Chemie und Prozesstechnik
Filtern
Dokumenttyp
- Zeitschriftenartikel (1175)
- Vortrag (1069)
- Posterpräsentation (442)
- Beitrag zu einem Tagungsband (175)
- Forschungsdatensatz (55)
- Sonstiges (33)
- Buchkapitel (24)
- Forschungsbericht (23)
- Dissertation (15)
- Beitrag zu einem Sammelband (13)
- Preprint (10)
- Handbuch (5)
- Video (5)
- Zeitschriftenheft (Herausgeberschaft für das komplette Heft) (3)
- Sammelband (Herausgeberschaft für den kompletten Band) (2)
- Tagungsband (Herausgeberschaft für den kompletten Band) (1)
- Newsletter (1)
Sprache
- Englisch (3051) (entfernen)
Schlagworte
- Nanoparticles (114)
- Fluorescence (112)
- Concrete (89)
- LIBS (81)
- Mechanochemistry (72)
- Quantum yield (71)
- Ultrasound (71)
- SAXS (69)
- Non-destructive testing (68)
- XPS (61)
Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (1087)
- 6 Materialchemie (973)
- 8 Zerstörungsfreie Prüfung (774)
- 6.1 Oberflächen- und Dünnschichtanalyse (348)
- 6.3 Strukturanalytik (322)
- 1.1 Anorganische Spurenanalytik (277)
- 8.2 Zerstörungsfreie Prüfmethoden für das Bauwesen (232)
- 8.0 Abteilungsleitung und andere (224)
- 1.2 Biophotonik (210)
- 4 Material und Umwelt (186)
Paper des Monats
- ja (26)
Soybean oil takes around half of the vegetable oil resources in the world, increasing in importance constantly. Besides, soy oil plants have experienced numerous accidents due to the coexistence of soy flour and hexane (as a solvent) in the extraction process, thus creating a hazardous environment. This study aims to find the maximum pressure, the maximum rate of pressure rise, and the minimum ignition energy of soy flour−hexane mixtures through specific experiments by varying the concentration of fuels in air and ignition mechanism (chemical igniters or exploding wires). The results have shown that soy flour alone is hard to ignite, whereas adding hexane even in small amounts increases the hazard and the severity of the explosions considerably. Eventually, the substitution of hexane with a greener and safer extraction agent should be of utmost focus.
This research was aimed at comparing the fire characteristics of different types of pepper in the context of explosion prevention. The following characteristics were studied: explosion pressure Pmax and Kst at selected concentrations, ignition temperature of the deposited dust layer from the hot surface, and minimum ignition energy. The comparison of the chemical properties of the used types of pepper was performed using TG/DSC. The results of the measurements suggest that different types of peppers exhibit different explosion characteristics. Each sample reached the maximum value of the explosion pressure and rate of pressure rise at different concentrations. The volume of the explosion chamber used also influenced the explosion characteristics. It is a consequence of the fact that the explosion characteristics strongly depend on the mechanism of action of a particular igniter. The minimum effect on the safety characteristics was observed when measuring the minimum ignition energy and the minimum ignition temperature of the dust layer from the hot surface. The results of the measurements suggest that different types of peppers exhibit different explosion characteristics. This information should then be considered in explosion prevention.
Referenzmaterialien sind entscheidend für die Qualitätssicherung von Laboratorien. Diese nutzen Referenzmaterialien unter anderem zur Validierung von Messverfahren und zur Kalibrierung von Geräten. Dabei ist zu beachten, dass zertifizierte Merkmalswerte stets eine gewisse Unsicherheit aufweisen. Die Ermittlung dieser Unsicherheitsbeiträge ist Gegenstand des Artikels. Des Weiteren wird ein Vorgehen beschrieben, wie die Unsicherheit von Messverfahren mit Hilfe eines Referenzmaterials bestimmt werden kann.
The affinity constant, also known as the equilibrium constant, binding constant, equilibrium association constant, or the reciprocal value, the equilibrium dissociation constant (Kd), can be considered as one of the most important characteristics for any antibody–antigen pair. Many methods based on different technologies have been proposed and used to determine this value. However, since a very large number of publications and commercial datasheets do not include this information, significant obstacles in performing such measurements seem to exist. In other cases where such data are reported, the results have often proved to be unreliable. This situation may indicate that most of the technologies available today require a high level of expertise and effort that does not seem to be available in many laboratories. In this paper, we present a simple approach based on standard immunoassay technology that is easy and quick to perform. It relies on the effect that the molar IC50 approaches the Kd value in the case of infinitely small concentrations of the reagents. A two-dimensional dilution of the reagents leads to an asymptotic convergence to Kd. The approach has some similarity to the well-known checkerboard titration used for the optimization of immunoassays. A well-known antibody against the FLAG peptide, clone M2, was used as a model system and the results were compared with other methods. This approach could be used in any case where a competitive assay is available or can be developed. The determination of an affinity constant should belong to the crucial parameters in any quality control of antibody-related products and assays and should be mandatory in papers using immunochemical protocols.
For industrial applications dealing with hydrogen, the definition of safety distances and the assessment of possible hazards emanating from releases is mandatory. Since hydrogen is usually stored and transported under pressure, one scenario to be considered is the momentum driven release of hydrogen from a leakage with subsequent ignition. In this scenario, the emitted heat radiation from the resulting jet flame to the surroundings has to be determined to define adequate safety distances. For hydrocarbon flames, different jet flame models are available to assess the hazards resulting from an ignited jet release. Since hydrogen flames differ from hydrocarbon flames in their combustion behavior, it has to be checked if these models are also applicable for hydrogen. To evaluate the accuracy of these models for hydrogen jet flames, tests at real-scale are carried out at the BAM Test Site for Technical Safety (BAM-TTS). Herein, the flame geometry and the heat radiation at defined locations in the surroundings are recorded for varying release parameters such as leakage diameter (currently up to 30 mm), release pressure (currently up to max. 250 bar) and mass flow (up to max. 0.5 kg/s). The challenge here is the characterization of the flame geometry in an open environment and its impact on the thermal radiation. Existing heat radiation data from the literature are mostly based on unsteady outflow conditions. For a better comparability with the steady state jet flame models, the experiments presented here are focused on ensuring a constant mass flow over the release duration to obtain a (quasi) stationary jet flame. In addition, stationary outflow tests with hydrocarbons (methane) were also carried out, which are intended to serve as reference tests for checking flame models based on hydrocarbon data.
Optical measurements of scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders play an important role in fundamental research and industry. Typical examples are luminescent nano- and microparticles and phosphors of different composition in different matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter for the performance of these materials is the photoluminescence quantum yield QY, i.e., the number of emitted photons per number of absorbed photons. QY of transparent luminophore solutions can be determined relatively to a fluorescence quantum yield standard of known QY. Such standards are meanwhile available as certified reference materials.[1] The determination of QY of scattering liquid and solid samples like dispersions of luminescent nanoparticles, solid phosphors, and optoceramics requires, however, absolute measurements with an integrating sphere setup. Although the importance of reliable absolute QY measurements has been recognized, no interlaboratory comparisons (ILCs) on measurement uncertainties and the identification of typical sources of uncertainty have been yet reported. Also, no scattering reference materials with known QY are available.
