Mixed-Matrix Organo-Silica-Hydrotalcite Membrane for CO2 Separation Part 2: Permeation and Selectivity Study.

This study introduces an innovative approach to designing membranes capable of separating CO2 from industrial gas streams at higher temperatures. The novel membrane design seeks to leverage a well-researched, high-temperature CO2 adsorbent, hydrotalcite, by transforming it into a membrane. This was achieved by combining it with an amorphous organo-silica-based matrix, extending the polymer-based mixed-matrix membrane concept to inorganic compounds. Following the membrane material preparation and investigation of the individual membrane in Part 1 of this study, we examine its permeation and selectivity here. The pure 200 nm thick hydrotalcite membrane exhibits Knudsen behavior due to large intercrystalline pores. In contrast, the organo-silica membrane demonstrates an ideal selectivity of 13.5 and permeance for CO2 of 1.3 × 10-7 mol m-2 s-1 Pa-1 at 25 °C, and at 150 °C, the selectivity is reduced to 4.3. Combining both components results in a hybrid microstructure, featuring selective surface diffusion in the microporous regions and unselective Knudsen diffusion in the mesoporous regions. Further attempts to bridge both components to form a purely microporous microstructure are outlined.

Degradation and Recondensation of Metal Oxide Nanoparticles in Laminar Premixed Flames.

The behavior of technical nanoparticles at high temperatures was measured systematically to detect morphology changes under conditions relevant to the thermal treatment of end-of-life products containing engineered nanomaterials. The focus of this paper is on laboratory experiments, where we used a Bunsen-type burner to add titania and ceria particles to a laminar premixed flame. To evaluate the influence of temperature on particle size distributions, we used SMPS, ELPI and TEM analyses. To measure the temperature profile of the flame, we used coherent anti-Stokes Raman spectroscopy (CARS). The comprehensible data records show high temperatures by measurement and equilibrium calculation for different stoichiometries and argon admixtures. With this, we show that all technical metal oxide nanoparticle agglomerates investigated reform in flames at high temperatures. The originally large agglomerates of titania and ceria build very small nanoparticles (<10 nm/"peak 2") at starting temperatures of <2200 K and <1475 K, respectively (ceria: Tmelt = 2773 K, Tboil = 3873 K/titania: Tmelt = 2116 K, Tboil = 3245 K). Since the maximum flame temperatures are below the evaporation temperature of titania and ceria, enhanced vaporization of titania and ceria in the chemically reacting flame is assumed.

Pyrolysis of mixed engineering plastics: Economic challenges for automotive plastic waste.

Chemical recycling of complex plastic waste via pyrolysis can reduce fossil resource dependence of the plastics value chain and greenhouse gas emissions. However, economic viability is crucial for its implementation, especially considering challenging waste streams with high shares of engineering plastics that have lower pyrolysis product quality than standard thermoplastics waste. Thus, this study conducts a techno-economic assessment determining the profitability factors of pyrolysis plants for automotive plastic waste in Germany including different plant capacities and calculating cost-covering minimum sales prices for the resulting pyrolysis oil. Main findings are that due to economies of scale, the cost-covering minimum sales prices vary between 1182 €/Mg pyrolysis oil (3750 Mg input/year) and 418 €/Mg pyrolysis oil (100,000 Mg input/year). The pyrolysis technology employed must be robust and scalable to realize these economies of scale. Large plant capacities face challenges such as feedstock availability at reasonable costs, constant feedstock quality, and pyrolysis oil quality, affecting pyrolysis oil pricing. Due to the limited yield and quality of pyrolysis oil produced from these technically demanding feedstocks, policy implications are that additional revenue streams such as gate fees or subsidies that are essential to ensure a positive business case are necessary. Depending on the assessed plant capacity, additional revenues between 720 and 59 €/Mg pyrolysis oil should be realized to be competitive with the price of the reference product heavy fuel oil. Otherwise, the environmental potential of this technology cannot be exploited.

