Formation and Structure of Metal Complexes with the Fungicides Tebuconazole and Propiconazole

Abstract

Divalent copper and zinc complexes with metal:azole ratio 1∶2 were readily formed at room temperature with the fungicides tebuconazole and propiconazole. The structure of copper and zinc tebuconazole acetate and zinc cis‐propiconazole chloride were examined by X‐ray crystallography. In copper tebuconazole acetate, the copper atom lies on a crystallographic inversion center and is coordinated to two triazole and two acetate ligands in a trans arrangement. The two binding tebuconazole N atoms and two close binding acetate O atoms form a square plane. The two remaining acetate O atoms have more distant interactions, thus forming an elongated octahedron around the copper atom. The coordination geometry of zinc tebuconazole acetate is tetrahedral and the metal is bound to two triazole and two acetate ligands. The geometry is distorted from regular owing to the size of the tebuconazole ligands. The butyl chains are less folded than for the copper tebuconazole complex, resulting in a more extended molecule. The coordination geometry of zinc cis‐propiconazole chloride is also tetrahedral with the metal atom bonded to two triazole and two chloride ligands.     

Effect of phosphatase/transglutaminase treatment on molar mass distribution and techno-functional properties of sodium caseinate

Sodium caseinate was enzymatically dephosphorylated by alkaline or acid phosphatase prior to incubation with microbial transglutaminase. It was demonstrated that a higher degree of protein cross-linking by transglutaminase was achieved in dephosphorylated sodium caseinate than in non-dephosphorylated sodium caseinate. During transglutaminase treatment, about 70% protein polymers >200.000 g/mol were produced from untreated sodium caseinate, but about 90% protein polymers >200.000 g/mol from dephosphorylated sodium caseinate. Phosphatase/transglutaminase-treated sodium caseinate exhibited techno-functional properties similar to transglutaminase-treated sodium caseinate, but performed improved interfacial stabilisation behaviour as well as higher viscosity.     

Correlation of spatially resolved photoluminescence and viscoelastic mechanical properties of encapsulating EVA in differently aged PV modules

The photoluminescence of ethylene vinyl acetate (EVA) in aged photovoltaic modules shows specific spatial patterns on the scale of the cells in the module that depend on the aging conditions. It is the aim of this work to investigate the correlation of these photoluminescence patterns to the viscoelastic mechanical properties of the encapsulating EVA. For this, the degradation under various conditions of two specimen sets of polycrystalline silicon photovoltaic mini‐modules, comprising EVA as encapsulating polymer, is investigated using spatially resolved, ultraviolet‐excited photoluminescence. Samples of the encapsulation EVA are systematically extracted from the modules for spatially resolved dynamic mechanical characterization. A correlation between the spatial distribution of the photoluminescence intensity and the values of storage modulus and loss factor of the EVA is found. An increase in the values for storage modulus and a decrease of the loss factor of the EVA from the edge of the cell towards the center are observed for all samples. We conclude that diffusion‐limited oxidation must be considered for aging studies of the encapsulation EVA and that photoluminescence detection can reveal the scale on which such diffusion processes occur. Copyright © 2016 John Wiley & Sons, Ltd.     

Evaluation of contaminant removal of reverse osmosis and advanced oxidation in full-scale operation by combining passive sampling with chemical analysis and bioanalytical tools

