Hydrodechlorination of dichlorobenzenes and their derivatives over Ni-Mo/C catalyst: kinetic analysis and effect of molecular structure of reactant

The kinetics of the catalytic hydrodechlorination (HDC) process of selected dichlorobenzenes (DCBs), dichlorotoluenes (DCTs) and dichlorodiphenyls (DCDs) was studied in the presence of a sulphided carbon-supported Ni-Mo catalyst. The HDC runs were performed in a magnetic stirred batch reactor in the range of 210-230 °C under the hydrogen pressure of 3 MPa. The kinetic constants were evaluated and the reaction network was proposed assuming the pseudo-first order kinetics of dechlorination process. The HDC of aromatic dichloroderivatives proceeded via a network of sequential-parallel reactions. At 210 °C DCBs, DCTs and DCDs followed mainly the pathway of direct transformation to respective aromatic hydrocarbon. At 230 °C, the contribution of sequential dechlorination to monochloroderivative became more predominant.     

Short-term effects of dimethoate on metabolic responses in Chrysolina pardalina (Chrysomelidae) feeding on Berkheya coddii (Asteraceae), a hyper-accumulator of nickel

Berkheya coddii Roessler (Asteraceae) is a hyper-accumulator of nickel, which can be used in phytomining and phytoremediation. Chrysolina pardalina Fabricius (Chrysomelidae) is a phytophagous leaf beetle, which may be useful in controlling population levels of B. coddii after it has been introduced into a new habitat. The aim of this study was to investigate the response of C. pardalina to topical application of dimethoate. Data recorded included the activity of acetylcholinesterase (AChE), the concentration of glutathione (GSH), and the activity of selected enzymes connected with GSH metabolism. Assays were carried out several times during the first 24h after exposure to dimethoate. At the dosages used in this study, dimethoate was not as toxic as expected. AChE activity was significantly decreased 14 and 24h after application. GST activity was significantly decreased 24h after application. GSTPx activity was significantly decreased 2, 14 and 24h after application. GR activity was significantly increased 4h after application. GSH concentration was significantly increased 24h after application. Long-term exposure to high levels of nickel may have caused adaptive changes in the enzymes that enable C. pardalina to deal with other stressors, including organophosphate pesticides.     

Tradable Permit Systems: Considering Uncertainty in Emission Estimates

We simulate the market for emission permits by considering uncertainty in emission inventory reports. The approach taken in this analysis is to enhance the emissions reported in each region by a certain part of their uncertainty when compliance with the Kyoto targets is being proved. While this formulation is not new in the literature, we define the uncertainty component in a way that enables comparison with the approach of effective permits presented in Nahorski, Horabik, and Jonas (2007) Compliance and emissions trading under the Kyoto protocol: Rules for uncertain inventories, (this issue). We show and explain that the transformation to effective permits bears additional costs apart from those resulting from shifting the Kyoto targets.     

Accuracy assessment of a small-area method for estimating the spatial distribution of the degree of tree damage

Tree damage, gauged by the amount of defoliation, is one of the basic criteria used to determine treatments for protected and economic forests. Monitoring should include an assessment of the degree of tree damage in different spatial scales. Therefore, in addition to the commonly applied large-area methods, small-area methods should be used. The aim of the paper is to present the results of the accuracy assessment of a small-area method, proposed by Podlaski (2005) [Podlaski, R. (2005). Inventory of the degree of tree defoliation in small areas. Forest Ecology and Management, 215, 361–377], for monitoring the degree of tree damage. The degree of tree damage was shown in sub-blocks P₃ of the system of information on natural environment (SINUS). To estimate the spatial distribution of the degree of tree defoliation, survey sampling, based on simple random sampling with replacement (SRSWR), was used. The degree of damage to fir (Abies alba Mill.) and beech (Fagus sylvatica L.) was analysed in the Święty Krzyż forest section in the Świętokrzyski National Park. The maximum total estimation errors for the proportion of trees with a degree zero of damage, and with second and third degrees of damage together (for α = 0.05) were at most 30.8% for fir and 24.3% for beech trees. For standard, small-area evaluations, these are satisfactory values. In the Święty Krzyż forest section, the number of P₃ sub-blocks with 0.00–5.00% of undamaged trees and with 80.01–100.00% of moderately- or severely-damaged trees was significantly greater for fir than for beech. These results indicate that the fir population was unhealthier than the beech group in the study area. P₃ sub-blocks of the SINUS system, in which the proportion of the healthiest trees was highest, were situated at the forest margin, bordering on meadows and arable fields (in the case of fir) and forming dense patches consisting of several sub-blocks, or occurring singly in the whole study area (in the case of beech). The results show the significant differentiation of forest tree health in small areas.     