A Novel Plenoptic Camera-Based Measurement System for the Investigation into Flight and Combustion Behavior of Refuse-Derived Fuel Particles.

In the past several decades, refuse-derived fuels (RDFs) have been widely applied in industrial combustion processes, for instance, in cement production. Since RDF is composed of various waste fractions with complex shapes, its flight and combustion behaviors can be relatively complicated. In this paper, we present a novel plenoptic camera-based spatial measurement system that uses image processing approaches to determine the dwell time, the space-sliced velocity in the depth direction, and the ignition time of various applied RDF fractions based on the obtained images. The image processing approach follows the concept of tracking-by-detection and includes a novel combined detection method, a 2.5D multiple particle tracking algorithm, and a postprocessing framework to tackle the issues in the initial tracking results. The thereby obtained complete spatial fuel trajectories enable the analysis of the flight behaviors elaborated in the paper. The acquired particles' properties (duration, velocity, and ignition time) reversely prove the availability and applicability of the developed measurement system. The adequacy and accuracy of the proposed novel measurement system are validated by the experiments of detecting and tracking burning and nonburning fuel particles in a rotary kiln. This new measurement system and the provided experimental results can benefit a better understanding of the RDF's combustion for future research.

Exploring the synergistic effects of biochar and arbuscular mycorrhizal fungi on phosphorus acquisition in tomato plants by using gene expression analyses.

Arbuscular mycorrhizal (AM) fungi are symbiotic organisms that contribute significantly to plant mineral nutrition, mainly phosphate. However, their benefits are constricted by the availability of phosphate in the soil, and thus they are recalcitrant as amendment in highly fertilized soils. Biochars are by-products of the pyrolysis of biomass in the absence of oxygen. They can improve soil properties and act as a source of nutrients for plants. However, depending on their origin, the final composition of biochars is extremely variable and thus, their efficiency unpredictable. In order to gain mechanistic insights into how the combined application of biochars and AM fungi contribute to plant phosphate nutrition and growth, we used gene expression analyses of key symbiotic marker genes. We compared for this analysis two biochars originated from very different feedstocks (chicken manure and wheat straw) on tomato plants with or without the AM fungus Rhizophagus irregularis. Our results show that the synergy between AM fungi and biochars as P biofertilizers is greatly governed by the origin of the biochar that determines the speed at which phosphate is released to the soil and absorbed by the plant. Thus, chicken manure biochar quickly impacted on plant growth by readily releasing P, but it turned out detrimental for symbiosis formation, decreasing colonization levels and expression of key symbiotic plant marker genes such as SlPT4 or SlFatM. In contrast, wheat straw biochar was inferior at improving plant growth but stimulated the establishment of the symbiosis, producing plants with the same concentration of phosphate as those with the chicken manure. Taken together, slow P releasing biochars from plant residues appears to be a more promising amendment for long terms experiments in which biofertilizers such as AM fungi are considered. Furthermore, our results indicate that implementing plant transcriptomic analyses might help to mechanistically dissect and better understand the effects of biochars on plant growth in different scenarios.

Comparing the Toxicological Responses of Pulmonary Air-Liquid Interface Models upon Exposure to Differentially Treated Carbon Fibers.

In recent years, the use of carbon fibers (CFs) in various sectors of industry has been increasing. Despite the similarity of CF degradation products to other toxicologically relevant materials such as asbestos fibers and carbon nanotubes, a detailed toxicological evaluation of this class of material has yet to be performed. In this work, we exposed advanced air-liquid interface cell culture models of the human lung to CF. To simulate different stresses applied to CF throughout their life cycle, they were either mechanically (mCF) or thermo-mechanically pre-treated (tmCF). Different aspects of inhalation toxicity as well as their possible time-dependency were monitored. mCFs were found to induce a moderate inflammatory response, whereas tmCF elicited stronger inflammatory as well as apoptotic effects. Furthermore, thermal treatment changed the surface properties of the CF resulting in a presumed adhesion of the cells to the fiber fragments and subsequent cell loss. Triple-cultures encompassing epithelial, macrophage, and fibroblast cells stood out with an exceptionally high inflammatory response. Only a weak genotoxic effect was detected in the form of DNA strand breaks in mono- and co-cultures, with triple-cultures presenting a possible secondary genotoxicity. This work establishes CF fragments as a potentially harmful material and emphasizes the necessity of further toxicological assessment of existing and upcoming advanced CF-containing materials.