We present here the results of a first ILC of 3 laboratories from academia and industry performed to identify and quantify sources of uncertainty of absolute QY measurements of scattering samples. Thereby, two types of commercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring QY of transparent and scattering dye solutions and solid phosphors. As representative and industrially relevant solid and scattering samples, YAG:Ce optoceramics of varying surface roughness were chosen, applied, e.g., as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank, utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While matching QY values could be obtained for transparent dye solutions and scattering dispersions, here using a blank with scattering properties closely matching those of the sample, QY measurements of optoceramic samples with different blanks revealed substantial differences, with the blank's optical
properties accounting for measurement uncertainties of more than 20 %. Based upon the ILC results, we recommend non-absorbing blank materials with a high reflectivity (>95 %) such as a 2 mm-thick PTFE target placed on the sample holder which reveals a near-Lambertian light scattering behavior, yielding a homogeneous light distribution within the integrating sphere.
The platinum group elements (PGEs) play an important role in reducing emissions from automotive vehicles through their use in catalytic convertors but also for catalysis in the pharmaceutical industry. The immense economic value of platinum (Pt), palladium (Pd) and rhodium (Rh) highlights the importance of highly accurate measurements. Therefore, there is a need for National Metrology Institutes (NMIs) and Designated Institutes (DIs) to demonstrate measurement capability in this space.
A pilot comparison (CCQM-P63) for precious metals in automotive catalyst took place in 2006, but with a limited number of institutes participating. Furthermore, this study was performed over 17 years ago. Therefore, there was a need to maintain existing capability and demonstrate new capability in a key comparison, in order to claim calibration and measurement capability claims (CMCs). With the core capability matrix, this study falls into the "Difficult to dissolve metals/metal oxides" which will support CMC categories 8 (Metal and metal alloys), 9 (Advanced materials) and 14 (Other materials).
Eleven NMIs and DIs participated in the Key Comparison CCQM-K160 Platinum Group Elements in Automotive Catalyst. Participants were requested to evaluate the mass fractions of Pt, Pd and Rh in mg/kg in an unused autocatalyst material (cordierite ceramic base). The Key Comparison Reference Values (KCRVs) and Degrees of Equivalence (DoEs) were calculated utilising the NIST Decision Tree for the measurands. The participants utilised a number of sample preparation and analytical methods including hot plate digestion, microwave digestion and sodium fusion, followed by either atomic absorption spectroscopy (AAS), inductively coupled plasma optical emission spectroscopy (ICP-OES) or inductively coupled plasma mass spectrometry (ICP-MS) detection. Several calibration techniques were used, namely external calibration, standard addition, isotope dilution mass spectrometry (IDMS) and an exact matching procedure. Additionally, one participant employed instrumental neutron activation analysis (INAA) with k0 standardisation which is a direct solid analysis method. The majority of participants claimed traceability to NIST primary calibrants or their own CRMs. Furthermore, several matrix CRMs were included or spiked samples for quality control. All institutes were required to determine the dry mass fraction using the stipulated protocol.
The NIST decision tree was implemented for the calculation of the KCRVs and DoEs. The participant results overall showed good agreement with the KCRV, despite the variety of dissolution procedures and measurement techniques for this highly complex matrix and challenging measurands. Successful participation in CCQM-K160 demonstrated measurement capabilities for the determination of mass fraction of Pt, Pd and Rh in the mg/kg range and will support broad scope CMC claims for a wide range of challenging matrices.
To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/.
The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).
Characterization and quantification of functional groups and coatings on nanoobjects an overview
(2024)
Characterization of Nanoparticles – Questions to Ask, Functional Nanoparticles (NPs) – Organic, Inorganic, and Hybrid Nanoparticles Nanomaterial Characterization Standardization – Addressing Remaining Gaps Surface FGs Particle Surface Chemistry - Why is it Important? Particle Surface Chemistry - A Key Driver for Performance, Applications, and Safety Aspects Method Development for Quantifying FGs and Ligands on Particle Surfaces FG Quantification – Method Choice & Criteria Relevant for Data Interpretation Quantifying the Amount of Total and Accessible FGs on Aminated Silica Nanoparticles (SiO2-NH2) Comparing the Total and Accessible –NH2 Content on Aminated Silica NPs of Different Size Characterization of Nanoparticles Standardization Standardized Measurements of Surface FGs on Nanoparticles EMP Project SMURFnano EMP Project SMURFnano Work Packages & Goals Certified Reference Materials from BAM
For industrial applications dealing with hydrogen, the definition of safety distances and the assessment of possible hazards emanating from releases is mandatory. Since hydrogen is usually stored and transported under pressure, one scenario to be considered is the momentum driven release of hydrogen from a leakage with subsequent ignition. In this scenario, the emitted heat radiation from the resulting jet flame to the surroundings has to be determined to define adequate safety distances. For hydrocarbon flames, different jet flame models are available to assess the hazards resulting from an ignited jet release. Since hydrogen flames differ from hydrocarbon flames in their combustion behavior, it has to be checked if these models are also applicable for hydrogen. To evaluate the accuracy of these models for hydrogen jet flames, tests at real-scale are carried out at the BAM Test Site for Technical Safety (BAM-TTS). Herein, the flame geometry and the heat radiation at defined locations in the surroundings are recorded for varying release parameters such as leakage diameter (currently up to 30 mm), release pressure (currently up to max. 250 bar) and mass flow (up to max. 0.5 kg/s). The challenge here is the characterization of the flame geometry in an open environment and its impact on the thermal radiation. Existing heat radiation data from the literature are mostly based on unsteady outflow conditions. For a better comparability with the steady state jet flame models, the experiments presented here are focused on ensuring a constant mass flow over the release duration to obtain a (quasi) stationary jet flame. In addition, stationary outflow tests with hydrocarbons (methane) were also carried out, which are intended to serve as reference tests for checking flame models based on hydrocarbon data.
Despite the physiological and pathophysiological significance of microenvironmental gradients, e.g., for diseases such as cancer, tools for generating such gradients and analyzing their impact are lacking. Here, we present an integrated microfluidic-based workflow that mimics extracellular pH gradients characteristic of solid tumors while enabling high-resolution live imaging of, e.g., cell motility and chemotaxis, and preserving the capacity to capture the spatial transcriptome. Our microfluidic device generates a pH gradient that can be rapidly controlled to mimic spatiotemporal microenvironmental changes over cancer cells embedded in a 3D matrix. The device can be reopened allowing immunofluorescence analysis of selected phenotypes, as well as the transfer of cells and matrix to a Visium slide for spatially resolved analysis of transcriptional changes across the pH gradient. This workflow is easily adaptable to other gradients and multiple cell types and can therefore prove invaluable for integrated analysis of roles of microenvironmental gradients in biology.
To reduce carbon dioxide emissions, energy carries such as hydrogen consider to be a solution. Consumption of hydrogen as a fuel meets several restrictions such as its low volumetric energy density in gas phase. To tackle this problem, storage as well as transportation in liquid phase is recommended. To be able to handle this component in liquid phase, an efficient thermal insulation e.g., MLI insulation is required. Some studies have been revealed vulnerability of this type of insulation against high heat flux, for instance a fire accident. Some investigations have been depicted the importance of consideration of the MLI thermal degradation in terms of its reflective layer. However, limited number of studies have been focused on the thermal degradation of spacer material and its effect on the overall heat flux.
