Institut für Integrierte Naturwissenschaften, Abt. Chemie
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The production and use of polymeric materials have been increasing continuously for
years. At the same time, the entry of microplastics (MP) – tiny particles resulting from the
wear and tear of these materials – into our environment is growing as well. By now,
awareness of MP has reached broad sections of the population and also research and
development on this field are similarly becoming increasingly important. However,
insufficient standardization and the lack of suitable analytical methods still make
recording and tracking of MP difficult, so that it remains largely unregulated. Mass-based
analytical methods are particularly advantageous for the establishment of legal
regulations. Apart from thermogravimetric methods, however, there are currently few
alternatives in this field. In this context, the use of nuclear magnetic resonance
spectroscopy (NMR), previously only qualitatively applied to MP, has now also been
examined for its quantitative benefits. This work deals with the current state of
quantitative NMR spectroscopy (qNMR) and tests possibilities for optimization and further
development for this purpose. Initially, the reduction of sample volumes and thus
minimized effort and measurement time of the method will be examined by combining
different polymer types into simultaneously measurable groups, as well as the suitability
of homopolymer calibrations for the detection of copolymers. Existing restrictions during
measurement will be adopted, and thus extractive procedures for sample preparation are
implemented. Finally, the influence of real environmental samples will be assessed, and
measures to reduce interfering factors will be taken in to account. As a result, the method
encompasses at least six polymer types, from PMMA, PS, BR, and PVC to PA and PET, as
well as separate approaches for polymers such as PAN and LDPE. A modular sample
preparation protocol, including extractive fractionation into measurement groups and a
chemical digestion method for matrix reduction, will be established and expanded to
include options for diffusion measurement and application to low-field instruments.
Practical application will be presented using real-world examples, such as freshwater
biofilms, as well as the use for quality control of certified reference materials.
Furthermore, initial insights into future development possibilities, like for the detection of
tire abrasion, will be provided.
The presence of synthetic chemicals in the environment can affect both ecosystems and
human health. In particular, the increasing contamination of the aquatic environment by
complex mixtures of anthropogenic trace substances has become a major global concern.
Once released into the environment, these compounds can undergo diverse
transformation processes to form a wide range of transformation products (TPs), which
are commonly unknown. Transformation inevitably alters the pattern of contamination and
exposure, as new substances are formed with frequently different physicochemical
properties, environmental behavior and toxicity in comparison to their precursor
compounds. For instance, TPs can exhibit significantly greater persistence and mobility in
the aquatic environment, posing a threat to both aquatic ecosystems and drinking water
resources. Therefore, TPs need to be considered in the risk assessment and authorization
process of chemicals. However, due to a combination of predictive, analytical, and
regulatory challenges, TPs currently remain largely unrecognized and unregulated. By
addressing these challenges, this thesis comprehensively characterizes the entry paths,
occurrence, fate, and (eco)toxicological relevance of selected TPs in the aquatic system in
Germany. These TPs have been largely overlooked in environmental studies and aquatic
monitoring programs for decades, despite their precursors being produced and used in
large quantities on a global scale.
The highly persistent and mobile substance trifluoroacetate (TFA) has garnered
significant attention in recent years due to its diverse sources, widespread occurrence in
the aquatic environment, and the lack of economically viable options to remove TFA from
contaminated waters. One of the most frequently discussed diffuse sources is the
formation of TFA in the atmosphere through the oxidation of volatile precursors and its
subsequent scavenging from the atmosphere by wet deposition. Despite the previously
reported occurrence of TFA in precipitation, the lack of recent and comprehensive data
has severely limited the understanding of the significance of wet deposition as a source of
TFA to the (aquatic) environment. Thus, in the present work, a nationwide field monitoring
campaign covering all precipitation events over a one-year sampling period was
conducted at eight sites across Germany. Samples were analyzed for TFA using ion
exchange chromatography (IC) coupled to negative-ion electrospray tandem mass
spectrometry (ESI-MS/MS). Of the analyzed samples, 16% exhibited TFA concentrations
≥ 1 μg/L. The precipitation-weighted average TFA concentration of 0.34 μg/L highlighted
that wet deposition alone is responsible for approximately 0.3 to 0.4 μg/L of TFA in
surface waters in Germany. The annual wet deposition fluxes ranged from 91 to
400 μg/m², with the highest fluxes observed in densely populated regions. The annual wet
deposition of TFA for Germany during the observation period was estimated to be 68 t.
