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.     

The spectroscopic studies of humic acid extracted from sediment collected at different seasons

Gocza?kowice Reservoir is the biggest water reservoir in the south of Poland. For our studies bottom sediments were collected from eight different places of the reservoir at various seasons of the year.EPR spectroscopy was applied to analyse both quantitatively and qualitatively the humic acids (HA) present in the samples. EPR spectra of the extracted HA exhibited broad lines from the paramagnetic metal ions and narrow lines from free radicals. The values of the free radical concentration obtained for HA amounted to 1.14-13.6 × 1016 spin g⁻¹ depending on the season and the place of sample collection. The values of the g factor obtained for HA were of the range 2.0027-2.0035.The EPR studies show that HA extracted from bottom sediment collected at various points of the Gocza?kowice Reservoir exhibit similar physical-chemical properties. It was also observed that the depth of the reservoir affects the content of the oxygen functional groups as well as the free radical concentration in HA.The identification of the functional groups was done by means of IR. UV/VIS spectroscopy was used to estimate the maturity of the HA.     

Study on the determination of PCDDs/Fs and HCB in exhaust gas

The subject of this study was to develop a method of simultaneous determination of PCDDs/PCDFs and HCB in exhaust gases from industrial installations. Sampling to determine PCDDs/PCDFs was conducted using the method described in PN-EN 1948-1: 2006, where the sorption material is polyurethane foam (PUF). In order to simultaneously collect PCDDs/PCDFs and HCB and to avoid sorbent bed breakthrough, it was necessary to apply an additional polyurethane sorption layer. Twenty-seven samples of exhaust gases from various cement plants and 40 samples of exhaust gases from hospital and industrial waste incineration plants collected in 2009/2010 in the entire territory of Poland were examined. The average content of PCDDs/Fs in samples from cement plants amounted to 0.076 ng I-TEQ N m(-3) (range of 0.002-0.62 ng I-TEQ N m(-3)), while the average content of HCB amounted to 10 ng N m(-3) (range of 0.98-60.5 ng N m(-3)). In the case of samples collected from waste incineration plants, the average concentration of PCDDs/Fs was 0.39 ng I-TEQN m(-3) (range of 0.002-5.68 ng I-TEQ N m(-3)). In the case of HCB, the average concentration was 238 ng N m(-3) (range of 3.21-2500 ng N m(-3)). Also, the interdependence of the concentration of PCDDs/PCDFs and HCB was determined in the analysed samples, with the ranges of low and high content of PCDDs/PCDFs being examined separately. In all cases, the determined values of the r correlation coefficient were within the range of 0.7-1.0, which indicates a good correlation between the concentrations of PCDDs/PCDFs and HCB.     

Specific accumulation of cadmium and other trace elements in Sarcodon imbricatus using ICP-MS with a chemometric approach

Fungi can effectively accumulate various metallic elements, metalloids and non-metals in fruiting bodies. This study provides information on the accumulation of Ag, As, Ba, Cd, Co, Cs, Cu, Cr, Li, Mn, Ni, Pb, Rb, Sr, V, Tl, U and Zn in the edible mushroom Sarcodon imbricatus (L.) P. Karst. using the technique of inductively coupled plasma – mass spectrometry with a dynamic reaction cell mode. Mushrooms were foraged from four regions in Poland. Baseline concentrations of minerals, expressed in mg kg^?1 dry biomass (db), were in the composite samples of caps in the range: for Ag (0.27–0.29), As (1.0–1.9), Ba (0.31–0.45), Cd (4.5–6.3), Co (0.23–1.9), Cu (28–35), Cr (0.19–0.29), Cs (20–38), Li (0.013–0.020), Mn (5.9–8.8), Ni (0.81–1.4), Pb (0.94–1.6), Rb (490–700), Sr (0.14–0.19), Tl (0.058–0.11), U (0.002–0.002), V (0.044–0.054) and Zn (140–160). Concentration levels of Ag, As, Cd, Cs, Pb and Zn were higher in caps than in stipes of S. imbricatus, whereas for other elements the distribution between caps and stipes was nearly equal or for some differed depending on the location. Certainly, the content of toxic Cd in S. imbricatus was elevated (0.45–0.63 mg kg^?1 in fresh caps) and therefore eating this mushroom could increase exposure to Cd. In addition, the content of toxic As in S. imbricatus was elevated.     