In this study, through systematic experimental measurements, the effect of thermal loads on glass fleece, glass paper as well as polyester spacers are investigated. The results are reported in various temperature and heat flux profiles. Interpreting the temperature profiles revealed as the number of spacers in the medium increases, the peak temperature detectable by the temperature sensor on the measurement plate decreases. Moreover, the contribution of each individual spacer in all cases regarding the experimental temperature range is assessed to be around 8%. This value may increase to around 50% for glass paper and polyester spacers, and to around 25% for glass fleece spacers as the number of spacer layers increases up to six layers.
To utilize the outcomes of the experiment later and integrate the results into numerical and CFD simulations, a model is proposed for the mentioned experimental temperature range up to 300°C to predict a heat flux attenuation factor. The model proposes a fitting factor that can reproduce the least square fitted line to the experimental data.
Study the Impact of Spacer at Thermal Degradation Process of MLI-based Insulation in Fire Condition
(2024)
To reduce carbon dioxide emissions, energy carries such as hydrogen consider to be a solution. Consumption of hydrogen as a fuel meets several restrictions such as its low volumetric energy density in gas phase. To tackle this problem, storage as well as transportation in liquid phase is recommended. To be able to handle this component in liquid phase, an efficient thermal insulation e.g., MLI insulation is required. Some studies have been revealed vulnerability of this type of insulation against high heat flux, for instance a fire accident. Some investigations have been depicted the importance of consideration of the MLI thermal degradation in terms of its reflective layer. However, limited number of studies have been focused on the thermal degradation of spacer material and its effect on the overall heat flux.
In this study, through systematic experimental measurements, the effect of thermal loads on glass fleece, glass paper as well as polyester spacers are investigated. The results are reported in various temperature and heat flux profiles. Interpreting the temperature profiles revealed as the number of spacers in the medium increases, the peak temperature detectable by the temperature sensor on the measurement plate decreases. Moreover, the contribution of each individual spacer in all cases regarding the experimental temperature range is assessed to be around 8%. This value may increase to around 50% for glass paper and polyester spacers, and to around 25% for glass fleece spacers as the number of spacer layers increases up to six layers.
To utilize the outcomes of the experiment later and integrate the results into numerical and CFD simulations, a model is proposed for the mentioned experimental temperature range up to 300°C to predict a heat flux attenuation factor. The model proposes a fitting factor that can reproduce the least square fitted line to the experimental data.
In the course of decarbonizing the energy industry, cryogenic energy carriers as liquefied hydrogen (LH2) and liquefied natural gas (LNG) are seen as having great potential. In technical applications, the challenge is to keep these energy carriers cold for a long time. This is achieved in the road transport sector and also stationary applications by thermal super insulations (TSI) which based on double-walled tanks with vacuum and multilayer insulation (MLI) in the interspace. This study focuses on the behaviour of widely used combustible MLI in a fire scenario, at vacuum and atmospheric pressure conditions. The former corresponds to the typical design condition and the latter to the condition after an outer hull rapture of a tank. Furthermore, two fire scenarios were taken into account: a standard-oriented approach and a hydrocarbon fire-oriented approach. For the study, a test rig was applied that allows testing of TSI at industrial conditions and subsequent analysis of TSI samples. The test rig allows thermal loading and performance analysis of TSI samples at the same time. Comparing the tests, the samples degraded differently. However, no sudden failure of the entire MLI was observed in any test. These results are relevant for the evaluation of incidents with tanks for the storage of cryogenic fluids and can thus contribute to the improvement of TSI and the development of emergency measures for the protection of persons and infrastructures.
In the course of decarbonizing the energy industry, cryogenic energy carriers as liquefied hydrogen (LH2) and liquefied natural gas (LNG) are seen as having great potential. In technical applications, the challenge is to keep these energy carriers cold for a long time. This is achieved in the road transport sector and also stationary applications by thermal super insulations (TSI) which based on double-walled tanks with vacuum and multilayer insulation (MLI) in the interspace. This study focuses on the behaviour of widely used combustible MLI in a fire scenario, at vacuum and atmospheric pressure conditions. The former corresponds to the typical design condition and the latter to the condition after an outer hull rapture of a tank. Furthermore, two fire scenarios were taken into account: a standard-oriented approach and a hydrocarbon fire-oriented approach. For the study, a test rig was applied that allows testing of TSI at industrial conditions and subsequent analysis of TSI samples. The test rig allows thermal loading and performance analysis of TSI samples at the same time. Comparing the tests, the samples degraded differently. However, no sudden failure of the entire MLI was observed in any test. These results are relevant for the evaluation of incidents with tanks for the storage of cryogenic fluids and can thus contribute to the improvement of TSI and the development of emergency measures for the protection of persons and infrastructures.
Ensuring the purity of air and water is essential for the overall well-being of life on earth and the sustainability of the planet's diverse ecosystems. To achieve the goal of zero pollution, as outlined in the 2020 European Green Deal by the European Commission,[1] significant efforts are in progress. A key aspect of this commitment involves advancing more efficient and economically viable methods for treating wastewater. This includes the systematic monitoring of harmful pollutants such as heavy metals, microplastics, pesticides, and pharmaceuticals.
One example is the presence of the anti-inflammatory drug diclofenac in water systems, primarily originating from its use as a gel or lotion for joint pain treatment. Diclofenac contamination in surface waters has been detected at approximately 10 μg L-1 (0.03 μM)[2] which is not solely due to widespread usage but also because of the drug's resistance to microbial degradation. Conventional wastewater treatment plants (WWTPs), which rely on biodegradation, sludge sorption, ozone oxidation, and powdered activated carbon treatment, struggle to efficiently remove diclofenac from wastewater.[3],[4] For instance, to enable WWTPs to efficiently monitor and optimize their processes, it would be advantageous to develop on-site detection and extraction methods for persistent pharmaceutical residues in aqueous samples.
In this work, a sol-gel process was used to prepare Nile blue-doped silica nanoparticles (dSiO2-NPs) with a diameter of ca. 30 nm that were further functionalized to enable reversible-addition-fragmentation chain-transfer (RAFT) polymerization. To achieve fluorescence detection, a fluorescent monomer was used as a probe for diclofenac in ethyl acetate, generating stable complexes through hydrogen bond formation. The diclofenac/fluorescent monomer complexes were imprinted into thin molecularly imprinted polymer (MIP) shells on the surface of the dSiO2-NPs. Thus, the MIP binding behaviour could be easily evaluated by fluorescence titrations to monitor the spectral changes upon addition of the analyte. Doping the core substrate with Nile blue generates effective dual fluorescent signal transduction. This approach does not solely depend on a single fluorescence emission band in response to analyte recognition. Instead, it enables the fluorescent core to function as an internal reference, minimizing analyte-independent factors such as background fluorescence, instrumental fluctuation, and operational parameters.[5] Rebinding studies showed that the MIP particles have excellent selectivity towards the imprinted template and good discrimination against the competitor ibuprofen, with a discrimination factor of 2.5. Additionally, the limit of detection was determined to be 0.6 μM. Thus, with further optimization of the MIP, there is potential for the development of a MIP-based biphasic extract-&-detect fluorescence assay for simple, sensitive and specific sensing of diclofenac in aqueous samples down to the required concentrations of 0.03 μM.