Recycling of polystyrene-based external thermal insulation composite systems - Application of combined mechanical and chemical recycling.

The material recycling of complex waste streams such as external thermal insulation composite systems (ETICS) is challenging, which is why their recycling in the sense of a circular economy is currently hardly established. Therefore, the combined mechanical and thermochemical recycling of ETICS based on expanded polystyrene (EPS) is investigated experimentally and by simulating full process chains in order to evaluate circular economy opportunities. Model ETICS as example for building and construction waste is pretreated mechanically, followed by either pyrolysis and / or gasification steps, and full mass and energy balances are derived. By the combined recycling, inorganic compounds can be separated to a large extent allowing a pre-concentrate generation. The plastic-rich pre-concentrate is converted into either pyrolysis oil with a high styrene monomer content of 51 wt% or to synthesis gas in the subsequent thermochemical conversions. The holistic approach enables a high carbon recycling rate between 53 and 68 wt%. In addition, the investigation reveals technology limitations and opportunities to be further developed and optimized.

Gene Expression Profiling of Mono- and Co-Culture Models of the Respiratory Tract Exposed to Crystalline Quartz under Submerged and Air-Liquid Interface Conditions.

In vitro lung cell models like air-liquid interface (ALI) and 3D cell cultures have advanced greatly in recent years, being especially valuable for testing advanced materials (e.g., nanomaterials, fibrous substances) when considering inhalative exposure. Within this study, we established submerged and ALI cell culture models utilizing A549 cells as mono-cultures and co-cultures with differentiated THP-1 (dTHP-1), as well as mono-cultures of dTHP-1. After ALI and submerged exposures towards α-quartz particles (Min-U-Sil5), with depositions ranging from 15 to 60 µg/cm2, comparison was made with respect to their transcriptional cellular responses employing high-throughput RT-qPCR. A significant dose- and time-dependent induction of genes coding for inflammatory proteins, e.g., IL-1A, IL-1B, IL-6, IL-8, and CCL22, as well as genes associated with oxidative stress response such as SOD2, was observed, even more pronounced in co-cultures. Changes in the expression of similar genes were more pronounced under submerged conditions when compared to ALI exposure in the case of A549 mono-cultures. Hereby, the activation of the NF-κB signaling pathway and the NLRP3 inflammasome seem to play an important role. Regarding genotoxicity, neither DNA strand breaks in ALI cultivated cells nor a transcriptional response to DNA damage were observed. Altogether, the toxicological responses depended considerably on the cell culture model and exposure scenario, relevant to be considered to improve toxicological risk assessment.

Comparing α-Quartz-Induced Cytotoxicity and Interleukin-8 Release in Pulmonary Mono- and Co-Cultures Exposed under Submerged and Air-Liquid Interface Conditions.