Dissipation of S-metolachlor in plant and soil and effect on enzymatic activities

The present study aimed at evaluating the dissipation of S-metolachlor (S-MET) at three doses in maize growing on diverse physico-chemical properties of soil. The effect of herbicide on dehydrogenase (DHA) and acid phosphatase (ACP) activity was estimated. A modified QuEChERS method using LC-MS/MS has been developed. The limit of quantification (0.001 mg kg^?1) and detection (0.0005 mg kg^?1) were very low for soil and maize samples. The mean recoveries and RSDs for the six spiked levels (0.001–0.5 mg kg^?1) were 91.3 and 5.8%. The biggest differences in concentration of S-MET in maize were observed between the 28th and 63rd days. The dissipation of S-MET in the alkaline soil was the slowest between the 2nd and 7th days, and in the acidic soil between the 5th and 11th days. DT₅₀ of S-MET calculated according to the first-order kinetics model was 11.1–14.7 days (soil) and 9.6–13.9 days (maize). The enzymatic activity of soil was higher in the acidic environment. One observed the significant positive correlation of ACP with pH of soil and contents of potassium and magnesium and negative with contents of phosphorus and organic carbon. The results indicated that at harvest time, the residues of S-MET in maize were well below the safety limit for maize. The findings of this study will foster the research on main parameters influencing the dissipation in maize ecosystems.     

The influence of chemical protection on the content of heavy metals in wheat (<Emphasis Type="Italic">Triticum aestivum</Emphasis> L.) growing on the soil enriched with granular sludge

The presence of heavy metals in Triticum aestivum L. growing on the soil enriched with granular sludge after chemical protection was observed. The five variants of treatments using herbicide (Chwastox Turbo 340SL) and four fungicides (Topsin M 500SC, Amistar 250SC, Artea 330EC, and Falcon 460EC) were performed. On control and experimental plots, the concentration of Ni, Pb, Cr, and Cu in wheat leaves were in the range 0.32–0.99, 0.92–1.57, 0.89–6.31, and 7.08–12.59 mg/kg and in grains 0.03 to 0.11, 0.14–0.25, 0.11–0.76, and 1.06–1.46 mg/kg, respectively. The concentration of Pb in grain protected by MCPA and 2,4-D with thiophanate-methyl and azoxystrobin was higher than the maximum levels of 0.20 mg/kg D.M. The bioconcentration factor (BCF) differed and depended on chemical protection. The highest value of BCF was achieved for Cd. The statistical analysis showed a significant correlation between concentration of metals and quality parameters of wheat. One observed significant negative correlations between Ni/Zeleny sedimentation value (r = ?0.51) and between Pb/starch content (r = ?0.57). Positive correlations were observed between Cd/yield, the number of grains/ergosterol concentration (respectively, r = 0.41, r = 0.55, r = 0.56), and Zn/thousand grain weight (r = 0.50) at a p ≤ 0.05.     

Analysis of selected fungi variation and its dependence on season and mountain range in southern Poland—key factors in drawing up trial guidelines for aeromycological monitoring

The aim of the study was to identify fungal spores, in particular plant pathogenic fungi, occurring in the air in selected mountain ranges. The results revealed not only the array of fungal species migrating with air currents from the Czech Republic and Slovakia but also how the season of the year affects the distribution of spores. Such studies may lay a foundation for future aeromycological monitoring, in accordance with the requirements for integrated plant protection. Aeromycological research was carried out between 2013 and 2016 at 3-month intervals in mountainous areas along the southern borders of Poland: the Bieszczady, the Pieniny, the Giant Mountains (Karkonosze) and the Babia Góra Massif. The research relied on impact method employing Air Ideal 3P sampler, which, by drawing in atmospheric air, also collects fungal spores. Regardless of altitudinal zonation, the changing weather conditions appeared to be the main reason for the variations in the number of the fungal spores under study in those years.     