The sampling revealed a pronounced seasonality, with the highest concentrations and wet
deposition fluxes of TFA observed in summer. Pearson correlation analyses indicated that
the transformation of TFA precursors in the troposphere is enhanced in summer due to
elevated concentrations of photochemically generated oxidants, primarily •OH, which
ultimately results in increased atmospheric TFA deposition. Overall, the study provided the
first published data on TFA in precipitation in Germany since 1995/96. The derived data
serves as a benchmark for future studies. In addition, it allows for the establishment of
mass balances and can be used to develop models to predict the loads of TFA entering
the aquatic environment from multiple sources.
The lack of robust historical data on the wet deposition fluxes of TFA also impeded long-
term trend analyses. Specifically, a postulated increase in atmospheric formation and
deposition of TFA due to substantial emission increases of numerous volatile TFA
precursors in recent decades remained unquantified. To address this knowledge gap,
archived plant samples were analyzed to evaluate the long-term temporal trends in the
atmospheric deposition of TFA in Germany. A robust and highly sensitive analytical
method for TFA in plant matrices was developed and validated. The method
encompassed a three-step sequential extraction procedure followed by the analysis of the
diluted sample extracts using IC-ESI-MS/MS. Subsequently, archived leaf samples of
various tree species and sampling sites from the German Environmental Specimen Bank
(observation period: 1989−2020) were analyzed for TFA. Statistical analysis revealed
significant (p < 0.05) positive trends in TFA concentrations in plant leaves, which is likely
the result of both phytoaccumulation and increasing emissions of gaseous TFA precursors
over the observation period. The concentrations increased by factors of up to 12 from
1989 to 2020. The highest concentrations (up to ∼1,000 μg/kg dry weight) were found in
Lombardy poplar leaves. Overall, the study presents the first trend analysis of TFA in biota
and raises awareness of the escalating atmospheric deposition of TFA over the past three
decades.
Sulfamate has previously been identified as a TP of the artificial sweeteners cyclamate
and acesulfame in wastewater and drinking water treatment. The preliminary results
indicated that sulfamate concentrations in wastewater treatment plant (WWTP) effluent
are substantially higher than those of other wastewater-borne contaminants. However,
despite its high global production and usage, no information was available on the sources,
occurrence, and environmental significance of sulfamate in the aquatic system in
Germany. To close this knowledge gap, a quantitative monitoring approach of different
urban water cycle compartments was conducted. Target analysis based on IC-ESI-MS/MS
revealed exceptionally high concentrations of sulfamate in wastewater (up to 1,900 μg/L),
surface water (up to 580 μg/L), and finished drinking water (up to 140 μg/L) in Germany.
Considering the limited data on short-term ecotoxicity, approximately 30% of the
sulfamate concentrations detected in groundwater and surface water samples exceeded
the derived predicted no-effect concentration (PNEC) of sulfamate. Therefore, the
potential impact of sulfamate on the aquatic ecosystem in Germany cannot be excluded.
Municipal WWTP effluent was identified as the primary source of sulfamate for the aquatic
system, as its concentrations correlated positively (r > 0.77) with the municipal wastewater
tracer carbamazepine in samples from different waterbodies. Ozonation and activated
sludge experiments demonstrated that sulfamate can be formed through chemical and
biological degradation of various precursors containing a sulfonamide group.
Nevertheless, the transformation of precursors to sulfamate in WWTPs and receiving
waters was found to be quantitatively insignificant, due to the substantial direct use of
sulfamic acid as a descaling agent in domestic and industrial applications. Laboratory
batch experiments, in conjunction with the findings from the sampling conducted at full-
scale waterworks, demonstrated that the commonly applied drinking water treatment
techniques, including ozonation and activated carbon filtration, are largely ineffective in
removing sulfamate. Bank filtration was identified as the only option to efficiently eliminate
sulfamate from contaminated raw water resources (removal: 62% to 99%). Overall, the
study presents the first comprehensive analysis of sulfamate in the urban water cycle and
suggests that there may be other high production volume inorganic chemicals that are
currently overlooked in environmental studies and monitoring programs.