Per- and polyfluoroalkyl substances (PFAS) represent a class of synthetic organofluorine chemicals extensively utilized in the manufacturing of various materials such as firefighting foams, adhesives, and stain- and oil-resistant coatings. In recent years, PFAS have been considered as emerging environmental contaminants, with particular focus on perfluoroalkyl carboxylic acids (PFCAs), the most prevalent type among PFAS. PFCAs are characterized by a fully fluorinated carbon backbone and a charged carboxylic acid headgroup. Notably, they have been designated as Substances of Very High Concern and added to the REACH Candidate List due to their persistence in the environment, non-biodegradability and toxicological effects.
Conventional techniques for the analysis of PFCA, such as GC-MS, HRMS and HPLC-based methods, are laborious, not portable, costly and require skilled personnel. In contrast, fluorescence assays can be designed as easy-to-operate, portable and cost-effective methods with high sensitivity and fast response, especially when analyte binding leads to a specific increase of a probe’s emission. Integration of such probes with a carrier platform and a miniaturized optofluidic device affords a promising alternative for PFCA monitoring.
Here, a novel guanidine BODIPY fluorescent indicator monomer has been synthesized, characterized, and incorporated into a molecularly imprinted polymer (MIP) for the specific detection of perfluorooctanoic acid (PFOA). The MIP layer was formed on tris(bipyridine)ruthenium(II) chloride doped silica core particles for optical internal reference and calibration-free assays. Such system allows selective and reliable detection of PFCA from surface water samples, with minimum interference by competitors, matrix effects and other factors. Integration of the assay into an opto-microfluidic setup resulted in a miniaturized and easy-to-operate detection system allowing for micromolar detection of PFOA in less than 15 minutes from surface water sample.
A damaging action of HNO3-55% only occurs in combination with its decomposition into nitrous gases, which can be caused by UV radiation. In a laboratory test, transparent HDPE jerrycans have been exposed to both UV radiation and 55 wt-% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The respective damages are compared with FTIR spectroscopy in ATR and HT-gel permeation chromatography (GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. The gradual increase in oxidative damage shows the good reproducibility of the lab exposure. The decomposition of nitric acid into nitrous gases by UV radiation – as well as the jerrycan oxidation – is also observed at lower HNO3 concentration (28 wt- %). Similar results are obtained after outdoor tests. Again, the damage occurs only after combined exposure, in contrast to the exposures to UV only and to HNO3 only, which were conducted in parallel. Outdoor exposures are most readily accepted as they represent possible end-use conditions. However, the reproducibility of these exposures is poor due to the large temporal variations in weather. There are also several safety risks, which is why the number of replicates remains limited. Since the outdoor and lab exposure tests show the same qualitative results, it is appropriate to conduct systematic studies in the laboratory. After 6 days of lab exposure, the oxidation damage is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. It should be noted that this amount can also occur in two sunny weeks.
A damaging action of HNO3-55% only occurs in combination with its decomposition into nitrous gases, which can be caused by UV radiation. In a laboratory test, transparent HDPE jerrycans have been exposed to both UV radiation and 55 wt-% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The respective damages are compared with FTIR spectroscopy in ATR and HT-gel permeation chromatography (GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. The gradual increase in oxidative damage shows the good reproducibility of the lab exposure. The decomposition of nitric acid into nitrous gases by UV radiation – as well as the jerrycan oxidation – is also observed at lower HNO3 concentration (28 wt- %). Similar results are obtained after outdoor tests. Again, the damage occurs only after combined exposure, in contrast to the exposures to UV only and to HNO3 only, which were conducted in parallel. Outdoor exposures are most readily accepted as they represent possible end-use conditions. However, the reproducibility of these exposures is poor due to the large temporal variations in weather. There are also several safety risks, which is why the number of replicates remains limited. Since the outdoor and lab exposure tests show the same qualitative results, it is appropriate to conduct systematic studies in the laboratory. After 6 days of lab exposure, the oxidation damage is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. It should be noted that this amount can also occur in two sunny weeks.
Silicon isotope fractionation during silicification is poorly understood and impedes our ability to decipher paleoenvironmental conditions from Si isotopes in ancient cherts. To investigate isotope fractionation during silica-for-carbonate replacement we analyzed the microscale Si and O isotope composition in different silica phases in a silicified zebra dolostone as well as their bulk δ18O and Δ’17O compositions. The subsequent replacement of carbonate layers is mimicked by decreasing δ18O and δ30Si. The textural relationship and magnitude of Si and O isotope fractionation is best explained by near-quantitative silica precipitation in an open system with finite Si. A Rayleigh model for silicification suggests positive Ɛ30/28Si during silicification, conforming with predictions for isotope distribution at chemical equilibrium from ab-initio models. Application of the modelled Ɛ30Si-T relationship yields silicification temperatures of approx. 50°C. To reconcile the δ18Ochert composition with these temperatures, the δ18O of the fluid must have been between -2.5 and -4 ‰, compositions for which the quartz phases fall close to the oxygen equilibrium fractionation line in three-isotope space. Diagenetic silica replacement appears to occur in O and Si isotopic equilibrium allowing reconstructions of temperatures of silicification from Si isotopes and derive the δ18O composition of the fluid – a highly desired value needed for accurate reconstructions of the temperature- and δ18O histories of the oceans.
The research project focuses on tackling the detection, measurement, and elimination of per- and polyfluoroalkyl substances (PFAS) from polluted groundwater, with a particular emphasis on addressing short (C4-C7) and ultrashort (C1-C3) chain PFAS. Given the widespread use of PFAS in various products, they are commonly found in groundwater near industrial and military sites in Germany and Israel. Moreover, recent regulations limiting the use of long chain PFAS have led industries to shift towards shorter chain alternatives. Hence, our efforts are geared towards refining detection, quantification, and removal methods for short and ultrashort chain PFAS. In terms of detection, ww are developing passive sampling devices capable of collecting and tracking the temporal distribution of PFAS species in groundwater. This will enable us to analyze contaminations in German and Israeli groundwater using cutting-edge analytical techniques. Additionally, contaminated groundwater will undergo a two-stage treatment process aimed at concentrating the relatively low PFAS concentrations using innovative membrane technologies such as closed-circuit reverse osmosis and mixed matrix composite nanofiltration membrane adsorbers. Subsequently, the streams containing higher PFAS concentrations will be treated through coagulation, with the remaining PFAS being adsorbed onto carbonaceous nanomaterials. The outcome of this research will include the creation of advanced tools for detecting, measuring, and eliminating PFAS from polluted groundwater, while also enhancing our understanding of the scope of these contaminations.
