-heating season, Hg concentrations in precipitation were similar. Hg wet deposition flux dominated in summer, when the production of biomass in the aquatic system was able to actively adsorb Hg. Input of metal to the sea was attributed to regional and distant sources. Maritime air masses, through transformation of Hg(0), were an essential vector of mercury in precipitation.     

Anaerobic co-digestion of swine and poultry manure with municipal sewage sludge

The anaerobic digestion of municipal sewage sludge (SS) with swine manure (SM) and poultry manure (PM) was undertaken. It was found that a mixture of sewage sludge with a 30% addition of swine manure gave around 400 dm³/kgVS of biogas, whereas the maximal biogas yield from ternary mixture (SS:SM:PM = 70:20:10 by weight) was only 336 dm³/kgVS. An inhibition of methanogenesis by free ammonia was observed in poultry manure experiments. The anaerobic digestion was inefficient in pathogen inactivation as the reduction in the number of E. coli an Enterobacteriaceae was only by one logarithmic unit. A substantial portion of pathogens was also released into the supernatant.     

The impact of land use and season on the riverine transport of mercury into the marine coastal zone

In Mediterranean seas and coastal zones, rivers can be the main source of mercury (Hg). Catchment management therefore affects the load of Hg reaching the sea with surface runoff. The major freshwater inflows to the Baltic Sea consist of large rivers. However, their systems are complex and identification of factors affecting the outflow of Hg from its catchments is difficult. For this reason, a study into the impact of watershed land use and season on mercury biogeochemistry and transport in rivers was performed along two small rivers which may be considered typical of the southern Baltic region. Neither of these rivers are currently impacted by industrial effluents, thus allowing assessment of the influence of catchment terrain and season on Hg geochemistry. The study was performed between June 2008 and May 2009 at 13 sampling points situated at different terrain types within the catchments (forest, wetland, agriculture and urban). Hg analyses were conducted by CVAFS. Arable land erosion was found to be an important source of Hg to the aquatic system, similar to urban areas. Furthermore, inflows of untreated storm water discharge resulted in a fivefold increase of Hg concentration in the rivers. The highest Hg concentration in the urban runoff was observed with the greatest amount of precipitation during summer. Moderate rainfalls enhance the inflow of bioavailable dissolved mercury into water bodies. Despite the lack of industrial effluents entering the rivers directly, the sub-catchments with anthropogenic land use were important sources of Hg in the rivers. This was caused by elution of metal, deposited in soils over the past decades, into the rivers. The obtained results are especially important in the light of recent environmental conscience regulations, enforcing the decrease of pollution by Baltic countries.     

Remediation capacity of Cd and Pb ions by mycelia of Imleria badia,Laetiporus sulphureus,and Agaricus bisporus in vitro cultures

The goal of this study was to evaluate cadmium and lead accumulation ability of in vitro cultures biomass containing selected edible mushroom species derived from the environment (Laetiporus sulphureus, Imleria badia) and those of commercial origin (Agaricus bisporus). Atomic absorption spectrometry was used to evaluate the content of Cd(II) and Pb(II) on the medium supplemented with Cd(II) or Pb(II), each of them at the same concentration of 5·10^?5 M. The highest concentration of Cd(II) ions was determined in the biomass from L. sulphureus in vitro cultures, while the highest concentration of Pb(II) ions was found in the biomass from A. bisporus in vitro cultures. The greatest Cd(II) and Pb(II) accumulation ability in mycelium per dry weight was shown for L. sulphureus. Among the test species, biomass of A. bisporus showed the lowest ability for the bioaccumulation of Cd(II); however, comparable ability for the remediation of Pb(II) was provided by the biomasses from A. bisporus and I. badia in vitro cultures. The results confirm the possibility of using these mushroom species for remediation and indicate the relationship between bioaccumulation of heavy metals and the test species.     