Despite pantoprazole (PPZ) being one of the most widely prescribed human
pharmaceuticals globally, consistently low concentrations of this proton-pump inhibitor in
environmental water samples have been documented. This can be attributed to the
extensive metabolism of PPZ within the human body, with only minor amounts of the
parent compound being excreted. Since environmental monitoring and risk assessment
for regulatory purposes focus on the parent substances of pharmaceuticals, it was
assumed that the current environmental exposure associated with the use of PPZ is
considerably underestimated. In the presented thesis, 4′-O-demethyl-PPZ sulfide (M1)
was identified as the most relevant PPZ metabolite for environmental analysis. This was
achieved by applying reversed-phase high-performance liquid chromatography (RP-
HPLC) coupled to high-resolution mass spectrometry (HRMS) to urine samples of a PPZ
user, as well as to municipal wastewater. M1, which had not been investigated in previous
monitoring studies, was found to be ubiquitous in WWTP influent and effluent (max.:
3 μg/L, detention frequency: 100%) as well as in surface water (max.: 1.2 μg/L; detection
frequency: 97%) in Germany. Its average surface water concentration was approximately
30 times higher than that of the parent compound PPZ. Moreover, quantitative structure-
toxicity relationship (QSTR) modeling indicated a lower preliminary freshwater PNEC for
M1 (4.8 μg/L) compared to PPZ (28 μg/L). The analysis of archived suspended particulate
matter (SPM) samples from the Rhine at Koblenz revealed that the concentrations of M1
increased significantly from 2005 to 2015 and were positively correlated with the
prescription volume of PPZ. Conventional biological wastewater treatment was found to
be insufficient to remove M1 (average removal: 22%). Laboratory-scale experiments and
the analysis of samples taken after different treatment steps of an advanced full-scale
WWTP demonstrated that post-treatment with activated carbon as well as ozonation can
significantly improve the removal of M1 and PPZ during wastewater treatment, thereby
reducing their release to the aquatic environment. During ozonation, a rapid oxidation of
M1 was observed, accompanied by the formation of several ozonation products, which
were proposed for the first time. The identity of the main ozonation TPs of M1 was
confirmed through the synthesis of reference compounds. Their detection in samples
collected after the ozonation step of a full-scale WWTP demonstrated the transferability of
the laboratory-scale ozonation experiments. M1 was found to be sufficiently removed from
contaminated source waters (max. raw water concentration: 0.25 μg/L) by bank filtration
under different redox conditions (removal ≥ 80 %) and by other commonly applied
purification processes in drinking water production. In summary, this study revealed that
the environmental exposure and risk associated with the use of PPZ have been previously
underestimated, which likely extends to other human pharmaceuticals. Therefore, these
findings call for more sophisticated approaches to environmental monitoring and risk
assessment of pharmaceuticals that take TPs into account.
This thesis provides an in-depth understanding of the entry paths, occurrence, fate, and
environmental significance of selected TPs in the aquatic system in Germany. It
significantly advances our understanding of the introduction of TFA into the water cycle,
by characterizing the source of wet deposition and elucidating long-term temporal trends
of atmospherically deposited TFA. Additionally, the thesis gives comprehensive insights
into the formation, behavior, removability, and potential (eco)toxicological risks of
sulfamate, PPZ and its TPs. The thesis addresses key challenges in assessing and
integrating TPs into chemical management and presents solutions to overcome these
challenges. Finally, it highlights the urgent need for increased focus on TPs in research,
aquatic monitoring, and regulation to safeguard the environment and human health.