Advanced water treatment of secondary treated effluent requires stringent quality control to achieve a water quality suitable for augmenting drinking water supplies. The removal of micropollutants such as pesticides, industrial chemicals, endocrine disrupting chemicals (EDC), pharmaceuticals, and personal care products (PPCP) is paramount. As the concentrations of individual contaminants are typically low, frequent analytical screening is both laborious and costly. We propose and validate an approach for continuous monitoring by applying passive sampling with Empore disks in vessels that were designed to slow down the water flow, and thus uptake kinetics, and ensure that the uptake is only marginally dependent on the chemicals' physicochemical properties over a relatively narrow molecular size range. This design not only assured integrative sampling over 27 days for a broad range of chemicals but also permitted the use of a suite of bioanalytical tools as sum parameters, representative of mixtures of chemicals with a common mode of toxic action. Bioassays proved to be more sensitive than chemical analysis to assess the removal of organic micropollutants by reverse osmosis, followed by UV/H?O? treatment, as many individual compounds fell below the quantification limit of chemical analysis, yet still contributed to the observed mixture toxicity. Nonetheless in several cases, the responses in the bioassays were also below their quantification limits and therefore only three bioassays were evaluated here, representing nonspecific toxicity and two specific end points for estrogenicity and photosynthesis inhibition. Chemical analytical techniques were able to quantify 32 pesticides, 62 PCPPs, and 12 EDCs in reverse osmosis concentrate. However, these chemicals could explain only 1% of the nonspecific toxicity in the Microtox assay in the reverse osmosis concentrate and 0.0025% in the treated water. Likewise only 1% of the estrogenic effect in the E-SCREEN could be explained by the quantified EDCs after reverse osmosis. In comparison, >50% of the estrogenic effect can typically be explained in sewage. Herbicidal activity could be fully explained by chemical analysis as the sampling period coincided with an illegal discharge and two herbicides dominated the mixture effect. The mass balance of the reverse osmosis process matched theoretical expectations for both chemical analysis and bioanalytical tools. Overall the investigated treatment train removed >97% estrogenicity, >99% herbicidal activity, and >96% baseline toxicity, confirming the suitability of the treatment train for polishing water for indirect potable reuse. The product water was indistinguishable from local tap water in all three bioassays. This study demonstrates the suitability and robustness of passive sampling linked with bioanalytical tools for semicontinuous monitoring of advanced water treatment with respect to micropollutant removal.     

Mixed oxide coatings for optics

Material mixtures offer new possibilities for synthesizing coating materials with tailored optical and mechanical properties. We present experimental results on mixtures of HfO2, ZrO2, and Al2O3, pursuing applications in UV coating technology, while the mixtures are prepared by magnetron sputtering, ion beam sputtering, plasma ion-assisted deposition (PIAD), and electron beam evaporation without assistance. The properties investigated include the refractive index, optical gap, thermal shift, and mechanical stress. The first high reflectors for UV applications have been deposited by PIAD.     

Charakterisierung der Dispersionsgüte von Carbon Nanotubes in Polymer‐Nanokompositen

A practical overview of possibilities and limits to characterize the state of dispersion of carbon nanotubes (CNT) in polymer based nanocomposites is given. The most important and widely available methods are discussed with practical employment in mind. One focus is the quantitative characterization of the state of dispersion in solid samples using microscopy techniques such as optical microscopy or transmission electron microscopy. For dispersions of CNTs in aqueous media, solvents or monomers a sedimentation analysis is presented. This way dispersability and dispersion state of CNTs can be assessed. Indirect methods such as electrical conductivity measurements and rheological tests, dynamic differential scanning calorimetry and mechanical test are discussed.     

Scalable Production of Nanographene and Doping via Nondestructive Covalent Functionalization

A new method for top‐down, one‐pot, gram‐scale production of high quality nanographene by incubating graphite in a dilute sodium hypochlorite solution at only 40 °C is reported here. The produced sheets have only 4 at% oxygen content, comparable with nanographene grown by chemical vapor deposition. The nanographene sheets are covalently functionalized using a nondestructive nitrene [2+1] cycloaddition reaction that preserves their π‐conjugated system. Statistical analyses of Raman spectroscopy and X‐ray photoelectron spectroscopy indicate a low number of sp³ carbon atoms on the order of 2% before and 4% after covalent functionalization. The nanographene sheets are significantly more conductive than conventionally prepared nanographene oxide, and conductivity further increases after covalent functionalization. The observed doping effects and theoretical studies suggest sp² hybridization for the carbon atoms involved in the [2+1] cycloaddition reaction leading to preservation of the π‐conjugated system and enhancing conductivity via n‐type doping through the bridging N‐atom. These methods are easily scalable, which opens the door to a mild and efficient process to produce high quality nanographenes and covalently functionalize them while retaining or improving their physicochemical properties.     

Mercury exposure in female artisanal small-scale gold miners (ASGM) in Mongolia: An analysis of human biomonitoring (HBM) data from 2008

Background

Many poor in developing countries have turned to artisanal small-scale gold mining (ASGM) in an attempt to improve their situation. However, the mercury used to extract gold from ore is discharged in vaporized form into the environment, where it poses a hazard for human health.

Methods

As part of an environmental epidemiological study in Mongolia—to evaluate the burden of environmental mercury contamination—urine, blood and hair samples were collected from residents of areas with or without mercury contamination. A total of 200 blood, urine and hair samples were analyzed for mercury and divided into three subgroups according to mercury content: (1) occupational exposure (high/medium); (2) environmental exposure (low); and (3) no exposure. Internal mercury distributions of the subgroups were compared using the Kruskal-Wallis and Mann-Whitney U-test. The Chi-square test and likelihood ratio proportion were used to compare the findings with threshold limits.

Results

The highest values and greatest differences were seen in the urine samples (p < 0.001, Kruskal-Wallis). The occupational group showing the highest exposure with a median mercury level of 4.36 μg/l (control group: 0.10 μg/l, p < 0.001), 7.18 μg/g creatinine and 12 results above the threshold limit HBM I (Human Biomonitoring I). Even participants from the low-exposure subgroup showed elevated mercury levels (median 2.88 μg/l urine and 2.98 μg/g creatinine, p < 0.001), with 10 individuals above the HBM I threshold limits.

Discussion

The body burden resulting from the use of mercury in artisanal gold mining is high not only in the miners themselves, an increased mercury hazard was also found for inhabitants of mining areas who were not actively involved in mining. Public health support measures are urgently needed to alleviate the situation.     

Bioanalytical tools for the evaluation of organic micropollutants during sewage treatment, water recycling and drinking water generation

A bioanalytical test battery was used for monitoring organic micropollutants across an indirect potable reuse scheme testing sites across the complete water cycle from sewage to drinking water to assess the efficacy of different treatment barriers. The indirect potable reuse scheme consists of seven treatment barriers: (1) source control, (2) wastewater treatment plant, (3) microfiltration, (4) reverse osmosis, (5) advanced oxidation, (6) natural environment in a reservoir and (7) drinking water treatment plant. Bioanalytical results provide complementary information to chemical analysis on the sum of micropollutants acting together in mixtures. Six endpoints targeting the groups of chemicals with modes of toxic action of particular relevance for human and environmental health were included in the evaluation: genotoxicity, estrogenicity (endocrine disruption), neurotoxicity, phytotoxicity, dioxin-like activity and non-specific cell toxicity. The toxicity of water samples was expressed as toxic equivalent concentrations (TEQ), a measure that translates the effect of the mixtures of unknown and potentially unidentified chemicals in a water sample to the effect that a known reference compound would cause. For each bioassay a different representative reference compound was selected. In this study, the TEQ concept was applied for the first time to the umuC test indicative of genotoxicity using 4-nitroquinoline as the reference compound for direct genotoxicity and benzo[a]pyrene for genotoxicity after metabolic activation.The TEQ were observed to decrease across the seven treatment barriers in all six selected bioassays. Each bioassay showed a differentiated picture representative for a different group of chemicals and their mixture effect. The TEQ of the samples across the seven barriers were in the same order of magnitude as seen during previous individual studies in wastewater and advanced water treatment plants and reservoirs. For the first time a benchmarking was performed that allows direct comparison of different treatment technologies and covers several orders of magnitude of TEQ from highly contaminated sewage to drinking water with TEQ close or below the limit of detection. Detection limits of the bioassays were decreased in comparison to earlier studies by optimizing sample preparation and test protocols, and were comparable to or lower than the quantification limits of the routine chemical analysis, which allowed monitoring of the presence and removal of micropollutants post Barrier 2 and in drinking water. The results obtained by bioanalytical tools were reproducible, robust and consistent with previous studies assessing the effectiveness of the wastewater and advanced water treatment plants. The results of this study indicate that bioanalytical results expressed as TEQ are useful to assess removal efficiency of micropollutants throughout all treatment steps of water recycling.