The occupational exposure to particles such as crystalline quartz and its impact on the respiratory tract have been studied extensively in recent years. For hazard assessment, the development of physiologically more relevant in-vitro models, i.e., air-liquid interface (ALI) cell cultures, has greatly progressed. Within this study, pulmonary culture models employing A549 and differentiated THP-1 cells as mono-and co-cultures were investigated. The different cultures were exposed to α-quartz particles (Min-U-Sil5) with doses ranging from 15 to 66 µg/cm2 under submerged and ALI conditions and cytotoxicity as well as cytokine release were analyzed. No cytotoxicity was observed after ALI exposure. Contrarily, Min-U-Sil5 was cytotoxic at the highest dose in both submerged mono- and co-cultures. A concentration-dependent release of interleukin-8 was shown for both exposure types, which was overall stronger in co-cultures. Our findings showed considerable differences in the toxicological responses between ALI and submerged exposure and between mono- and co-cultures. A substantial influence of the presence or absence of serum in cell culture media was noted as well. Within this study, the submerged culture was revealed to be more sensitive. This shows the importance of considering different culture and exposure models and highlights the relevance of communication between different cell types for toxicological investigations.

Thermal treatment of carbon-fibre-reinforced polymers (Part 2: Energy recovery and feedstock recycling).

The use of carbon fibre (CF)-reinforced plastics has grown significantly in recent years, and new areas of application have been and are being developed. As a result, the amount of non-recyclable waste containing CF is also rising. There are currently no treatment methods for this type of waste. Within this project different approaches for the treatment of waste containing CF were investigated. Main subject of the research project were large-scale investigations on treatment possibilities and limits of waste containing CF in high temperature processes, with focus on the investigation of process-specific residues and possible fibre emission. The results showed that the two conventional thermal waste treatment concepts with grate and rotary kiln firing systems are not suitable for a complete oxidation of CFs due to the insufficient process conditions (temperature and dwell time). The CFs were mainly discharged via the bottom ash/slag. Due to the partial decomposition during thermal treatment, World Health Organization (WHO) fibres occurred in low concentrations. The tests run in the cement kiln plant have shown the necessity of comminution for waste containing CF. With respect to the short testing times and moderate quantities of inserted CF, a final evaluation of the suitability of this disposal path was not possible. The use of specially processed waste containing CF (carbon-fibre-reinforced plastic (CFRP) pellets) as a carbon substitute in calcium carbide production led to high carbon conversion rates. In the unburned furnace dust, which is marketed as a by-product of the process, CFs in relevant quantities could be detected.

Agglomeration State of Titanium-Dioxide (TiO2) Nanomaterials Influences the Dose Deposition and Cytotoxic Responses in Human Bronchial Epithelial Cells at the Air-Liquid Interface.

Extensive production and use of nanomaterials (NMs), such as titanium dioxide (TiO2), raises concern regarding their potential adverse effects to humans. While considerable efforts have been made to assess the safety of TiO2 NMs using in vitro and in vivo studies, results obtained to date are unreliable, possibly due to the dynamic agglomeration behavior of TiO2 NMs. Moreover, agglomerates are of prime importance in occupational exposure scenarios, but their toxicological relevance remains poorly understood. Therefore, the aim of this study was to investigate the potential pulmonary effects induced by TiO2 agglomerates of different sizes at the air-liquid interface (ALI), which is more realistic in terms of inhalation exposure, and compare it to results previously obtained under submerged conditions. A nano-TiO2 (17 nm) and a non-nano TiO2 (117 nm) was selected for this study. Stable stock dispersions of small agglomerates and their respective larger counterparts of each TiO2 particles were prepared, and human bronchial epithelial (HBE) cells were exposed to different doses of aerosolized TiO2 agglomerates at the ALI. At the end of 4h exposure, cytotoxicity, glutathione depletion, and DNA damage were evaluated. Our results indicate that dose deposition and the toxic potential in HBE cells are influenced by agglomeration and exposure via the ALI induces different cellular responses than in submerged systems. We conclude that the agglomeration state is crucial in the assessment of pulmonary effects of NMs.

Starve to Sustain-An Ancient Syrian Landrace of Sorghum as Tool for Phosphorous Bio-Economy?