Water is the basis of all life, a biotope for a variety of organisms and an important component of the
natural balance. For this reason, it is essential to protect water from contamination by anthropogenic
organic micropollutants (MPs) and to develop various innovative strategies for the treatment and reuse
of wastewater. Conventionally biologically treated municipal wastewater contains many organic MPs
that pose a potential threat to aquatic ecosystems and drinking water resources. To date, the focus has
been on physicochemical processes such as activated carbon treatment or ozonation to improve the
removal of MPs in wastewater treatment plants (WWTPs), while knowledge of biological removal
processes and ways to optimize the biological removal of organic MPs is comparatively limited.
Especially in arid and semi-arid regions, treated wastewater is also an important resource for wastewater
reuse for irrigation or drinking water treatment. In consequence of increasing droughts due to climate
change, the reuse of treated wastewater is also increasingly being discussed in Germany. Often the water
is reused after targeted groundwater recharge, while concepts for optimizing the removal of MPs during
soil passages are still scare. In order to assess the potential and limitations of biological wastewater
treatment as well as targeted groundwater recharge for the removal of organic MPs, a better knowledge
of the biological biotransformation processes and the environmental conditions influencing them is
required. Microbial communities and their enzyme pools play a key role in these processes. However,
the influence of environmental conditions on the composition and functional characteristics of microbial
communities, and how this in turn affects the biotransformation potential of MPs with different
structural characteristics, has been little studied. In addition, knowledge about MP-biotransforming
bacteria is often derived from enrichment or even pure culture studies, which are not directly transferable
to the environment.
Against this background, this dissertation focuses on the systematic investigation of the
biotransformation of MPs in contact with activated sludge (simulation of biotransformation processes
in biological treatment stages of WWTPs) and filter materials (simulation of processes in groundwater
recharge systems) under defined laboratory conditions. The aim is to elucidate relationships between
the composition and functional characteristics of microbial communities, microbiologically determined
biotransformation processes and their optimal process conditions, as well as the chemical structure and
primary enzymatically catalyzed biotransformation reactions of MPs.
The first part of the work focuses on the composition of microbial communities and the
biotransformation of MPs depending on defined process parameters in five differently operated
wastewater reactors, divided into two reactor cascades at pilot scale and one full-scale WWTP. The first
cascade consisted of three reactors, the first of which served as a reference reactor with conventional
activated sludge (CAS) treatment. The following reactors operate under anoxic to anaerobic and strictly
anaerobic conditions, respectively. The other cascade consists of two reactors, the first anaerobic and the second aerobic, followed by a simplified vessel to prevent nitrate output, as half of the effluent was
recirculated to the first anaerobic reactor. All five reactors and the WWTP were analyzed for the
biotransformation of 33 MPs and the composition of the microbial community by LC-MS/MS and 16S
rRNA gene sequencing, respectively. The results showed a slight but significant improvement in the
overall biotransformation of MPs in the reactor cascades (about 20%) compared to the WWTP. In
particular, the biotransformation of compounds that are not or only slightly degradable (< 30%) in
conventional wastewater treatment, such as diatrizoate, venlafaxine and diclofenac, was significantly
improved (about 70%). Twelve of the 33 MPs showed an increase in biotransformation of at least 30%
compared to the reference reactor and the WWTP. In detail, the reactor cascade consisting of the
anaerobic pre-treatment showed three times more MPs than the reactor cascade with the anaerobic post-
treatment. Although the environmental conditions (nutrient availability and redox conditions) differed
considerably between the reactors, molecular analysis of the microbial community revealed a core
community of 143 genera, with 54% of the taxa belonging to the phylum Proteobacteria, with the beta
subdivision as the most dominant class. On the other hand, a specialized community consisting of 90
genera was identified that contributed most to the differences between the reactor communities. These
genera were shown to reflect the prevailing nutrient, redox and operating conditions of each treatment.
It was also found that the relative abundances of several genera of the specialized community correlated
with the biotransformation of certain MPs as well as with process parameters (especially redox
conditions). These genera may not necessarily be directly involved in the biotransformation of MPs, but
could be promising biological indicators for the establishment and control of operating conditions
favorable to the biotransformation of certain MPs. For the two reactor cascades analyzed, it was
concluded that the redox conditions as well as the carbon supply were essential factors for the
composition of the specialized community and the biotransformation of the MPs. In addition, the 16S
rRNA gene amplicon sequencing proved to be a complementary tool to confirm process conditions by
correlation. In conclusion, the efficiency of MP biotransformation in conventional WWTPs depends on
key parameters such as redox conditions, biodiversity or the presence of several genera of specialized
microbial communities identified as indicator organisms.
