TY - JOUR A1 - Goedecke, Caroline A1 - Mülow-Stollin, Ulrike A1 - Hering, S. A1 - Richter, Janine A1 - Piechotta, Christian A1 - Paul, Andrea A1 - Braun, Ulrike T1 - A first pilot study on the sorption of environmental pollutants on various microplastic materials JF - Journal of Environmental Analytical Chemistry N2 - With the drastic increase in plastic production, the input of plastic particles into the environment has become a recognised problem. Xenobiotics are able to sorb to polymer materials, and this process is further enhanced where they Encounter microplastics (plastic fragments <5 mm). In this work we studied the sorption of metformin, a type-2 diabetes drug, and difenoconazole, a fungicide, onto the virgin polymer materials polyamide (PA), polypropylene (PP), and polystyrene (PS). Additionally, PP was cryo-milled and PA was treated with acid to investigate the influence of an increase in surface area and chemical modification. The material properties were also studied by dynamic scanning calorimetry (DSC), gel permeation chromatography (GPC) and Fourier transform infrared spectroscopy (FTIR). Sorption experiments were performed on the basis of a full factorial design examining the effect of agitation, pH value, and salinity. Experimental results showed that difenoconazole sorbs readily to all microplastics, whereas the more polar analyte metformin did not show any affinity to the materials used. For difenoconazole the governing factor in all cases is agitation, while both pH and salinity exhibited only a slight influence. The modification of polymers leads to enhanced sorption, indicating that an increase in surface area (cryo-milled PP) or inner volume (acid-treated PA) strongly favours adsorption. Moreover, long-term experiments demonstrated that the time until equilibrium is reached depends strongly on the particle size. KW - Difenoconazole KW - Metformin KW - Plastic debris KW - Polymer KW - Dynamic scanning calorimetry PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-402393 DO - https://doi.org/10.4172/2380-2391.1000191 SN - 2380-2391 VL - 4 IS - 1 SP - Article 1000191, 1 EP - 8 PB - Omics International CY - Los Angeles AN - OPUS4-40239 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow-Stollin, Ulrike A1 - Piechotta, Christian A1 - Szewzyk, U. T1 - Investigation of transformation of triazole fungicides using model systems N2 - In order to provide nutrition for a growing world population pesticides are a necessary tool. Crop protection agents may be considered safe, if handled correctly. Nevertheless, they are subject to transformation processes and metabolization in the environment and technical installations. Transformation products (TP) and metabolites may be more harmful than the mother substance and thereby pose a threat to environmental and human health. With 19 % market share in 2014, triazole pesticides are the class of organic fungicides which are most commonly used in Germany. However, only little data is available concerning their TP and metabolites. In this study the fate of the triazole fungicides propiconazole and difenoconazole in soil and water using model reaction systems mimicking their pathway in the environment and the industrial water treatment is investigated. During application the substances may directly contaminate soil as well as surface waters. In these compartments, transformation by global irradiation needs to be considered. Due to their moderate mobility both pesticides may also end up in ground water from which drinking water is produced. Owing to the vigorous conditions during drinking water production the formation of a variety of technical TP can be expected. Additionally, for all compartments the degradation by bacteria is a factor which needs to be taken into account. For this survey, the potential for metabolization by model organisms is investigated. In this work degradation and transformation of the fungicides is monitored using quantitative target analysis. Major components in the reaction mixtures are identified by non-target analysis. GC-EI-MS-spectra, HR-MS-measurements, or the comparison with native standards are utilised for structural elucidation. For identification, products will be isolated and characterized by NMR. Toxicity assessment of these TP is essential to define threshold values in the environment. The model reaction systems will be presented and possible TP will be shown. T2 - ISEAC 39 CY - Hamburg, Germany DA - 19.07.2016 KW - Emerging pollutants KW - Electrochemistry KW - Fenton KW - Humic substances PY - 2016 AN - OPUS4-37016 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow-Stollin, Ulrike A1 - Piechotta, Christian A1 - Szewzyk, Ulrich T1 - Extensive study of the fate of triazole fungicides using model systems N2 - In order to provide nutrition for a growing world population pesticides are a necessary tool. Crop protection agents may be considered safe, if handled correctly. Nevertheless, they are subject to transformation processes and metabolisation in the environment and technical installations. Transformation products (TP) and metabolites may exhibit properties other than those of the mother substance. They can be more harmful and thereby pose a threat to environmental and human health. With 19 % market share in 2014, triazole pesticides are the class of organic fungicides which are most commonly used in Germany.1 However, only little data is available concerning their TP and metabolites. During this study the fate of the triazole fungicides propiconazole and difenoconazole in soil and water using model reaction systems mimicking their pathway in the environment and the industrial water treatment is investigated. During application the substances may directly contaminate soil as well as surface waters. Both pesticides are considered persistent in soil and very stable towards aqueous photolysis.2 In this case however, the role of natural organic matter has not yet been examined. Since both pesticides also show moderate mobility in soils they may end up in ground water from which drinking water is produced. During this process, waters are treated with chlorine agents, ozone, and energy-rich UV radiation. Owing to the vigorous conditions the formation of a variety of technical TP can be expected. Additionally, for all environmental compartments the degradation of the fungicides by bacteria is a factor which needs to be