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Eingeladener Vortrag
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Gegenstand der vorzustellenden Arbeiten ist die Prüfung der Umwelt-beständigkeit und -verträglichkeit von Materialien und Produkten hinsichtlich der Emission von potenziellen Schadstoffen in die Umwelt. Hierzu werden chemisch-physikalische Einflüsse (Bewitterung) und mikrobielle Beanspruchungen an Modellmaterialien evaluiert. So werden die Freisetzungsraten von Schadstoffen in Abhängigkeit der Beanspruchung beschrieben. Als Modellmaterialien kommen die Polymere Polystyrol (PS) und Polypropylen (PP) zum Einsatz. Synergistische Effekte der Bewitterungsparameter und der mikrobiologischen Beanspruchung sollen dabei ebenso betrachtet werden, wie die gezielte Alterung. Auch findet eine Beschreibung des Verhaltens der ausgetragenen Schadstoffe in den Umweltkompartimenten Boden oder Wasser statt. Hier sind mit Hilfe der zu entwickelnden Screening- und non-Target-Analyseverfahren die Transformation und der Metabolismus durch Mikroorganismen zu beschreiben. Aus den Ergebnissen sollen Korrelationen zwischen den künstlichen Alterungsverfahren und realen Szenarien abgeleitet werden.
A method for the determination of the novel brominated flame retardant tetrabromobisphenol A bis(2,3-dibromopropylether), 1,1'-(isopropylidene)bis[3,5-dibromo-4-(2,3-dibromo-propoxy)-benzene] (TBBPA-dbpe), was developed. Technical TBBPA-dbpe was purified and the results of a thorough physical characterisation are reported. The application of APCI-MS is discussed and the fragmentation patterns are described. Quantification of TBBPA-dbpe was done by HPLC-DAD using external calibration. The validation of the method was accomplished using sediment and sewage sludge samples spiked with defined amounts of authentic TBBPA-dbpe. The average recovery rates of TBBPA-dbpe from spiked samples ranged from 35 to 91% (sediment) and from 57 to 98% (sewage sludge) depending on the respective extraction method. Pressurised fluid extraction (PFE) and fluidised bed extraction were superior to classical Soxhlet and sonication procedures and yielded recovery rates between 90 and 98% with relative standard deviations of 2%. The limits of detection (DTC), identification (ID) and determination (DTM) using HPLC-DAD were 10, 21 and 30 ng g-1 in sediment and 22, 44 and 72 ng g-1 in sewage sludge, respectively.
For the first time, µ-X-ray fluorescence (µ-XRF) mapping combined with fluorine K-edge µ-X-ray absorption near-edge structure (µ-XANES) spectroscopy was applied to depict per- and polyfluoroalkyl substances (PFAS) contamination and inorganic fluoride in samples concentrations down to 100 µg/kg fluoride. To demonstrate the matrix tolerance of the method, several PFAS contaminated soil and sludge samples as well as selected consumer product samples (textiles, food contact paper and permanent baking sheet) were investigated. µ-XRF mapping allows for a unique element-specific visualisation at the sample surface and enables localisation of fluorine containing compounds to a depth of 1 µm. Manually selected fluorine rich spots were subsequently analysed via fluorine K-edge µ-XANES spectroscopy. To support spectral interpretation with respect to inorganic and organic chemical distribution and compound class determination, linear combination (LC) fitting was applied to all recorded µ-XANES spectra. Complementarily, solvent extracts of all samples were target-analysed via LC-MS/MS spectrometry. The detected PFAS sum values range from 20 to 1136 µg/kg dry weight (dw). All environmentally exposed samples revealed higher concentration of PFAS with a chain length >C8 (e.g. 580 µg/kg dw PFOS for Soil1), whereas the consumer product samples showed a more uniform distribution with regard to chain lengths from C4 to C8. Independent from quantified PFAS amounts via target analysis, µ-XRF mapping combined with µ-XANES spectroscopy was successfully applied to detect both point-specific concentration maxima and evenly distributed surface coatings of fluorinated organic contaminants in the corresponding samples.
Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted
and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but
consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values
of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations.
LAS-Kalibrierstandards
(2007)
Arsenolipids represent a relevant step in the biosynthesis of organoarsenicals from inorganic arsenic compounds. Their fate after human consumption is still uncertain.
By means of a HPLC-ICP-MS/ESI-Q-TOF-MS method, 16 lipid soluble arsenic compounds, including seven formerly unknown organoarsenicals, have been identified in commercial herring fillet.
The structural assignment was done by exact mass and high resolution MS/MS data. This is the first identification of arsenolipids in herring (Clupea harengus). They contribute with (3.6±0.2) mg kg-1 arsenic to 62.3% of the total arsenic content of (5.7±0.3) mg of arsenic per kg dry mass. Current studies indicate that a metabolization by humans to cancerous dimethylarsinic acid is very likely. The presented results are highly relevant as herring is a very popular food fish species in Europe. Moreover, the screening of different fish species revealed that arsenolipids are more widespread than previously assumed.
A procedure has been developed for the determination of arsenobetaine in fish matrix by HPLC–ESI-MS/MS. Hereby (trimethylarsonium)-1,2-13C-acetate (arsenobetaine) is used as internal calibration standard. Arsenobetaine was determined in a fish material (Sea Bass) with an expanded uncertainty of 3.8%.
The influence of fire accelerants on the fire behavior during living room fires was experimentally investigated by performing 5 different room fire scenarios. During the tests flre-technological quantities were determined as well as chemical-analytical studies were carried out. The focus was on the detection of smoke gases and the proof of used fire accelerants. The evaluation of traceable fire accelerants and the reconstruction of the fire development are based on a precise Chemical analysis of the combustion products.
In this work an innovative methodology was developed to combine available analyticai techniques to draw conclusions from solid, liquid and gaseous fire residues about the fire process. Each ofthe fire rooms was equipped with the same living room inventory. The location and amount of fire accelerant (a mixture of diesel/gasoline) differed in 4 of 5 tests. Orte room fire experiment was carried out without fire accelerant.
The following fire technological characteristics were determined during the room fire experiments: mass loss (of the complete room), temperatures (at several locations in the room), heat release and smoke gas emission (measured at three different locations: in the chimney, in the fire room and at the door opening).
While the smoke gases were analysed by using Fourier Transform Infrared spectroscopy, the fire residues and swipe samples (particles) were examined by Headspace-Solid Phase Microextraction-
Gaschromatography-Mass spectrometry. These procedures make it possible to detect low concentrations of volatile components of the fire accelerants. The Chemical analyticai results of the fire accelerant detection are presented.
The reaction pathways of amino acids and reducing sugars are now fully understood. The focus in the last few years, however, has turned to the reaction of peptides and proteins with reducing sugars. We have investigated the reaction of γ-aminobutanoic acid, the heptapeptide Nα-Acetyl-Lys-Lys-β-Ala-Lys-β-Ala-Lys-Gly, and the model protein β-casein in Maillard reactions with 1-13C arabinose. Characterization of 13C-labeled acetic acid and norfuraneol by gas chromatographymass spectrometry and nuclear magnetic resonance revealed new formation pathways. The results demonstrate significant differences in the labeling pattern of the products depending on the amine used, indicating different formation pathways of acetic acid and norfuraneol.
Hands-off linear interaction energy approach to binding mode and affinity estimation of estrogens
(2013)
With this work we target the development of a predictictive model for the identification of small molecules which bind to the estrogen receptor alpha and, thus, may act as endocrine disruptors. We propose a combined thermodynamic approach for the estimation of preferential binding modes along with corresponding free energy differences using a linear interaction energy (LIE) ansatz. The LIE model is extended by a Monte Carlo approach for the computation of conformational entropies as recently developed by our group. Incorporating the entropy contribution substantially increased the correlation with experimental affinity values. Both squared coefficients for the fitted data as well as the more meaningful leave-one-out cross-validation of predicted energies were elevated up to rFit2 = 0.87 and qLOO2 = 0.82, respectively. All calculations have been performed on a set of 31 highly diverse ligands regarding their structural properties and affinities to the estrogen receptor alpha. Comparison of predicted ligand orientations with crystallographic data retrieved from the Protein database pdb.org revealed remarkable binding mode predictions.