Bio- and toxic elements in mushrooms from the city of Umeå and outskirts,Sweden

Edible mushrooms (Albatrellus ovinus, Boletus edulis, Clitocybe odora, Gomphidius glutinosus, Leccinum scabrum, Leccinum versipelle, Lycoperdon perlatum, Suillus bovinus, Suillus luteus, and Xerocomus subtomentosus) collected from unpolluted areas of the city of Umeå and its outskirts in the northern part of Sweden were examined for contents of toxic metallic elements (Cd, Pb, and Ag) and essential macro- and microelements (K, Na, Ca, Mg, Cu, Fe, Mn, and Zn) using a validated method and a final measurement by flame atomic absorption spectroscopy (F-AAS). The median values of the toxic metallic element concentrations (in mg kg^?1 dry biomass, db) ranged from: 0.12–3.9, 0.46–5.1, and 0.91–6.2 for Ag, Cd and Pb, respectively. For the essential metallic elements, the median values of concentrations ranged from: 24000–58000, 15–2000, 59–610, 520–1900, 2.0–97, 16–150, 15–120, and 4.3–26 mg kg^?1 db for K, Na, Ca, Mg, Cu, Zn, Fe, and Mn, respectively. The baseline concentrations of the metallic elements determined in mushrooms were mainly affected by the fungal species. The assessed probable maximal dietary intake of Cd (0.002 mg kg^?1 body mass) solely from a mushroom meal was only slightly below a revised value of the tolerable weekly intake for this element, while for Pb (0.003 mg kg^?1 body mass) it was tenfold below the provisionally tolerable weekly intake.     

Dissipation of difenoconazole in apples used for production of baby food

Dissipation of fungicide difenoconazole (3-chloro-4-[(2RS,4RS;2RS,4SR)-4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-2-yl]phenyl 4-chlorophenyl ether) was studied following its application on apples intended for production of baby food. The apples (varieties: Jonagold Decosta, Gala and Idared) were sprayed with the formulation to control pathogens causing fungal diseases: powdery mildew (Podosphaera leucotricha ELL et Ev./Salm.) and apple scab (Venturia inaequalis Cooke/Aderh.). A validated gas chromatography-based method with simultaneous electron capture and nitrogen phosphorus detection (GC-ECD/NPD) was used for the residue analysis. The analytical performance of the method was highly satisfactory, with expanded uncertainties ≤ 19% (a coverage factor, k = 2, and a confidence level of 95%). The dissipation of difenoconazole was studied in pseudo-first-order kinetic models (for which the coefficients of determination, R², ranged between 0.880 and 0.977). The half-life of difenoconazole was 12–21 days in experiments conducted on three apple varieties. In these experiments, the initial residue levels declined gradually and reached the level of 0.01 mg kg^?1 in 50–79 days. For the residue levels to remain below 0.01 mg kg^?1 (the maximum acceptable concentration for baby foods), difenoconazole must be applied approximately 3 months before harvest, at a dose of 0.2 L ha^?1 (50 g of an active ingredient per ha).     

Pesticide contaminants in selected species of edible wild mushrooms from the north-eastern part of Poland

ABSTRACT

The aim of this study was to determine the level of chlorinated hydrocarbon residues in selected edible mushrooms from north-eastern Poland. The experiment was carried out on 45 samples consisting of 15 fruiting bodies each of the following species: Boletus edulis, Imleria badia and Cantharellus cibarius. Dried samples were subjected to extraction of lipids with a Soxhlet and a standard procedure—based on the decomposition of lipids by concentrated sulfuric acid and the release of organic insecticides to the hexane layer—was used to determine chlorinated hydrocarbons. The quantitative determination of DDT, DDE, DDD and γ-HCH were conducted using gas chromatography with electron capture detection (GC-ECD). Chlorinated hydrocarbons were found in all tested samples. The contents of these compounds varied between all three species. Mean content of γ-HCH in B. edulis, I. badia and C. cibarius was: 2.60; 4.83; 7.52 µg kg^?1 of lipids, while the content of ΣDDT was: 57.02; 25.20; 127.10 µg kg^?1 of lipids, respectively. These results show that mushrooms from the north-eastern part of Poland can be used as potential bio-indicators of environmental contamination with chlorinated hydrocarbons. Moreover, the studied fungi could still be used as food due to the low levels of analyzed organochlorine compounds.     