Ultrashort PFAS (≤ 3 carbon atoms) were overlooked for a long time in analytical monitoring. Beside through the use of these substances, they contribute to the PFAS background in the environment through (environmental/ bio-) degradation and incomplete destruction3 of PFAS with longer carbon chains or other fluorinated compounds. As part of the German-Israeli Cooperation in Water Technology Research project „Detection, quantification, and treatment of per- and polyfluoroalkyl substances in groundwater“ (DEFEAT-PFAS), we are developing an as simple as possible direct headspace (HS-)GC-MS method to detect trifluoroacetic acid (TFA) and perfluoropropanioc acid (PFPrA), as well as trifluoroethanol (TFEtOH), pentafluoropropanol(PFPrOH) and hexafluoroiospropanol (HFIP) in water samples. Here we present the results of the PFAS mentioned in spiked ultrapure water solutions.
Detection, Quantification and Treatment of Per and Polyfluoroalkyl substances (PFAS) in Groundwater
(2024)
The research project focuses on tackling the detection, measurement, and elimination of per- and polyfluoroalkyl substances (PFAS) from polluted groundwater, with a particular emphasis on addressing short (C4-C7) and ultrashort (C1-C3) chain PFAS. Given the widespread use of PFAS in various products, they are commonly found in groundwater near industrial and military sites in Germany and Israel. Moreover, recent regulations limiting the use of long chain PFAS have led industries to shift towards shorter chain alternatives. Hence, our efforts are geared towards refining detection, quantification, and removal methods for short and ultrashort chain PFAS. In terms of detection, ww are developing passive sampling devices capable of collecting and tracking the temporal distribution of PFAS species in groundwater. This will enable us to analyze contaminations in German and Israeli groundwater using cutting-edge analytical techniques. Additionally, contaminated groundwater will undergo a two-stage treatment process aimed at concentrating the relatively low PFAS concentrations using innovative membrane technologies such as closed-circuit reverse osmosis and mixed matrix composite nanofiltration membrane adsorbers. Subsequently, the streams containing higher PFAS concentrations will be treated through coagulation, with the remaining PFAS being adsorbed onto carbonaceous nanomaterials. The outcome of this research will include the creation of advanced tools for detecting, measuring, and eliminating PFAS from polluted groundwater, while also enhancing our understanding of the scope of these contaminations.
Diese Präsentation stellt die gegenwärtige Situation zur Einstufung von primer caps (Anzündhütchen) gemäß Richtlinie 2014/28/EU und UN Model Regulations Rev.23 (Volume I) dar. Spezifische Eigenschaften und Gefährdungen werden dargestellt und eine Abgrenzung zur Richtlinie 2013/29/EU aufgezeigt.
The DACHS (Database for Automation, Characterization and Holistic Synthesis) project aims to create completely traceable experimental data, covering syntheses, measurements, analyses, and interpretations. DACHS_MOFs focuses on the synthesis and characterisation of metal-organic frameworks, across multiple, automation-assisted experimental series (AutoMOFs), with the overall goal of producing reproducible MOF samples through tracking of the synthesis parameters.
DACHS_MOFs is simultaneously used to test the DACHS principles.
This upload contain synthesis data from AutoMOFs_1 in HDF5 format (.h5). Each .h5 file contains detailed information on the chemical, experimenal, and synthesis parameters used during the synthesis of a single AutoMOF sample.
We developed a two-step semi-synthesis for the preparation of isotopically labeled EAs, starting from native EAs. This universal strategy enabled the successful synthesis of all isotopically labeled priority EAs. The structure of the isotopically labeled EAs was confirmed by HPLC-HR-MS/MS using native, unlabeled EAs as a reference standard. The next step will be the implementation of the isotopically labeled standards in the European standard procedure EN 17425 to improve the quantification of EAs in foodstuffs.
Peptide pools consist of short amino acid sequences and have proven to be versatile tools in various research areas in immunology and clinical applications. They are commercially available in many different compositions and variants. However, unlike other reagents that consist of only one or a few compounds, peptide pools are highly complex products which makes their quality control a major challenge. Quantitative peptide analysis usually requires sophisticated methods, in most cases isotope-labeled standards and reference materials. Usually, this would be prohibitively laborious and expensive. Therefore, an approach is needed to provide a practical and feasible method for quality control of peptide pools. With insufficient quality control, the use of such products could lead to incorrect experimental results, worsening the well-known reproducibility crisis in the biomedical sciences. Here we propose the use of ultra-high performance liquid chromatography (UHPLC) with two detectors, a standard UV detector at 214 nm for quantitative analysis and a high-resolution mass spectrometer (HRMS) for identity confirmation. To be cost-efficient and fast, quantification and identification are performed in one chromatographic run. An optimized protocol is shown, and different peak integration methods are compared and discussed. This work was performed using a peptide pool known as CEF advanced, which consists of 32 peptides derived from cytomegalovirus (CMV), Epstein–Barr virus (EBV) and influenza virus, ranging from 8 to 12 amino acids in length.
The non-steroidal anti-inflammatory drug (NSAID) diclofenac (DCF) is an important environmental contaminant occurring in surface waters all over the world, because, after excretion, it is not adequately removed from wastewater in sewage treatment plants. To be able to monitor this pollutant, highly efficient analytical methods are needed, including immunoassays. In a medical research project, monoclonal antibodies against diclofenac and its metabolites had been produced. Based on this monoclonal anti-DCF antibody, a new indirect competitive enzyme-linked immunosorbent assay (ELISA) was developed and applied for environmental samples. The introduction of a spacer between diclofenac and the carrier protein in the coating conjugate led to higher sensitivity. With a test midpoint of 3 mg L−1 and a measurement range of 1–30 mg L−1, the system is not sensitive enough for direct analysis of surface water. However, this assay is quite robust against matrix influences and can be used for wastewater. Without adjustment of the calibration, organic solvents up to 5%, natural organic matter (NOM) up to 10 mg L−1, humic acids up to 2.5 mg L−1, and salt concentrations up to 6 g L−1 NaCl and 75 mg L−1 CaCl2 are tolerated. The antibody is also stable in a pH range from 3 to 12. Cross-reactivity (CR) of 1% or less was determined for the metabolites 40-hydroxydiclofenac (40-OH-DCF), 5-hydroxydiclofenac (5-OH-DCF), DCF lactam, and other NSAIDs. Relevant cross-reactivity occurred only with an amide derivative of DCF, 6-aminohexanoic acid (DCF-Ahx), aceclofenac (ACF) and DCF methyl ester (DCF-Me) with 150%, 61% and 44%, respectively. These substances, however, have not been found in samples. Only DCF-acyl glucuronide with a cross-reactivity of 57% is of some relevance. For the first time, photodegradation products were tested for cross-reactivity. With the ELISA based on this antibody, water samples were analysed. In sewage treatment plant effluents, concentrations in the range of 1.9–5.2 mg L−1 were determined directly, with recoveries compared to HPLC-MS/MS averaging 136%.