Hyphenated techniques for the analysis of linear alkylbenzenesulfonates in technical formulation
(2010)
The derivatization of organoarsenic compounds by different reagents like thioglycolates or dithiols and the subsequent analysis by GC–MS as a molecular specific technique was investigated and described. The possible derivatization reagents methyl- and ethylthioglycolate (TGM and TGE), 1,3-propane- and 1,5-pentanedithiol (PDT and PeDT), which transfer the polar and nonvolatile analytes dimethylarsenate (DMA), monomethylarsonate (MMA), arsenite and arsenate into volatile compounds, were evaluated. The application for real samples like fish material was also studied.
In addition the gas chromatographic separation and resolution was optimized and experiments were carried out to determine the highest derivatization rates. Derivatization reagents were evaluated in terms of quantity and stability of the formed chemical species.
All derivatization products were characterized by mass spectrometry in order to identify the separated arsenic species.
The most efficient conversion of DMA and MMA was observed by using ethylthioglycolate as derivatization agent. Finally, the derivatization procedure and the GC–MS-method were validated to determine linearity, precision, selectivity, analytical limiting values and recoveries. For the proposed method a limit of detection (LOD) of 5.8 pg for DMA and 14.0 pg for MMA was found. The accuracy was established by comparing the mean value measured for DMA in the certified reference material BCR-627 (tuna fish) with the certified one.
MMA was not quantified in marine samples due to its low content. In shrimp samples DMA was not detectable. For codfish a DMA-content of 0.20±0.004 mg kg-1, for 'Surströmming' an amount of 0.38±0.02 mg kg-1 and for herring, which showed the highest amount of DMA, a content of 1.15±0.03 mg kg-1 was determined.
The chemical analysis of fire debris represents a crucial part in fire investigations to determine the cause of a fire. A headspace solid-phase microextraction (HS-SPME) procedure for the detection of ignitable liquids in fire debris using a fiber coated with a mixture of three different sorbent materials (Divinylbenzene/Carboxen/Polydimethylsiloxane, DVB/CAR/PDMS) is described. Gasoline and diesel fuel were spiked upon a preburnt matrix (wood charcoal), extracted and concentrated with HS-SPME and then analyzed with gas chromatography/mass spectrometry (GC/MS). The experimental conditions—extraction temperature, incubation and exposure time—were optimized. To assess the applicability of the method, fire debris samples were prepared in the smoke density chamber (SDC) and a controlled-atmosphere cone calorimeter. The developed methods were successfully applied to burnt particleboard and carpet samples. The results demonstrate that the procedure that has been developed here is suitable for detecting these ignitable liquids in highly burnt debris.
The present study was focused on the determination and identification of arsenic species in methanolic extracts of cod liver. Arsenic species were fractionated and the fractions analysed by RP-HPLC-ICP-MS coupled with ESI-Q-TOF-MS. The total concentration of arsenic in the fresh cod liver was analysed by ICP-MS to be 1.53 ± 0.02 mg As kg-1 w.w. and the extraction recovery was ca. 100% and the column recovery >93%. Besides polar inorganic and methylated arsenic species (>70%) more hydrophobic arsenic-containing fatty acids and hydrocarbons occurred. Based on the mass spectrometric data proposals for molecular structures were elaborated for 20 of the organic As species included 10 arsenic-containing fatty acids (AsFA) and an arsenic-containing hydrocarbon (AsHC) mentioned for the first time in fresh cod liver. Arsenobetaine was found as main water-soluble arsenic compound in cod liver followed by higher molecular mass arsenic-containing fatty acids and hydrocarbons.
