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).     

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.     

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.     

An Evaluation of Several In-Lake Restoration Techniques to Improve the Water Quality Problem (Eutrophication) of Saint-Augustin Lake,Quebec, Canada

Increasing phosphorus (P) content and decreasing water quality of Saint-Augustin Lake, Quebec City, Canada, has led to implementation of an Integrated Watershed Management Plan to restore the lake. As a part of the plan, the effects of different restoration techniques on lake water quality and biological community (i.e., biological compatibility) were assessed during an isolated water enclosure study and laboratory microcosm assay, respectively. The restoration techniques include: (i) coagulation of P by alum only (20 mg L⁻¹), (ii) active capping of sediments using a calcite layer of 10 cm, and (iii) a complete method involving both alum coagulation and calcite capping. The results showed that the total P (TP) was greatly decreased (76–95 %) by alum + calcite, followed by calcite only (59–84 %). Secchi depth was 106 % greater and chlorophyll a concentrations were declined by 19–78 % in the enclosure which received both alum and calcite. Results of the biological compatibility test showed that total phytoplankton biomass declined by 31 % in microcosms composed of alum + calcite. No significant (P > 0.05) toxic effect was found on the survival of Daphnia magna and Hyalella azteca in both alum only and alum + calcite microcosms. Although the alum + calcite technique impaired the survival of Chironomus riparius, the midge emergence was much higher compared to alum only and control. Overall, the alum + calcite application was effective in controlling P release from sediment and lowering water column P concentrations, and thus improving the water quality and aquatic life of Saint-Augustin Lake. However, the TP concentrations are still higher than the critical limit (20 μg L⁻¹) for aquatic life and the water column remained in the eutrophic state even after treatment. Increased TP concentrations, to higher than ambient levels of the lake, in the water column of all four enclosures, due to bioturbation artefact triggered by the platform installation, likely cause insufficient dosages of alum and/or calcite applied and reduced their effectiveness.     

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.     

A system coupling hybrid biological method with UV/O<Subscript>3</Subscript> oxidation and membrane separation for treatment and reuse of industrial laundry wastewater

The possibilities of application of a three-step system combining hybrid biological treatment followed by advanced UV/O₃ oxidation with in situ generated O₃ and membrane separation (ultrafiltration (UF) and nanofiltration (NF)) to treat and reuse the wastewater from an industrial laundry are presented. By the application of a hybrid moving bed biofilm reactor (HMBBR), the total organic carbon concentration was reduced for about 90 %. However, since the HMBBR effluent still contained organic contaminants as well as high concentrations of inorganic ions and exhibited significant turbidity (8.2 NTU), its further treatment before a possible reuse in the laundry was necessary. The UV/O₃ pretreatment prior to UF was found to be an efficient method of the membrane fouling alleviation. During UF, the turbidity of wastewater was reduced below 0.3 NTU. To remove the inorganic salts, the UF permeate was further treated during NF. The NF permeate exhibited very low conductivity (27–75 μS/cm) and contained only small amounts of Ca²⁺ and Mg²⁺; thus ,it could be reused at any stage of the laundry process.     

Adaptation strategies and referencing trial of Scots and black pine populations subjected to heavy metal pollution

The impact of industrial heavy metal pollution on Scots pine (Pinus sylvestris L.) and black pine (Pinus nigra Arn.) populations was investigated. Sampled pine stands, which were located in Upper Silesia (southern Poland) in an area strongly polluted by heavy metals, consisted of resistant and sensitive trees. To evaluate the adaptation process, genetic structure and diversity was tested using isozyme analysis. Higher levels of Zn, Pb, Cd and Cu were detected in needles of sensitive trees compared with resistant ones. With respect to morphology, Scots pines were more distinctly impaired than black pines. Although black pines had lower heavy metal concentrations, levels in 1-year-old needles, other than Cu, significantly exceeded “reference plant” values (Markert 1994). In both species, resistant trees demonstrated a lower degree of genetic variation than metal-sensitive trees with respect to some enzyme loci (SHDH A, PGI, PGM, MDH C and DIA). This observation was corroborated in sensitive trees by the smaller number of identified alleles and alleles per locus, absence of private alleles and significant excess of homozygotes in relation to expected Hardy–Weinberg equilibrium values. Assuming that only resistant trees of both species survive under conditions of prolonged soil contamination, the observed genetic structure implies that remaining populations will be depleted of some alleles of unknown adaptive value to future selection pressures. Genetic changes induced by heavy metals suggest an important role for specific enzymes—FEST, SHDH A and B, GOT B and PGI—in the adaptation process. Our results may serve as a basis for selection and propagation of individuals appropriate for re-cultivation of areas chemically degraded by industrial activity.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in cord blood from women in Poland

The purpose of this study was to assess human exposure in the prenatal period to selected PBDEs (BDE-47, BDE-99, BDE-153) and PCBs (CB-77, CB-101, CB-118, CB-126, CB-138, CB-153, CB-170, CB-180) basing on the analysis of these compounds in cord blood. The experimental material consisted of 89 cord blood samples taken from women resident in Warsaw and its vicinity. In over 90% of all tested samples the presence of congeners CB-153, CB-138, CB-180 and BDE-47 was identified. The least frequently found were CB-126 and BDE-153, which were present at relatively low concentration levels. Among all analysed PCBs, the highest average concentrations were found in the case of congeners CB-138 (11.8 ng/g of fat) and CB-153 (43.4 ng/g of fat), whereas the lowest was in the case of CB-170 (0.4 ng/g of fat) and CB-126 (0.1 ng/g of fat). In the case of PBDEs the greatest share in the total concentration was that of the congeners BDE-47 and BDE-99, whereas the smallest share was that of the higher brominated congener BDE-153. These results suggest that human exposure to the examined compounds begins already in the period of intrauterine life. The comparison of our own results with the findings of other authors indicates that the PCBs and PBDEs levels in cord blood of women living in Poland do not differ from the respective concentrations in cord blood of other female inhabitants of Europe.     

LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09?µg L^?1 to 100?µg L^?1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85–109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.     

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%).