Concentrations in lakes ranged from 3 to 4.4 ng L−1 and were, after pre-concentration, determined with an average recovery of 100%
Luminophore stained micro- and nanobeads made from organic polymers like polystyrene (PS) are broadly used in the life and material sciences as luminescent reporters, for bead-based assays, sensor arrays, printable barcodes, security inks, and the calibration of fluorescence microscopes and flow cytometers. Initially mostly prepared with organic dyes, meanwhile luminescent core/shell nanoparticles (NPs) like spherical semiconductor quantum dots (QDs) are increasingly employed for bead encoding. This is related to their narrower emission spectra, tuneability of emission color, broad wavelength excitability, and better photostability. However, correlations between particle architecture, morphology, and photoluminescence (PL) of the luminescent nanocrystals used for encoding and the optical properties of the NP-stained beads have been rarely explored. This encouraged us to perform a screening study on the incorporation of different types of luminescent core/shell semiconductor nanocrystals into polymer microparticles (PMPs) by a radical-induced polymerization reaction. Nanocrystals explored include CdSe/CdS QDs of varying CdS shell thickness, a CdSe/ZnS core/shell QD, CdSe/CdS quantum rods (QRs), and CdSe/CdS nanoplatelets (NPLs).
Thereby, we focused on the applicability of these NPs for the polymerization synthesis approach used and quantified the preservation of the initial NP luminescence. The spectroscopic characterization of the resulting PMPs revealed the successful staining of the PMPs with luminescent CdSe/CdS QDs and CdSe/CdS NPLs. In contrast, usage of CdSe/CdS QRs and CdSe QDs with a ZnS shell did not yield luminescent PMPs. The results of this study provide new insights into structure–property relationships between NP stained PMPs and the initial luminescent NPs applied for staining and underline the importance of such studies for the performance optimization of NP-stained beads.
Fluorescent labels have strongly contributed to many advancements in bioanalysis, molecular biology, molecular imaging, and medical diagnostics. Despite a large toolbox of molecular and nanoscale fluorophores to choose from, there is still a need for brighter labels, e.g., for flow cytometry and fluorescence microscopy, that are preferably of molecular nature. This requires versatile concepts for fluorophore multimerization, which involves the shielding of dyes from other chromophores and possible quenchers in their neighborhood. In addition, to increase the number of readout parameters for fluorescence microscopy and eventually also flow cytometry, control and tuning of the labels’ fluorescence lifetimes is desired. Searching for bright multi-chromophoric or multimeric labels, we developed PEGylated dyes bearing functional groups for their bioconjugation and explored their spectroscopic properties and photostability in comparison to those of the respective monomeric dyes for two exemplarily chosen fluorophores excitable at 488 nm. Subsequently, these dyes were conjugated with anti-CD4 and anti-CD8 immunoglobulins to obtain fluorescent conjugates suitable for the labeling of cells and beads. Finally, the suitability of these novel labels for fluorescence lifetime imaging and target discrimination based upon lifetime measurements was assessed. Based upon the results of our spectroscopic studies including measurements of fluorescence quantum yields (QY) and fluorescence decay kinetics we could demonstrate the absence of significant dye-dye interactions and self-quenching in these multimeric labels. Moreover, in a first fluorescence lifetime imaging (FLIM) study, we could show the future potential of this multimerization concept for lifetime discrimination and multiplexing.
Trace elemental analysis in human serum is integral in both clinical and research settings. Analyzing the level of some specific elements like Se and Zn helps indicate the nutritional and health status. Furthermore, elucidating the roles of trace elements in various physiological and pathological conditions can shed light on disease mechanisms and potential treatments. Inductively coupled plasma mass spectrometry (ICP-MS) stands out as a preeminent method for trace elemental analysis, given its exceptional sensitivity and minimal sample requirements. However, ICP-MS has challenges, such as argon-related interferences that hinder the accurate quantification of elements like Ca, Fe, and Se. The naturally most abundant isotopes of Ca (40Ca), Fe (56Fe), and Se (80Se) are subject to isobaric interference from 40Ar+, 40Ar16O+, and 40Ar2+, thereby complicating their direct measurement and preventing isotope dilution analysis.
In response to these challenges, nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) emerges as a viable alternative to ICP-MS, eliminating argon consumption and associated interferences. This study employed MICAP-MS to quantify Ca, Fe, and Se in 11 certified reference human serums using matrix-matched calibration and isotope dilution with the isotopes 40Ca, 56Fe, and 80Se. The results obtained with both methods were validated against certified values, and the suitability of MICAP-MS for isotope dilution was evaluated. Additionally, the performance of MICAP-MS in the Na matrix was investigated and discussed alongside the impact of organic species.
Self-healing polymers have been developed to improve durability and reduce costs associated with maintenance during service. The addition of thermoplastics to thermosets to produce mendable polymers appears as a promising selfhealing technique. In this study, poly (ethylene-co-methacrylic acid) (EMAA) was added to epoxy resin and the effects of EMAA addition on epoxy properties were evaluated. Specimens with two different contents of thermoplastic and particles sizes were manufactured. A two-level full factorial experimental design was used to evaluate the effect of particle size and particle content on properties of epoxy modified with addition of EMAA. Tensile tests and dynamic mechanical analysis (DMA) were used and the evaluated responses were tensile strength, modulus of elasticity, and glass transition temperature (Tg). X-ray computed tomography (XCT) was used to investigate particle size and concentration after manufacturing. It was found that the particle concentration has greater effects on stress–strain behavior of epoxy while Tg was not significantly affected by neither of the analyzed entrance variables.
Lithium-ion batteries are a key technology for tackling challenges in energy and climate crisis, but up to 30 % are discarded right after production. Quality is closely related to the homogeneity of the used materials and coatings. Fluorine compounds, both in the polymer and from degradation of the electrolyte, are of special interest for the formation and aging of LIBs. Glow-discharge optical emission spectroscopy (GD-OES) emerged as a fast and convenient method for depth-profiling of battery materials. However, fluorine remains a spectroscopic challenge due to a high excitation energy and only few strong emission lines in the UV/Vis spectral range.
We investigated the partial substitution of argon with neon in the plasma gas. The main emission line at 685.603 nm was monitored by both photo multiplier tube (PMT) with Czerny-Turner monochromator at 20 µm slit-size, and charge-coupled device (CCD) with 1200 lines/mm grating. For calibration, we used a set of hot-pressed copper cylinders with varying calcium fluoride amount fraction, ranging from 1.6 % to 4.4 %. Plasma gas mixtures with a mole fraction of 5 %, 10 % and 20 % neon in argon were used. Sensitivity in comparison to pure argon was increased by factor 4, 7 and 14, respectively. In general, PMT detection was more sensitive than CCD. As expected, sputter rates decreased with higher neon content in the plasma gas. Depth-profiling of the cathodes was performed in pulsed mode at constant voltage and pressure, which resulted in stable plasma conditions. We achieve matrix-independent quantitative information on fluorine distribution by correction based on sputter rates.
This advancement in GD-OES provides a more accurate analytical approach for evaluating the homogeneity of lithium-ion battery materials, potentially leading to more sustainable and cost-effective manufacturing processes.