Against the background of previous knowledge that biofilms from moving bed biofilm reactors
(MBBRs), which have been used so far in a few WWTPs, are more efficient in biotransforming certain
MPs, the second study used laboratory batch experiments to investigate the extent to which the
biotransformation potential of carrier-attached biofilms and suspended sludge from hybrid MBBRs
differ between three WWTPs, and whether these differences were also reflected in the composition of
the bacterial communities. The 31 MPs investigated were grouped according to their biotransformation
rates and examined for relationships between the biotransformation behavior and the known primary
biotransformation reactions are discernible. In general, the study confirmed the potential of hybrid
MBBRs for improved biotransformation of a variety of MPs. This could be attributed to an increased
biotransformation potential of the carrier-attached biofilms, especially for oxidatively degradable substances such as trimethoprim, diclofenac and mecoprop. Correlation analyses showed statistically
significant relationships between the occurrence of certain bacterial genera (e.g. Acidibacter, Nitrospira
or Rhizomicrobium) and the biotransformation rates of certain MPs. Thus, some of the identified genera
were also discussed as suitable indicators for the biotransformation potential of suspended sludge or
carrier-attached biofilm.
In the third part of the work, the biotransformation of up to 78 MPs was investigated under different
redox and substrate conditions in a defined column system at laboratory scale as well as ex situ under
uniform incubation conditions by incubating the column filter material in batch experiments. MPs were
categorized based on their biotransformation behavior and how well these categories matched primary
transformation reactions known from the literature or predicted using the Eawag pathway prediction
system for modelling microbial biotransformation pathways. The column system investigated consisted
of two large columns filled with technical sand, an intermediate aeration and four smaller columns, all
connected in series. In the first column, characterized by a carbon-rich environment with high biomass
and strong oxygen depletion, 23 MPs were efficiently removed (>80% removal), while 19 substances
were better or exclusively removed under carbon-limited oligotrophic conditions in the columns after
re-aeration. While the MPs removed predominantly in the first column were mostly attributed to
biotransformation by comparatively ubiquitous and fast transformation reactions such as the oxidation
of alcohols or amide hydrolysis, the biotransformation of MPs removed more efficiently under the oxic
and oligotrophic conditions in the rear columns was characterized by slower transformation reactions
such as N-dealkylation of primary and secondary amines or the hydroxylation of aromatic rings. In
addition, several specific reactions described in the literature, such as the cleavage of C-Cl and C-O
bonds, could only be identified under oligotrophic conditions. The results suggest that conditions of
limited carbon availability may favor the development of alternative metabolic biotransformation
pathways. Furthermore, the observed association between system-specific MP removal and the expected
primary biotransformation reactions from the literature and prediction systems could serve as a basis for
accurately identifying the relevant enzymes in future studies, using metagenomic or metatranscriptomic
data.
Based on these considerations, molecular biological investigations were carried out in the fourth part of
this work by generating sequence-based data complementary to the biotransformation rate constants
during the batch experiments carried out in the third study. A first aim was to identify a statistical relation
between the microbial composition, the process conditions and the nutrient availability as well as the
biotransformation potential of 42 MPs depending on the biomass in the columns of the system.