Spatial distribution of major and trace elements in the water of Swarzędzkie Lake (Poland)

In order to characterize the contamination of the Swarzedzkie Lake and generate elemental distribution patterns 18 elements have been determined in samples of water, taken just above the bottom sediments. Analyses were carried out using two instrumental techniques - ICP-OES and ICP-MS. Two main sources of contamination were identified - diffuse pollution from agriculture and stormwater from the town. Three separate groups of elements were distinguished using cluster analysis and two groups using principal component analysis. These three groups are characterized as geogenic elements (Ag, As, Mg and Sb), elements supplied by the agricultural catchment (Ca, Mn, Sr, Na, K and Al) and elements originated from the urban contamination (Ni, Cr, Cu, Fe, V, Ba, Zn and Pb). PCA differentiated the above group of urban elements from the rest, originated from diffuse sources, with exception of alluminium, which was situated between two distinguished groups.     

The study of rare earth elements in farmer's well waters of the Podwiśniówka acid mine drainage area (south-central Poland)

The principal objective of the current study was to elucidate the potential influence of acid mine drainage (AMD) pond on neighboring farmer's wells in the Podwi?niówka area (south-central Poland), using North American Shale Composite (NASC)-normalized rare earth element (REE) concentration profiles. The well waters generally displayed a distinctly positive Eu anomaly similar to that of parent rocks and AMD sediment. In contrast, the AMD pit pond water exhibited the typical roof-shaped NASC-normalized REE concentration pattern with a strong positive Gd anomaly. The low pH (mean of 2.9) of this pond water is induced by oxidation of pyrite that occurs in quartz veins and rocks exposed in the abandoned Podwi?niówka quarry. The principal source of REEs in turn is a crandallite series of aluminum–phosphate–sulfate (APS) minerals (gorceixite with florencite and Ce-bearing goyazite) that prevail in most clayey shales. These data indicate that the REE contents of the AMD pit pond and well waters are linked to bedrock mineralogy and lithology, but not to pyrite mineralization. The diverse REE patterns of NASC-normalized REE concentrations of the AMD and well waters may suggest complex sorption and desorption processes that occur at the rock–water interface influenced by different pH, Eh, temperature, and other factors. This is evidenced by a presence of strong positive Ce anomaly in the rocks, a lack of Ce anomaly in the AMD water and sediment, and the dominant negative anomaly of this element in the well waters. Variations in correlation coefficients (r ²) of REE concentrations between the rocks and the well waters may also result from a different contribution of quartzites, clayey shales, or tuffites to the REE signal of well waters as well as from mixing of shallow groundwater with infiltrating rainwater or meltwater with different REE profiles.     

Evaluation of applicability of the Sartorius Airport MD8 sampler for detection of Bacillus endospores in indoor air

This study was designed to evaluate the measuring range and lowest limit of detection of Bacillus endospores in the ambient room air when the Sartorius MD8 sampler, and two different culture methods for bacterial enumeration were used. Different concentrations of bioaerosol were generated inside the test chamber filled with either the high-efficiency particulate air (HEPA)-filtered air or with the ambient room air. The detection of endospores in the HEPA-filtered air was achievable: (1) when they were aerosolized at a concentration above 7.56?×?10³ CFU/m³ and analyzed with spread plate method, and (2) when they were aerosolized at a concentration above 4.00?×?10² CFU/m³ and analyzed with pour plate method. The detection of endospores in the ambient room air was possible: (1) when they were aerosolized at a concentration above 9.1?×?10³ CFU/m³ and analyzed with spread plate method, and (2) when they were aerosolized at a concentration above 5.6?×?10² CFU/m³ and analyzed with pour plate method. The microorganisms present in the ambient room air interfere with precise quantification of Bacillus endospores when their concentration is relatively low. The results of this study may be helpful in critical assessment of the results obtained from monitoring the air for bacterial endospores.