To address the challenges of the climate crisis, multiple solutions for sustainable energy sources and storage systems are needed. One such solution is lithium-ion batteries (LIBs). Currently, 5 to 30 % of LIBs are discarded immediately after manufacturing. The homogeneous distribution of all materials used in the coating of cathodes and anodes is critical for the quality of LIBs. Furthermore, during formation i.e., the first steps of the charge/discharge cycling, the solid-electrolyte interphase forms on the anode particles, which has a huge impact on the performance. The same happens to some extent on the cathode, forming the cathode-electrolyte interphase. Fluorinated polymers and electrolytes are used in the manufacturing of LIBs. The electrolyte in particular is prone to degradation during formation and aging of the batteries. The interface of the cathode material with the aluminum current collector is also a critical point where degraded fluorine components cause pitting corrosion and at the same time promote passivation of the metal foil. Monitoring the spatial distribution of fluorine on these surfaces and interfaces is essential for sustainable LIB production.
In order to reduce global warming, the use of hydrogen as a renewable energy source is becoming more important. To enable this transition, unprecedently large amounts of hydrogen need to be safely transported and stored. Since hydrogen is usually stored and transported under pressure, one scenario to be considered is the release of hydrogen from a leakage with subsequent ignition. The resulting jet flame must be characterized with respect to the thermal radiation emitted into the environment to define safety distances. Various models that characterize the resulting flame shape and radiation already exist in the literature, but these are mainly based on empirical data from hydrocarbon jet flames. To verify the applicability of these models to hydrogen, real-scale tests are carried out at the BAM Test Site for Technical Safety (BAM-TTS) with the aim to assess the flame geometry and the emitted thermal radiation. Parameters such as leakage diameter (currently up to 30 mm), pressure (currently up to max. 250 bar) and mass flow (up to max. 0.5 kg/s) are varied. In particular, the focus will be laid on the measurement and modelling of the thermal radiation. The challenge here is the characterization of the flame geometry in an open environment and its impact on the thermal radiation. Existing heat radiation data from literature are mostly based on unsteady outflow conditions. The experimental setup used here allows for the generation of a steady-state outflow for several minutes and thus a direct comparability with existing (steady-state) models. Furthermore, stationary outflow tests with hydrocarbons (methane) were also carried out, which are intended to serve as reference tests for checking flame models based on hydrocarbon data. Following from the experimental investigations, modelling parameters such as the Surface Emissive Power (SEP) and the radiant heat fraction for hydrogen and methane will be compared to literature data.
Science Café Adlershof is having its next edition in 2024 on February 20th '24! We will have one speaker next week: Alexander Winckelmann is a PhD student at Bundesanstalt für Materialforschung und -Prüfung and will give a talk about his stay abroad in Switzerland - there will be free chocolates! There will be enough time to ask questions or simply chat with the guests and participants.
A systematic series of industrial-relevant polystyrene-based anion exchange resins that are functionalized with hydro- or fluorocarbon chains are compared regarding their adsorption behavior toward perfluorocarboxylic acids (PFCA) in respect to their charge, chain length, and type of chain. The results clearly show the dominance of electrostatic interactions in the adsorption process as uncharged adsorber materials showed no adsorption at all. In contrast, the charged adsorber materials showed in general a PFCA removal of 80% to 30% over the experiment depending on effluent fraction.
Unexpectedly, for perfluorobutanoic acid (PFBA) the highest removal rate is found with consistently >90%. Despite observing significant benefits in the adsorption of PFCA for fluoroalkylated adsorbers in comparison to their non-fluorinated counterparts, this effect of fluoroalkylation is comparatively small and can not be clearly attributed to fluorophilic interactions between the fluoroalkyl chains. These findings help clarifying that the introduction of fluorocarbon moieties in adsorber materials is not necessary in order to remove fluorocarbon molecules from the environment.
Changes in Black Truffle (Tuber melanosporum) Aroma during Storage under Different Conditions
(2024)
The enticing aroma of truffles is a key factor for their culinary value. Although all truffle species tend to be pricy, the most intensely aromatic species are the most sought after. Research into the aroma of truffles encompasses various disciplines including chemistry, biology, and sensory science. This study focusses on the chemical composition of the aroma of black truffles (Tuber melanosporum) and the changes occurring under different storage conditions. For this, truffle samples were stored under different treatments, at different temperatures, and measured over a total storage time of 12 days. Measurements of the truffle aroma profiles were taken with SPME/GC–MS at regular intervals. To handle the ample data collected, a systematic approach utilizing multivariate data analysis techniques was taken. This approach led to a vast amount of data which we made publicly available for future exploration. Results reveal the complexity of aroma changes, with 695 compounds identified, highlighting the need for a comprehensive understanding. Principal component analyses offer initial insights into truffle composition, while individual compounds may serve as markers for age (formic acid, 1-methylpropyl ester), freshness (2-Methyl-1-propanal; 1-(methylthio)-propane), freezing (tetrahydrofuran), salt treatment (1-chloropentane), or heat exposure (4-hydroxy-3-methyl-2-butanone). This research suggests that heat treatment or salt contact significantly affects truffle aroma, while freezing and cutting have less pronounced effects in comparison. The enrichment of compounds showing significant changes during storage was investigated with a metabolomic pathway analysis. The involvement of some of the enriched compounds on the pyruvate/glycolysis and sulfur pathways was shown.
Amphiphilic nanogels (ANGs) are promising carriers for hydrophobic cargos such as drugs, dyes, and catalysts.
Loading content and release kinetics of these compounds are controlled by type and number of hydrophobic groups in the amphiphilic copolymer network. Thus, understanding the interactions between cargo and colloidal carrier is mandatory for a tailor-made and cargo-specific ANG design. To systematically explore the influence of the network composition on these interactions, we prepared a set of ANGs of different amphiphilicity and loaded these ANGs with varying concentrations of the solvatochromic dye Nile Red (NR). Here, NR acts as a hydrophobic model cargo to optically probe the polarity of its microenvironment. Analysis of the NR emission spectra as well as measurements of the fluorescence quantum yields and decay kinetics revealed a decrease in the polarity of the NR microenvironment with increasing hydrophobicity of the hydrophobic groups in the ANG network and dye–dye interactions at higher loading concentrations. At low NR concentrations, the hydrophobic cargo NR is encapsulated in the hydrophobic domains. Increasing NR concentrations resulted in probe molecules located in a more hydrophilic environment, i.e., at the nanodomain border, and favored dye–dye interactions and NR aggregation.
These results correlate well with release experiments, indicating first NR release from more hydrophilic network locations. Overall, our findings demonstrate the importance to understand carrier–drug interactions for efficient loading and controlled release profiles in amphiphilic nanogels.
On-line coupled high performance liquid chromatography-gas chromatography-flame ionisation detection (HPLC-GC-FID) was used to compare the effect of hydrogen, helium and nitrogen as carrier gases on the chromatographic characteristics for the quantification of mineral oil hydrocarbon (MOH) traces in food related matrices. After optimisation of chromatographic parameters nitrogen carrier gas exhibited characteristics equivalent to hydrogen and helium regarding requirements set by current guidelines and standardisation such as linear range, quantification limit and carry over. Though nitrogen expectedly led to greater peak widths, all required separations of standard compounds were sufficient and humps of saturated mineral oil hydrocarbons (MOSH) and aromatic mineral oil hydrocarbons (MOAH) were appropriate to enable quantitation similar to situations where hydrogen or helium had been used. Slightly increased peak widths of individual hump components did not affect shapes and widths of the MOSH and MOAH humps were not significantly affected by the use of nitrogen as carrier gas. Notably, nitrogen carrier gas led to less solvent peak tailing and smaller baseline offset. Overall, nitrogen may be regarded as viable alternative to hydrogen or helium and may even extend the range of quantifiable compounds to highly volatile hydrocarbon eluting directly after the solvent peak.