Synthesis and antifungal activity of 2H-1,4-benzoxazin-3(4H)-one derivatives

A series of 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l) was easily synthesized by two-step process involving O-alkylation of 2-nitrophenols with methyl 2-bromoalkanoates and next “green” catalytic reductive cyclization of the obtained 2-nitro ester intermediates (3a-l). Further, 6,7-dibromo (5a-c) and N-acetyl (6) derivatives were prepared by bromination and acetylation of unsubstituted 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-c). The novel compounds (3a-l, 4d-l, 5a-c and 6) were fully characterized by spectroscopic methods (MS, ¹H and ¹³C NMR). 2-Alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l, 5a-c and 6) were screened for antifungal activity. Preliminary assays were performed using two methods: in vitro against seven phytopathogenic fungi—Botrytis cinerea, Phythophtora cactorum, Rhizoctonia solani, Phoma betae, Fusarium culmorum, Fusarium oxysporum and Alternaria alternata—and in vivo against barley powdery mildew Blumeria graminis. The tested compounds displayed moderate to good antifungal activity at high concentration (200 mg L^?1). The most potent compounds were 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a), 2-ethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)-one (4g) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6), which completely inhibited the mycelial growth of seven agricultural fungi at the concentration of 200 mg L^?1 in the in vitro tests. Moreover, 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6) were also screened for antifungal activity at concentrations of 100 mg L^?1 and 20 mg L^?1. In the concentration of 100 mg L^?1, the N-acetyl derivative (6) completely inhibited the growth of three strains of fungi (F. culmorum, P. cactorum and R. solani), while 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) completely inhibited only R. solani strain. At the concentration of 20 mg L^?1, compound 6 showed good activity only against P. cactorum strain (72%).     

Assessing participatory and multi-level characteristics of biodiversity and landscape protection legislation: the case of Poland

In this paper, we present a comprehensive framework for analysing formal rules regulating the involvement of various actors in protected areas decision-making over time and apply it to Poland. Based on the analysis of legal acts and policy documents, we suggest that since the democratic transition started in 1989, the governance of Polish protected areas has been increasingly multi-level and participatory. However, different designations indicate different levels of involvement by non-state actors, with Natura 2000 standing out from the traditional protected areas. Regarding governance issues, establishing and taking management decisions were characterised by the greatest changes in actors’ involvement. While participation of non-public actors is still limited mostly to information and consultation, the involvement of non-state public actors of various levels increased significantly. The paper highlights the importance of a systematic analysis of legal rules as a starting point for empirical investigation of the governance of protected areas.     

Do morphometric parameters and geological conditions determine chemistry of glacier surface ice? Spatial distribution of contaminants present in the surface ice of Spitsbergen glaciers (European Arctic)

The chemism of the glaciers is strongly determined by long-distance transport of chemical substances and their wet and dry deposition on the glacier surface. This paper concerns spatial distribution of metals, ions, and dissolved organic carbon, as well as the differentiation of physicochemical parameters (pH, electrical conductivity) determined in ice surface samples collected from four Arctic glaciers during the summer season in 2012. The studied glaciers represent three different morphological types: ground based (Blomlibreen and Scottbreen), tidewater which evolved to ground based (Renardbreen), and typical tidewater glacier (Recherchebreen). All of the glaciers are functioning as a glacial system and hence are subject to the same physical processes (melting, freezing) and the process of ice flowing resulting from the cross-impact force of gravity and topographic conditions. According to this hypothesis, the article discusses the correlation between morphometric parameters, changes in mass balance, geological characteristics of the glaciers and the spatial distribution of analytes on the surface of ice. A strong correlation (r = 0.63) is recorded between the aspect of glaciers and values of pH and ions, whereas dissolved organic carbon (DOC) depends on the minimum elevation of glaciers (r = 0.55) and most probably also on the development of the accumulation area. The obtained results suggest that although certain morphometric parameters largely determine the spatial distribution of analytes, also the geology of the bed of glaciers strongly affects the chemism of the surface ice of glaciers in the phase of strong recession.