Phosphorus (P) is an essential macronutrient, playing a role in developmental and metabolic processes in plants. To understand the local and systemic responses of sorghum to inorganic phosphorus (Pi) starvation and the potential of straw and ash for reutilisation in agriculture, we compared two grain (Razinieh) and sweet (Della) sorghum varieties with respect to their morpho-physiological and molecular responses. We found that Pi starvation increased the elongation of primary roots, the formation of lateral roots, and the accumulation of anthocyanin. In Razinieh, lateral roots were promoted to a higher extent, correlated with a higher expression of SbPht1 phosphate transporters. Infrared spectra of straw from mature plants raised to maturity showed two prominent bands at 1371 and 2337 cm-1, which could be assigned to P-H(H2) stretching vibration in phosphine acid and phosphinothious acid, and their derivates, whose abundance correlated with phosphate uptake of the source plant and genotype (with a higher intensity in Razinieh). The ash generated from these straws stimulated the shoot elongation and root development of the rice seedlings, especially for the material derived from Razinieh raised under Pi starvation. In conclusion, sorghum growing on marginal lands has potential as a bio-economy alternative for mineral phosphorus recycling.

Impact of Nanocomposite Combustion Aerosols on A549 Cells and a 3D Airway Model.

The use of nanomaterials incorporated into plastic products is increasing steadily. By using nano-scaled filling materials, thermoplastics, such as polyethylene (PE), take advantage of the unique properties of nanomaterials (NM). The life cycle of these so-called nanocomposites (NC) usually ends with energetic recovery. However, the toxicity of these aerosols, which may consist of released NM as well as combustion-generated volatile compounds, is not fully understood. Within this study, model nanocomposites consisting of a PE matrix and nano-scaled filling material (TiO2, CuO, carbon nano tubes (CNT)) were produced and subsequently incinerated using a lab-scale model burner. The combustion-generated aerosols were characterized with regard to particle release as well as compound composition. Subsequently, A549 cells and a reconstituted 3D lung cell culture model (MucilAir™, Epithelix) were exposed for 4 h to the respective aerosols. This approach enabled the parallel application of a complete aerosol, an aerosol under conditions of enhanced particle deposition using high voltage, and a filtered aerosol resulting in the sole gaseous phase. After 20 h post-incubation, cytotoxicity, inflammatory response (IL-8), transcriptional toxicity profiling, and genotoxicity were determined. Only the exposure toward combustion aerosols originated from PE-based materials induced cytotoxicity, genotoxicity, and transcriptional alterations in both cell models. In contrast, an inflammatory response in A549 cells was more evident after exposure toward aerosols of nano-scaled filler combustion, whereas the thermal decomposition of PE-based materials revealed an impaired IL-8 secretion. MucilAir™ tissue showed a pronounced inflammatory response after exposure to either combustion aerosols, except for nanocomposite combustion. In conclusion, this study supports the present knowledge on the release of nanomaterials after incineration of nano-enabled thermoplastics. Since in the case of PE-based combustion aerosols no major differences were evident between exposure to the complete aerosol and to the gaseous phase, adverse cellular effects could be deduced to the volatile organic compounds that are generated during incomplete combustion of NC.

A novel TEM grid sampler for airborne particles to measure the cell culture surface dose.

The applied surface dose is a key parameter for the measurement of toxic effects of airborne particles by air liquid interface exposure of human lung cells. Besides online measurement of the deposited particle mass by quartz crystal microbalance frequently other dose metrics such as particle size distribution, surface and agglomeration state are required. These particle properties and their spatial distribution can be determined by digital processing of micrographs obtained by transmission electron microscopy (TEM). Here, we report the development and characterization of a novel holder for film coated TEM copper grids, which allows for sampling under identical geometric and ambient conditions as in a cell culture chamber. The sample holder avoids artefacts by reliable grounding of the grids and improves handling of the grids to prevent damage of the sensitive film. This sample holder is applied during exposure experiments with titanium dioxide nanoparticles. The measured dose of 0.2 µg/cm² corresponds well to the mass loading signal of the quartz crystal microbalance. Additionally, the spatial distribution of particles on the sampling surface shows a good homogeneity of deposition. This novel sampling method allows verifying other dosimetry methods and gives additional information about particle properties and homogeneity of the dose.