taken into account. For this survey, iron-oxidising bacteria of the leptothrix variety were chosen as model organisms. Their potential for the metabolisation of the analytes is investigated. In this work degradation and transformation of the fungicides is monitored using quantitative target analysis. Major components in the reaction mixtures are identified by non-target analysis. GC-EI-MS-spectra, HR-MS-measurements, or the comparison with native standards are utilised for structural elucidation. For identification, products will be isolated and characterised by NMR. Toxicity assessment of these TP is essential to define threshold values in the environment. The model reaction system considering the interaction with organic matter will be presented and possible TP will be shown. T2 - NonTarget 2016 CY - Ascona, Switzerland DA - 29.05.2016 KW - pesticides KW - fungicides KW - non-target KW - environment PY - 2016 AN - OPUS4-36384 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow, Ulrike A1 - Lehnik-Habrink, Petra A1 - Näther, Stephanie A1 - Piechotta, Christian T1 - Robustheitstest zur Untersuchung der optimalen Extraktionsbedingungen von organischen Schadstffen aus Boden T2 - 127. VDLUFA-Kongress 2015 T2 - 127. VDLUFA-Kongress 2015 CY - Göttingen DA - 2015-09-15 PY - 2015 AN - OPUS4-34508 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow, Ulrike A1 - Lehnik-Habrink, Petra A1 - Piechotta, Christian T1 - Transformation of triazole fungicides T2 - Environmental monitoring of biocides in Europa - specif strategies T2 - Environmental monitoring of biocides in Europa - specif strategies CY - Berlin DA - 2015-06-25 PY - 2015 AN - OPUS4-34511 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow, Ulrike A1 - Lehnik-Habrink, Petra A1 - Näther, Stephanie A1 - Piechotta, Christian T1 - Ruggedness study investigating extractability of PCB and OCP from soil T2 - 15th International Conference on Chemistry and the Environment (EuChems) T2 - 15th International Conference on Chemistry and the Environment (EuChems) CY - Leipzig DA - 2015-09-20 PY - 2015 AN - OPUS4-34513 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ye, S. A1 - Loll, B. A1 - Berger, A. A1 - Mülow, Ulrike A1 - Alings, C. A1 - Wahl, M. A1 - Koksch, B. T1 - Fluorine teams up with water to restore inhibitor activity to mutant BPTI JF - Chemical Science N2 - Introducing fluorine into molecules has a wide range of effects on their physicochemical properties, often desirable but in most cases unpredictable. The fluorine atom imparts the C–F bond with low polarizability and high polarity, and significantly affects the behavior of neighboring functional groups, in a covalent or noncovalent manner. Here, we report that fluorine, present in the form of a single fluoroalkyl amino acid side chain in the P1 position of the well-characterized serine-protease inhibitor BPTI, can fully restore inhibitor activity to a mutant that contains the corresponding hydrocarbon side chain at the same site. High resolution crystal structures were obtained for four BPTI variants in complex with bovine b-trypsin, revealing changes in the stoichiometry and dynamics of water molecules in the S1 subsite. These results demonstrate that the introduction of fluorine into a protein environment can result in “chemical complementation” that has a significantly favorable impact on protein–protein interactions. KW - serine-protease inhibitor KW - crystal structures KW - Peptide synthesis PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-358987 DO - https://doi.org/10.1039/C4SC03227F IS - 9 SP - 5246 EP - 5254 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-35898 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow, Ulrike A1 - Falkenhagen, Jana A1 - Neamtu, Mariana A1 - Piechotta, Christian T1 - Transformation des Herbizids Metamitron in Modellsystemen: Identifizierung von Produkten und Bestimmung von Abbauraten T2 - Anakon 2015 T2 - Anakon 2015 CY - Graz, Austria DA - 2015-03-23 PY - 2015 AN - OPUS4-33547 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow, Ulrike A1 - Piechotta, Christian T1 - Technical transformation of triazole fungicides T2 - 11. Lanenauer Wasserforum T2 - 11. Lanenauer Wasserforum CY - Langenau DA - 2015-11-08 PY - 2015 AN - OPUS4-35022 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mülow-Stollin, Ulrike A1 - Goedecke, Caroline A1 - Hering, S. A1 - Richter, Janine A1 - Piechotta, Christian A1 - Paul, Andrea A1 - Braun, Ulrike T1 - Investigation of sorption of environmental pollutants to virgin and aged microplastics N2 - Plastics are a diverse group of materials used in packaging, construction, medical applications, and many more. Due to their favourable properties their production and consequently their input into natural systems has increased drastically over the last decades. In the environment (photo-)oxidation processes and mechanical abrasion may then lead to the decomposition of the plastics. During this process microplastics (<5 mm) are formed. It has been noted that xenobiotics which are present in the same compartments can sorb to microplastics. However, knowledge on this topic is still limited. The work presented here aimed to investigate the sorption of the type 2 diabetes drug metformin and the triazole fungicide difenoconazole to virgin polyamide (PA), polypropylene (PP), and polystyrene (PS). Additionally, sorption to cryo-milled PP and acid-treated PA was studied. The latter was also characterised by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and dynamic scanning calorimetry (DSC). Sorption experiments were planned on the basis of a full factorial design with agitation, salinity, and pH value as parameters. Results of the study revealed that metformin did not show any affinity towards the tested materials. Difenoconazole however, sorbed to all microplastics. Data analysis showed that agitation is the main influencing factor, whereas salinity and the pH value held little to no significance. Mechanical and chemical treatment of the polymers led to enhanced sorption of difenoconazole. Long-term sorption experiments confirmed the hypothesis that particle size strongly influences the time until sorption-desorption equilibrium is reached. T2 - ANAKON 2017 CY - Tübingen, Germany DA - 03.04.2017 KW - Microplastic KW - Pollutants KW - Environment PY - 2017 AN - OPUS4-40255 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -