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Environmental sustainability and –stability of materials concerning the migration of pollutants
(2019)
In addition to previously reported results on the accelerated weathering of polystyrene samples (PS) containing 1 wt. % hexabromocyclododecane (HBCD), we present the first results of our investigations of polypropylene samples (PP) containing 0.1 wt. % BDE-209. All studied polymer samples were exposed to a defined weathering schedule in a climate chamber in accordance to regulation EN ISO 4892-3:2006. For the determination of BDE-209 in the collected raining water the samples were prepared in accordance to a validated protocol. Before the analyses each sample was spiked with isotopically labeled BDE-209. Subsequently the samples were extracted with isooctane. The obtained extracts were concentrated, and the resulting solutions were analyzed by GC/MS. Additionally, the total bromine content was monitored for the weathered and untreated samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and X-ray fluorescence analysis (XRF) as a non-destructive and rapid method. In general, the resulting data from the accelerated weathering will be compared to those from the natural weathering experiments. Here, the surfaces of the test pieces were analyzed by LA-ICP-MS and XRF as well. Moreover, soil bed tests were conducted in a well characterized model soil. This soil (boulder-clay, sand with 12 % loam, particle size in total 0.2-4 mm) is filled in a free-draining basin inside of an air-conditioned cellar. In this manner, TOC, water capacity and humidity are recorded parameters. To induce a leaching process from the samples by the raining water, the target water content is calculated to 8%. The actual humidity is measured by a tensiometer, assuring the duration of the raining period. A defined humidity is a fundamental parameter for a biological activity in the soil. The test polymers were placed up to the half in the soil. Microbial activity of the soil is monitored by a reference polymer (polyurethane) and should induce the release of HBCD and BDE-209 out of the test materials. These released analytes will be captured by passive samplers (silicone tubes) placed in a distinct distance to the polymer samples in the soil. The soil bed experiments are complementary to the weathering experiments due to the biological activity in the soil.
Environmental sustainability and –stability of Materials concerning the Migration of pollutants
(2018)
MaUS is an acronym for ”Material und Umweltsimulationen“. Plastics are in the focus of environmental politics due to their long-term behaviour and therefore to their persistence. Not only that they appear as visible contaminants in the sea and on the beach, but their unknown behaviour concerning their additives as well as the related transformation products are anxious. Therefore, we wish to establish a certified reference method to provide a method for testing plastics.
Aim of this project is the development of fast motion standard reference methods for testing plastics regarding to their environmental compatibility. To establish these testing methods, we use polystyrene (PS) and polypropylene (PP) with environmental relevant brominated flame retardants, known for their persistent bioaccumulative and toxic (PBT) properties. In case of PS the material contains 1 wt% of 1,2,5,6,9,10-hexabromocyclododecan (HBCD) and in case of PP 0.1 wt% bromodiphenylether (BDE-209), which is known as a substance of very high concern (SVHC). Furthermore, we use polycarbonate (PC), which is still used as material in baby flasks and releases Bisphenol A (BPA), an estrogenic active substance.
As an additional material PTFE is used for its importance as a source for two ubiquitous environmental substances (PFOS and PFOA), whose toxicological effects are still incompletely known.
The focus in this current work is set on the transfer of potential pollutants out of applied materials mentioned above into environmental compartments like water or soil. Here an accelerated aging concept should be developed to shortened time consuming natural processes. For these resulting simulations we use a programmable weathering chamber with dry and wet periods and with high and low temperatures. These programmes run for several weeks and according to a defined sampling schedule we take water samples, run a clean-up procedure by SPE (Molecular imprinted polymers (MiPs) resp. polymer-based cartridges (Waters Oasis HLB)) and analyse them by HPLC-UV resp. LC-MS/MS. Of most interest in case of flame retardants are photocatalytic transformation products. Therefore, we conduct a non-target-screening resp. a suspected target-screening by LC-MS/MS and HRMS.
Plastics are a diverse group of materials used in packaging, construction, medical applications, and many more. Due to their favourable properties their production and consequently their input into natural systems has increased drastically over the last decades. In the environment (photo-)oxidation processes and mechanical abrasion may then lead to the decomposition of the plastics. During this process microplastics (<5 mm) are formed. It has been noted that xenobiotics which are present in the same compartments can sorb to microplastics. However, knowledge on this topic is still limited. The work presented here aimed to investigate the sorption of the type 2 diabetes drug metformin and the triazole fungicide difenoconazole to virgin polyamide (PA), polypropylene (PP), and polystyrene (PS). Additionally, sorption to cryo-milled PP and acid-treated PA was studied. The latter was also characterised by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and dynamic scanning calorimetry (DSC). Sorption experiments were planned on the basis of a full factorial design with agitation, salinity, and pH value as parameters. Results of the study revealed that metformin did not show any affinity towards the tested materials. Difenoconazole however, sorbed to all microplastics. Data analysis showed that agitation is the main influencing factor, whereas salinity and the pH value held little to no significance. Mechanical and chemical treatment of the polymers led to enhanced sorption of difenoconazole. Long-term sorption experiments confirmed the hypothesis that particle size strongly influences the time until sorption-desorption equilibrium is reached.