Furthermore, the metabolic activities of the microbial communities of the first two columns of the
system were analyzed and the identified active enzymes were assigned to known metabolic pathways
and the activities were compared. In addition, the extent to which the biotransformation potential of the
columns was also reflected in the activity of enzymes that have been proven to belong to biotransformation pathways of MPs was investigated. To this end, modern sequencing methods were
used to generate data on the composition of the microbial community (16S rRNA gene sequencing) and
its actual activity in the form of expressed genes (metatranscriptome sequencing). The biotransformation
rates from the batch experiments of the third study were used by normalizing them with the gene copy
numbers (kbio), which were representative of the biomass. For half of the MPs, the highest normalized
kbio values were identified in the rear columns with increased carbon-limiting conditions. Furthermore,
most of the MPs investigated, such as sulfathiazole, sulfamethoxazole or rufinamide, showed an
improved biotransformation potential in these columns. The higher biotransformation potential under
carbon-limiting conditions was also confirmed by metatranscriptomic analysis, where an increased
metabolic capability and a higher functional activity to degrade MPs were observed in the carbon-
limiting column compared to the first nutrient-rich column. Taxonomic analysis revealed a decreasing
trend in biodiversity with a simultaneous increase in carbon-limiting conditions. Furthermore, the
microbial community differed depending on the nutrient and process conditions of the column materials
analyzed. However, within the carbon-limiting columns, the microbial community was similar and were
dominated by the genus Pseudomonas. By relating the biotransformation of MPs to the relative
abundance of taxa in the carbon-limiting columns, the genera of the phylum Acidobacteria and the
classes Alpha- and Gammaproteobacteria showed particularly high associations. In addition, four genera
showed a statistically positive correlation with the two structurally similar MPs sulfamethoxazole and
sulfathiazole.
Overall, no general improvement in biotransformation could be found for all MPs under the conditions
considered, with system- and condition-specific changes observed for individual compounds. However,
the studies indicated favorable environmental conditions for groups of MPs that showed increased
biotransformation linked with high abundant taxa, especially under carbon-limiting conditions and in
carrier-attached biofilms.
Within the scope of this work, new test methods were developed to determine the characteristic product properties of ladle well filler sands. Background is that up to now, there are no approved test methods for these product properties such as pourability, sintering behavior and infiltration behavior.
To substantiate this deficiency in testing methods, the general state-of-the-art testing methods of cohesionless bulk materials is presented and a variety of publications on ladle well filler sands are reviewed for their applied testing methodology.
The development of new test methods for the characterization of ladle well filler sands was based on test methods that were in part already standardized, such as the permeability measurement (infiltration) according to DIN 18130-1 from the field of geotechnics, the determination of the flow time with flow cups for coating materials (flowability) according to DIN EN ISO 2431:2011 and the monotonic heating method (MMH) according to ASTM E2584-20 for determining the thermal conductivity.
Since these test methods were not designed for examining free-flowing, non-cohesive bulk materials and therefore not for examining ladle well filler sand, it was necessary to adapt the parameters of the standardized test methods for use with well filler.
The parameters of the test methods mentioned (DIN 18130-1; DIN EN ISO 2431 and ASTM E2584-20) were checked for applicability and transferability to ladle well filler sand and new suitable parameters were added. The reproducibility of the results of the test methods was checked by a series of tests and the decisive influencing factors of ladle well filler sand on the results were determined.
The relevance of the results of the newly developed test methods was verified based on results from the European research project ILORA ("Improvement of Ladle Opening Rates", funded by the "Research Fund for Coal and Steel" RFCS, 2013-2016) and numerous publications with results from other research projects.
From the results of the newly developed test methods, key figures for the pourability, sintering behavior and infiltration behavior of ladle well filler sands were derived. The combination of these key figures was converted into a holistic analysis of ladle well filler sands, finally leading to an evaluation grid for well fillers. It is exactly that grid respectively network, that now allows for the first time to make qualified and reliable statements about the suitability for use of ladle well filler sands prior to industry application, which significantly facilitates the new development of such well fillers.
Microplastics (MP), i.e., plastic particles < 5 mm, are perceived as a threatening envi-
ronmental and human health issue. Growing public interest in this class of contaminants
requires standardized and harmonized methods for their quantification. While an abun-
dance of analytical methods (both particle-based and mass-based) for the detection of
microplastics is available, existing studies on the quantity of MP in the environment lack
comparability. Therefore, the aim of this work was to establish a fast, reliable screen-
ing method for the quantification of the most common synthetic polymers in complex
environmental samples.