Säulenperkolationsversuche werden u.a. zur Ermittlung der Freisetzung von Schadstoffen aus Böden durchgeführt. Im Entwurf der novellierten Bundesboden-schutz- und Altlastenverordnung ist neben Schüttelverfahren (DIN 19527 und 19529) ein Säulenperkolationsverfahren (DIN 19528) zur Eluatgewinnung aus Böden festgeschrieben. Mit diesem Verfahren kann im Vergleich zu den Schüttelversuchen auch der zeitliche Verlauf der Schadstofffreisetzung erfasst und bewertet werden. Allerdings sind die Verfahren bisher nur für anorganische Stoffe und wenige prioritäre organische Schadstoffe validiert worden (PAK, MKW, PCB, Phenole).
Aber auch Schadstoffe wie perfluorierte Tenside (PFT), die z.B. für die Veredlung von Papier, Textilien und Haushaltsgeräten eingesetzt werden oder Biozide, mit denen Bauprodukte zum Schutz vor mikrobiellem Befall ausgerüstet werden (z.B. Fassadenbeschichtungen und Holz), geraten auf Grund ihrer gesundheits- und umwelt-schädlichen Eigenschaften immer stärker in die Diskussion.
Estrogens are endocrine disrupting chemicals and of high concerns due to demonstrated harmful effects on the environment and low effect levels. For monitoring and risk assessment, several estrogens were included in the "watch list" of the EU Water Framework Directive which sets very low environmental quality standard (EQS) levels for Estrone (E1) and 17β-Estradiol (E2) of 0.4 ng L−1 and for 17α-Ethinylestradiol (EE2) of 0.035 ng L−1 requiring sensitive detection methods, as well as extensive sample preparation. A sensitive, derivatization-free, isotope dilution calibration HPLC-MS/MS method for a panel of 5 selected estrogens (including the 3 estrogens of the EU WFD watchlist), and a procedure for the reproducible preparation of a representative whole water matrix including mineral water, humic acids and solid particulate matter are presented. These are used in a diligent comparison of classical solid phase extraction (SPE) on hydrophilic-lipophilic balanced (HLB) phase to SPE on an estrogen-specific molecularly imprinted polymer phase (MISPE) for ultra-trace levels of the analytes (1–10 ng L−1). Additionally, a two-step procedure combining HLB SPE disks followed by MISPE is evaluated. The tow-step procedure provides superior enrichment, matrix removal and sample throughput while maintaining comparable recovery rates to simple cartridge SPE. Estimated method quantification limits (MQLs) range from 0.109–0.184 ng L−1 and thus meet EQS-levels for E1 and E2, but not EE2. The representative whole water matrix provides a reproducible comparison of sample preparation methods and lays the foundation for a certified reference material for estrogen analysis. The presented method will serve as the basis for an extended validation study to assess its use for estrogen monitoring in the environment.
Warfarin ist seit den 1950er Jahren einer der bekanntesten Gerinnungshemmer. Beim Menschen wird es bis heute zur Vorbeugung von Thrombose und der Behandlung von Vorhofflimmern und Arrhythmie eingesetzt. Doch schon einige Jahre vor der FDA Zulassung (U. S. Food and Drug Administration) als Medikament wurde es zur Bekämpfung von Nagetieren eingesetzt. Bis heute wurde es nur teilweise durch weitaus wirksamere antikoagulante Rodentizide (ARs) der zweiten Generation, sogenannte Superwarfarine, ersetzt. In der Fachliteratur finden sich zahlreiche Beispiele für sekundäre und tertiäre Vergiftung mit ARs bei Wildtieren und anderen Nichtzieltieren. Bisher ist relativ wenig über die Bioakkumulation, Persistenz und Toxizität von ARs und deren Transformationsprodukten (TPs) in der terrestrischen und aquatischen Umwelt, sowie der Nahrungskette bekannt.