Waste incineration of Polytetrafluoroethylene (PTFE) to evaluate potential formation of per- and Poly-Fluorinated Alkyl Substances (PFAS) in flue gas.

In recent years, concerns over some per- and polyfluorinated alkyl substances (PFAS) have grown steadily. PFAS are a large group of chemical substances with widely differing properties. While one class of PFAS, fluoropolymers, have been demonstrated to meet the OECD criteria for polymers of low concern during the in use phase of their lifecycle, questions remain regarding waste handling at the end of useful life for products containing fluoropolymers. To show that polytetrafluoroethylene (PTFE) can be almost fully transformed into fluorine (F) (as hydrofluoric acid (HF)) and to study the possible generation of low molecular weight per- and polyfluorinated alkyl substances (PFAS), PTFE combustion under typical waste incineration conditions at the BRENDA (German acronym for "Brennkammer mit Dampfkessel") pilot plant at Karlsruhe Institute of Technology (KIT) was investigated. Results indicate that, within procedural quantitation limits, no statistically significant evidence was found that the PFAS studied were created during the incineration of PTFE. Therefore, municipal incineration of PTFE using best available technologies (BAT) is not a significant source of the studied PFAS and should be considered an acceptable form of waste treatment.

Modelling grate combustion of biomass and low rank fuels with CFD application.

A reactor cascade model is used for the numerical simulation of the fixed bed combustion of biomass, municipal solid waste and other low rank fuels. Non-spherical particle geometries are accounted for via their plain specific surface. The model is able to reproduce key quantities like ignition delay time, ignition rate, reaction front velocity and mass conversion rate in close agreement with experimental data. This provides a basis to transfer the fixed bed results to the situation of continuous combustion on forward acting grates. A simplified numerical procedure is presented for this purpose. It allows to estimate the structure of a fuel bed moving on the grate as well as the overbed gas temperature and composition. These data serve as input for separate CFD applications which simulate the gas flow in small scale and in industrial scale power plants together with the associated heat transfer processes. Validation of the modelling is presented for lab scale and bench scale experiments as well as for an industrial municipal solid waste incinerator.

Screw pyrolysis technology for sewage sludge treatment.

Sewage sludge quantities have grown continuously since the introduction of the European Directive (UWWTD 91/271/EEC) relating to the treatment of urban wastewater. In the present, most of the sewage sludge is combusted in single fuels incineration plants or is co-fired in waste incineration or coal power plants. The combustion of sewage sludge is a proven technology. Other treatments, such as fluidized bed gasification, were successfully adopted to produce suitable syngas for power production. Besides, the number of large wastewater treatment plants is relatively small compared to the local rural ones. Moreover, alternative technologies are arising with the main target of nutrients recovery, with a special focus on phosphorus. The aforementioned issues, i.e. the small scale (below 1MW) and the nutrients recovery, suggest that pyrolysis in screw reactors may become an attractive alternative technology for sewage sludge conversion, recovery and recycling. In this work, about 100kg of dried sewage sludge from a plant in Germany were processed at the newly developed STYX Reactor, at KIT. The reactor combines the advantages of screw reactors with the high temperature filtration, in order to produce particle and ash free vapors and condensates, respectively. Experiments were carried out at temperatures between 350°C and 500°C. The yield of the char decreased from 66.7wt.% to 53.0wt.%. The same trend was obtained for the energy yield, while the maximum pyrolysis oil yield of 13.4wt.% was obtained at 500°C. Besides mercury, the metals and the other minerals were completely retained in the char. Nitrogen and sulfur migrated from the solid to the condensate and to the gas, respectively. Based on the energy balance, a new concept for the decentral production of char as well as heat and power in an externally fired micro gas turbine showed a cogeneration efficiency up to about 40%.