This paper outlines significant advancements in our previously developed aerial gas tomography system, now optimized to reconstruct 2D tomographic slices of gas plumes with enhanced precision in outdoor environments. The core of our system is an aerial robot equipped with a custom-built 3-axis aerial gimbal, a Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensor for CH4 measurements, a laser rangefinder, and a wide-angle camera, combined with a state-of-the-art gas tomography algorithm. In real-world experiments, we sent the aerial robot along gate-shaped flight patterns over a semi-controlled environment with a static-like gas plume, providing a welldefined ground truth for system evaluation. The reconstructed cross-sectional 2D images closely matched the known ground truth concentration, confirming the system’s high accuracy and reliability. The demonstrated system’s capabilities open doors for potential applications in environmental monitoring and industrial safety, though further testing is planned to ascertain the system’s operational boundaries fully.
This paper explores combining a gimbal-mounted tunable diode laser absorption spectroscopy (TDLAS) sensor and a video camera to create a virtual gas camera for methane leak detection. This provides a low-to-zero-cost extension of typical TDLAS gas tomography systems. A prototype setup mounted on a ground robot is evaluated. Results acquired using a simulated methane leak show the feasibility of the virtual gas camera, accurately detecting methane leaks by overlaying concentrations onto a visual image. While the acquisition time is significantly longer than for traditional gas cameras, potential enhancements are discussed. The study concludes that the virtual gas camera is feasible and useful, despite its longer acquisition time. It serves as a valuable software-only addition to typical TDLAS gas tomography systems, offering quickly-available on-site data augmentation for visual leak assessment at low-to-zero cost.
This paper outlines significant advancements in our previously developed aerial gas tomography system, now optimized to reconstruct 2D tomographic slices of gas plumes with enhanced precision in outdoor environments. The core of our system is an aerial robot equipped with a custom-built 3-axis aerial gimbal, a Tunable Diode Laser Absorption Spectroscopy (TDLAS) sensor for CH4 measurements, a laser rangefinder, and a wide-angle camera, combined with a state-of-the-art gas tomography algorithm. In real-world experiments, we sent the aerial robot along gate-shaped flight patterns over a semi-controlled environment with a static-like gas plume, providing a welldefined ground truth for system evaluation. The reconstructed cross-sectional 2D images closely matched the known ground truth concentration, confirming the system’s high accuracy and reliability. The demonstrated system’s capabilities open doors for potential applications in environmental monitoring and industrial safety, though further testing is planned to ascertain the system’s operational boundaries fully.
This report contains detailed information on the preparation of the reference material as well as on homogeneity and stability investigations of the property of interest, the equivalent particle diameter, and on the analytical methods to determine the additional properties. The values for particle size distribution are based on the results from laser diffraction measurements of 3 different devices with at least 3 replicate measurements of 4 randomly chosen units of the reference material P206.
The presentation provides an overview of the current European initiatives to introduce the Digital Product Passport (DPP). Starting from the political background, reference is made to the implementation in various European directives. According to current considerations, explosives and pyrotechnics are not excluded from this. The introduction of the DPP system requires the development of a solid basis of relevant standards, which are now being developed. The aim of BAM's efforts will be to digitally align the classification processes with a view to these developments.
Scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders are increasingly relevant for fundamental research and industry. Examples are luminescent nano- and microparticles and phosphors of different compositions in various matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter to characterize the performance of these materials is the photoluminescence/fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. To identify and quantify the sources of uncertainty of absolute measurements of Φf of scattering samples, the first interlaboratory comparison (ILC) of three laboratories from academia and industry was performed by following identical measurement protocols. Thereby, two types ofcommercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring the Φf of transparent and scattering dye solutions and solid phosphors, namely, YAG:Ce optoceramics of varying surface roughness, used as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While the Φf values of the liquid samples matched between instruments, Φf measurements of the optoceramics with different blanks revealed substantial differences. The ILC results underline the importance of the measurement geometry, sample position, and blank for reliable Φf data of scattering the YAG:Ce optoceramics, with the blank’s optical properties accounting for uncertainties exceeding 20%.
The talk summarizes challenges in microplastic analysis. It shows the preparation of microplastic reference materials as well as the testing on homogeneity and stability. The reference material is used in an international laboratory comparison to compare different detection methods used for microplastic analysis. The methods used were µ-IR (FTIR+LDIR) for number-based methods and TED-GC/MS and Py-GC/MS for mass-based methods. The ILC was done under the umbrella of VAMAS TWA 45. Results of the participants are presented.
Per- and polyfluoroalkyl substances (PFAS) were classified as a group of highly concerning chemicals over the last decades. Because of the high persistence of PFAS, their previous use led to contamination of the environment and human population. Due to ongoing use and incomplete remediation or destruction methods, the PFAS background in the environment is growing continuously.
The presence of ultrashort PFAS (with ≤3 carbon atoms) in the environment is often overlooked despite their contributions to PFAS levels. These compounds may directly contaminate the environment and arise from degradation of polyfluorinated compounds as well as incomplete PFAS destruction in certain industrial processes. Nonetheless, few approaches for targeted analysis of ultrashort PFASs have been developed, except for trifluoroacetic acid (TFA). Beside liquid (LC-MS/MS), supercritical fluid (SFC-MS/MS), and ion chromatography (IC-MS)-based systems, gas chromatography coupled with mass spectrometry (GC-MS) is a promising method for detection and quantification of ultrashort PFAS.
The goal of this study was to develop a simple headspace GC-MS method for the quantification of ultrashort perfluorocarboxylic acids (PFCAs) and polyfluorinated alcohols (PFOHs) in water samples. In contrast to PFOHs, functionalization of PFCAs was required for quantification. This was done by esterification with methanol at 80 °C, which can be carried out directly in the headspace GC-MS system.
Moreover, several parameters were optimized to achieve a low limit of quantification (LOQ) for the analytes used: i) The ratio of the aqueous solution, methanol, and available gas phase within the analysis vessel, ii) the concentration of additional acid in esterification mixtures of PFCAs, iii) shaking frequency and iv) shaking time before analysis. After optimizing the procedure, we were able to quantify ultrashort PFCAs and PFOHs. Thus, our developed headspace GC-MS method has the potential to be used as an alternative target analysis for ultrashort-chain PFCAs and PFOHs in various water samples (groundwater, wastewater).
Preliminary results of an interlaboratory comparison on microplastics organised by plasticsfate
(2023)
Microplastics are everywhere in the environment, but analytics is challenging. Since harmonisation is missing as well es suitable reference materials, BAM did under th umbrella of VAMAS funded by the EU Horizon 2020 project PlasticsFate a ILC for microplastic detection methods. Methods adressed were IR, Raman, Py-GC/MS and TED-GC/MS. The talk gives a first presentation and evaluation on the results.