This was accomplished by a two-step pressurized liquid extraction (PLE) followed by
analysis via pyrolysis coupled to gas chromatography and mass spectrometry (Py–GC–
MS). In the first extraction step, a large part of the organic matrix was removed with
methanol at 100 ∘C and 100 bar, followed by a second step with tetrahydrofuran at
185 ∘C and 100 bar to extract the polymers that were subsequently adsorbed to silica
gel and measured with Py–GC–MS. With the developed method, limits of quantification
in an environmentally relevant concentration range of 7–8 μg g−1 for the most common
thermoplastic polymers polyethylene (PE), polypropylene (PP), and polystyrene (PS)
were achieved.
In order to improve the robustness of the method, poly(styrene-d5) (PSd5) was initially
applied as internal standard. However, further analyses revealed a deuterium–hydrogen
exchange during Py–GC–MS measurement, which was catalyzed by the inorganic ma-
trix. This effect was thereupon systematically investigated and poly(4-fluorostyrene) was
established as a new, stable internal standard.
While the developed method enabled the quantification of PE, PP, and PS, several other
polymers had to be excluded. In particular, the quantification of poly(ethylene tereph-
thalate) (PET) proved challenging via Py–GC–MS. A variety of catalytic effects by the
inorganic matrix was revealed and systematically investigated, e.g., changes in pyrolysis
product distribution. Several different sample preparation approaches failed to resolve
these issues. PLE led to a depolymerization of PET which was also catalyzed by the
inorganic sample matrix.
After further optimization and reduction of false positives, the developed method has
the potential to be included in future standardized procedures for MP quantification. It
provides a fast, robust analysis of MP in complex samples, while also considering widely overlooked matrix effects. Potential quantification approaches for other polymers that are
not included in the developed method (e.g., tire wear particles, paint particles) are also
discussed in this thesis.
Feuerfestmaterialien nehmen in industriellen Prozessen, die hohe Temperaturen erfordern, eine maßgebliche Rolle ein. Eine vollständige Charakterisierung ihrer Eigenschaften ist erforderlich, um potentielle Defizite zu identifizieren und adäquate Struktur-Eigenschafts-Korrelationen prognostizieren zu können. Die vorliegende Arbeit evaluiert anhand von drei exemplarischen Anwendungsbeispielen die Eignung der Röntgen-Computertomographie (engl.: X-Ray Computertomography, XRT) als Analysemethode zur Untersuchung feuerfester Materialien. Der Schwerpunkt liegt hierbei auf Strategien zur Untersuchung des Gefüges hinsichtlich seiner Strukturen, Defekte sowie Porosität bzw. Porenverteilung und -morpho-logie und darüber hinaus auch auf der Analyse von Rissen. Die XRT ermöglicht die hochauflösende, zerstörungsfreie, dreidimensionale (3D) und reproduzierbare Untersuchung innerer und äußerer Strukturen des Körpers. Die im Rahmen dieser Arbeit durchgeführten Studien verdeutlichen, welches Potential sich insbesondere bei der Kombination der XRT mit konventionellen Methoden ergibt.
During the development phase of plastic components, simulations are being used to an increasing extent. Against the background of product requirements and the inevitable necessity of conserving resources, the expanded use of simulation tools is an essential part of the solution. Among available methods, but so far underutilized with respect to real-life processes, is the molecular dynamics simulation. By the use of this method it is possible to visualize the physical processes occurring on the microscopic level, as e.g. those that arise during plastics processing. This thesis examines how boundary conditions, which mimic the extrusion blow molding process, affect the behavior of polyethylene on the microscopic level. A mesoscopic model (coarse-graining) is applied to describe the polymer. Initially, this model is verified by determining material properties. The uniaxial tensile test is modeled on the micro-scale to identify parameters such as the elastic modulus, yield stress, and Poisson’s ratio. Additionally, thermal properties, particularly those characterizing the crystallization behavior, are identified. The objective of these investigations is the microscopic observation and quantification of effects that occur during dynamic stretching and crystallization processes. The calculated properties show good agreement with the experimental data, especially regarding the thermal parameters. Qualitatively, the stress-strain behavior is reproduced in alignment with experimentally observed results. However, the short time scale of the simulation models leads to micromechanical behavior that is more extreme than what is monitored on a macroscopic level. By extending the simulation models, biaxial stretching processes are simulated. These stretching processes resemble the situation during the inflation of the parison in the extrusion blow molding process. The examination of various cooling conditions, particularly by the use of mold constraints, is another focus of the investigations. The analysis of the biaxially stretched simulations reveals that disentanglement processes during stretching dominate the further development of polymer systems. It is possible to quantify the dynamics of crystallization processes depending on the degree of stretching and cooling conditions through various parameters (distribution of entanglement points, local orientations). The results indicate that coarse-grained molecular dynamics simulations are able to significantly enhance the micromechanical understanding of local events occurring during plastic processing.