The effect of thymol and its derivatives on reactions generating reactive oxygen species

The effects of thymol (TOH), thymoquinone (TQ) and dithymoquinone (TQ2) on the reactions generating reactive oxygen species (ROS) such as superoxide anion radical (O2*-), hydroxyl radical (HO*) and singlet oxygen (1O2) were tested using the chemiluminescence (CL) and spectrophotometry methods. All tested compounds acted as scavengers of various ROS. The rate constant of 1O2-dimols quenching by thymol was calculated.     

Remediation aspect of microbial changes of plant rhizosphere in mercury contaminated soil

Phytoremediation, an approach that uses plants to remediate contaminated soil through degradation, stabilization or accumulation, may provide an efficient solution to some mercury contamination problems. This paper presents growth chamber experiments that tested the ability of plant species to stabilize mercury in soil. Several indigenous herbaceous species and Salix viminalis were grown in soil collected from a mercury-contaminated site in southern Poland. The uptake and distribution of mercury by these plants were investigated, and the growth and vitality of the plants through a part of one vegetative cycle were assessed. The highest concentrations of mercury were found at the roots, but translocation to the aerial part also occurred. Most of the plant species tested displayed good growth on mercury contaminated soil and sustained a rich microbial population in the rhizosphere. The microbial populations of root-free soil and rhizosphere soil from all species were also examined. An inverse correlation between the number of sulfur amino acid decomposing bacteria and root mercury content was observed. These results indicate the potential for using some species of plants to treat mercury contaminated soil through stabilization rather than extraction. The present investigation proposes a practical cost-effective temporary solution for phytostabilization of soil with moderate mercury contamination as well as the basis for plant selection.     

Spatiotemporal dynamics of spring and stream water chemistry in a high-mountain area

The present study deals with the application of the self-organizing map (SOM) technique in the exploration of spatiotemporal dynamics of spring and stream water samples collected in the Chocho?owski Stream Basin located in the Tatra Mountains (Poland). The SOM-based classification helped to uncover relationships between physical and chemical parameters of water samples and factors determining the quality of water in the studied high-mountain area. In the upper part of the Chocho?owski Stream Basin, located on the top of the crystalline core of the Tatras, concentrations of the majority of ionic substances were the lowest due to limited leaching. Significantly higher concentration of ionic substances was detected in spring and stream samples draining sedimentary rocks. The influence of karst-type springs on the quality of stream water was also demonstrated.     

The variability of PCDD/F concentrations in the effluent of wastewater treatment plants with regard to their hydrological environment

The occurrence, concentrations, patterns, and loads of 17 2,3,7,8-substituted congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in treated wastewater collected at the outlets from 14 wastewater treatment plants (WTPs), divided into three size categories. The analysis also considered the effect of wastewater outflow on the final concentrations of PCDDs/Fs, as the samples were collected during flooding and stable hydrological conditions. None of the studied WTPs were found to completely remove toxic congeners of PCDDs/Fs from wastewater: the PCDD concentrations in the outgoing effluent during stable wastewater flow ranged from 2.99 to 177.19 pg/L, PCDFs from 6.05 to 51.30 pg/L, and the Toxic Equivalent (TEQ) was between 0.94 and 4.87 pg/L. The results from high wastewater flow were less diversified, ranging from 5.04 to 8.85 pg/L for PCDDs, from 11.47 to 32.33 pg/L for PCDFs and from 2.00 to 4.65 pg/L for TEQ. The smallest WTPs demonstrated the highest average total and TEQ concentrations due to limited volume, short retention time and outdated technology, and, hence, insufficient treatment efficiency. The largest WTPs have the potential to substantially affect the quality of river water, as despite being associated with the lowest concentrations, they released much greater volumes of treated wastewater and, hence, the greatest amounts of analyzed compounds. Elevated TEQ values were observed at high flow in all WTP size categories indicating the impact of high and stable wastewater flow on the concentrations of the observed PCDDs/Fs.