Um Einblicke in mögliche Transformations- und Abbauprozesse von Warfarin unter umweltrelevanten Bedingungen zu erhalten und um diese Einflüsse zu simulieren, wurde hierzu eine elektrochemische Reaktorzelle in Kopplung mit einem Massenspektrometer verwendet. So können mögliche Phase-I-Metabolite und sogenannte „oxidation products“ vorausgesagt werden. Hinsichtlich des Verhaltens während der Wasseraufbereitung in Kläranlagen wurden technisch relevante Prozesse wie Chlorung, UV-Bestrahlung und Ozonung in Modellen simuliert, um hier potenzielle Abbauwege und -prozesse aufzuklären. Gebildete Transformationsprodukte wurden daher mittels unterschiedlicher chromatografischer Verfahren getrennt und massenspektrometrisch identifiziert, charakterisiert und verglichen.
Monitoring programs should generate high-quality data on the concentrations of substances and other pollutants in the aquatic environment to enable reliable risk assessment. Furthermore, the need for comparability over space and time is critical for analysis of trends and evaluation of restoration of natural environment. Additionally, research work and exercises at the European level have highlighted that reliable measurements of estrogenic substances at the PNEC level are still challenging to achieve.
The project EDC-WFD Metrology for monitoring endocrine disrupting compounds under the EU Water Framework Directive aims to develop traceable analytical methods for determining endocrine disrupting compounds and their effects, with a specific focus on three estrogens of the first watch list (17-beta-estradiol (17βE2), 17-alpha-ethinylestradiol (EE2), and estrone (E1)). Estrogens 17-alpha-estradiol (17E2) and estriol (E3) will be included to demonstrate the reliability of the developed methods and to support the requirements of Directive 2013/39/EC, Directive 2009/90/EC and Commission Implementation Decision (EU) 2018/840, hence improving the comparability and compatibility of measurement results within Europe. During the EDC-WFD project four selected effect-based methods (EBM) will be deeply investigated in order to improve their rationale use and their support in water quality assessment. In particular, the EBM sensitivity, specificity and accuracy on reference materials with single or mixture solutions of the five substances at a concentration of EQS values will be explored.
This contribution will present the objectives and methods applied within the EDC-WFD project.
Natural and synthetic estrogens are key endocrine-disrupting chemicals. Despite occurring at ultra-trace levels (below ng L-1), it is believed that they are contributing to an increase in feminized fish and other endocrine disruptive effects, and hence, their inclusion in the Watch list was not unexpected. One of the main sources ofestrogens to surface waters is wastewater effluent. Once in surface waters, they can partition into different compartments, i.e., water and suspended particulate matter. For this reason, there is an urgent need for a methodology to monitor estrogen levels below the environmental quality standards (EQS) set by the Water Framework Directive requirements.
In this study, a precise and accurate gas chromatography-mass spectrometry method (GC-MS/MS) for the analysis of estrone (E1), 17β-estradiol (17β-E2), 17α-estradiol (17α- E2), 17-alpha-ethinylestradiol (EE2), and estriol (E3) in whole water samples with ng L-1 limit of quantification (LOQ) was developed and validated in accordance with CEN/TS 16800:2020 guidelines.
Arsenolipids (AsL) of the type arsenic-containing fatty acids (AsFA) and hydrocarbons (AsHC) are known to occur in seafood and their identification is today a challenge due to the need of data for toxicological assessment. The aim of this investigation was to enhance the data concerning AsL in commercial canned cod liver. Therefore, the present study focuses on the quantification and identification of AsL by LC–ICP-MS combined with ESI-MS. The molecular structure of 17 AsL was elucidated on the basis of their exact mass and their product ion spectra and two new AsFA tentatively identified. The total arsenic concentration in four different canned cod liver analyzed by ICP-MS ranged from 2.6 to 5.5 mg As/kg with an extraction recovery of 98%. The AsL detected by RP-IPC–MS comprise 58–95% of the total arsenic content, indicating that AsL are a major class of arsenic in canned cod liver. Much of the AsL detected in the canned cod liver extracts are, however, not yet identified.
Practical applications: The results obtained in the present research show the possibility to apply the current extraction and detection method in different biological samples for the determination of AsL. Additionally, this information can be used for further studies to assess the risk of AsL for consumer health. On the other hand, the MS/MS results could be used for the future identification of AsL without the ICP-MS detection and thus, low the cost of the analysis.