The political targets for CO2 reduction in industrial processes are leading to a technological change in the area of pig iron production. In future, pig iron will be produced by using the direct reduction process instead of the blast furnace process. Direct reduction plants are currently operated with natural gas, this is to be replaced by hydrogen in the future in order to meet the climate targets. Within this work, the influence of hydrogen-containing atmospheres on currently used refractory materials from the Al2O3-SiO2 system was investigated. An experiment was developed to simulate the corrosion of refractory materials in the laboratory under realistic test conditions. Taking into account the atmosphere, the temperature and the sample material, a variety of practical corrosion tests were carried out. By applying a comprehensive analysis strategy, relevant corrosion effects on the materials were subsequently described as a result of the gas composition. The test temperature was in the range of 716 °C < T < 1150 °C. Physical and chemical-mineralogical tests were used to investigate the corrosion effects. In addition, the intensity of the corrosion effects was evaluated based on the gas compositions used. Pure hydrogen atmospheres in particular led to strong gas corrosion, while the presence of water vapor inhibited the chemical reactions. The mixture of methane and hydrogen can create an aggressive H2 / CO atmosphere, which also can lead to the formation of solid carbon. This phenomenon changes the possible causes of damage to refractory material; the crystallization pressure of carbon inside the structure of the refractory can also contribute to material failure. Furthermore, the corrosion reactions could be described by coupling imaging analysis methods and element determination. It was shown that, in contrast to the general opinion in the state of the art, there was not exclusively a decrease in SiO2-amount. Several reactions took place in the investigated, industrially used materials, which led to the local chemical attack of SiO2 (silicate glass phase) and caused a parallel crystallization of cristobalite. The chemical attack of hydrogen on the silicate glass phase can be defined as the primary corrosion reaction in the range of 716 °C < T < 1150 °C in a pure hydrogen atmosphere. In addition, the reaction kinetics as a function of temperature were experimentally investigated and described. Based on these analyses, material properties can be defined that are particularly suitable for the future use of defined refractory qualities within reduction processes.
The title compound, [Fe(C5H5)(C21H24NO2)], which is produced by the oxidation of 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole, crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The central heterocyclic pyrrole ring system subtends dihedral angles of 13.7 (2)° with respect to the attached cyclopentadienyl ring and of 43.6 (7)° with the major component of the disordered phenyl group bound to the N atom. The 4-tert-butylphenyl group, as well as the non-substituted Cp ring are disordered with s.o.f. values of 0.589 (16) and 0.411 (16), respectively. In the crystal, molecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O—H···O hydrogen bonds between the hydroxy substituent and the carbonyl O atom of the adjacent molecule.
X-ray computed tomography (XRT) is a three-dimensional (3D), non-destructive, and reproducible investigation method capable of visualizing and examining internal and external structures of components independent of the material and geometry. In this work, XRT with its unique abilities complements conventionally utilized examination methods for the investigation of microstructure weakening induced by hydrogen corrosion and furthermore provides a new approach to corrosion research. The motivation for this is the current inevitable transformation to hydrogen-based steel production. Refractories of the system Al2O3-SiO2 are significant as lining materials. Two exemplary material types A and B, which differ mainly in their Al2O3:SiO2 ratio, are examined here using XRT. Identical samples of the two materials are measured, analyzed, and then compared before and after hydrogen attack. In this context, hydrogen corrosion-induced porosity and its spatial distribution and morphology are investigated. The results show that sample B has an higher resistance to hydrogen-induced attack than sample A. Furthermore, the 3D-representation revealed a differential porosity increase within the microstructure.