MaUS is an acronym for ”Material und Umweltsimulationen“. Plastics are in the focus of environmental politics due to their long term behaviour and therefore to their persistence. Not only that they appear as visible contaminants in the sea and on the beach, but their unknown behaviour concerning their additives as well as the related transformation products are anxious. Therefore, we wish to establish a certified reference method to provide a method for testing plastics.
Aim of this project is the development of fast motion standard reference methods for testing plastics regarding to their environmental compatibility. To establish these testing methods, we use polystyrene (PS) and polypropylene (PP) with environmental relevant brominated flame retardants, known for their persistent bioaccumulative and toxic (PBT) properties. In case of PS the material contains 1 wt% of 1,2,5,6,9,10-hexabromocyclododecan (HBCD) and in case of PP 0.1 wt% bromodiphenylether (BDE-209), which is known as a substance of very high concern (SVHC). Furthermore, we use polycarbonate (PC), which is still used as material in baby flasks and releases Bisphenol A (BPA), an estrogenic active substance.
As an additional material PTFE is used for its importance as a source for two ubiquitous environmental substances (PFOS and PFOA), whose toxicological effects are still incompletely known.
The focus in this current work is set on the transfer of potential pollutants out of applied materials mentioned above into environmental compartments like water or soil. Here an accelerated aging concept should be developed to shortened time consuming natural processes. For these resulting simulations we use a programmable weathering chamber with dry and wet periods and with high and low temperatures. These programmes run for several weeks and according to a defined sampling schedule we take water samples, run a clean-up procedure by SPE (Molecular imprinted polymers (MiPs) resp. polymer based cartridges (Waters Oasis HLB)) and analyse them by HPLC-UV resp. LC-MS/MS. Of most interest in case of flame retardants are photocatalytic transformation products. Therefore, we conduct a non-target-screening resp. a suspected target-screening by LC-MS/MS and HRMS.
Los contaminantes atmosféricos son con frecuencia responsables
de la aceleración de la degradación de la piedra
en los edificios y monumentos históricos de las zonas
urbanas. Son muchos los factores que influyen de manera
decisiva en el comportamiento de las piedras naturales
ante los contaminantes gaseosos. Dos de esos factores
son la composición de la atmósfera y el tipo de piedra.
Las areniscas en particular son propensas al ataque de
los contaminantes atmosféricos debido a su naturaleza
porosa, pero muchas de las reacciones de las areniscas
no carbonatadas con estos gases no se conocen bien. El
estudio presentado tiene por objeto comprender los procesos
y factores que controlan el distinto comportamiento
de las areniscas respecto al dióxido de azufre. Para el
estudio se investigaron siete areniscas distintas procedentes
del sur y del este de Alemania. Las areniscas mostraban
una diferencia significativa en la composición de
su aglomerado. Por lo que respecta a la absorción de
SO2, las distintas variedades de arenisca mostraron un
comportamiento completamente diferente. Curiosamente,
la cantidad de SO2 depositada no estaba relacionada con
la superficie específica de las areniscas, este parámetro
está relacionado con el contenido en óxidos de hierro.
Air pollutants often accelerate stone deterioration in historical
buildings and monuments in urban areas. Many factors
condition natural stone behaviour with respect to
gaseous pollutants. Two of the more prominent of such
factors are the composition of the atmosphere and the
type of stone. Due to their porosity, sandstones are particularly
vulnerable to air pollutant attack. Many of the reactions
between noncarbonaceous sandstones and these
gases are not well understood, however. The present
study aimed to acquire an understanding of the processes
and factors governing sandstone behaviour when exposed
to sulphur dioxide. Seven different sandstones from southern
and eastern Germany were analyzed for the study.
The binder composition of the stones varied significantly.
They also exhibited completely different behaviour in connection
with SO2 deposition. Interestingly, while the
amount of SO2 deposited was unrelated to the specific surface
area of the sandstones, this parameter was closely
correlated to the iron oxide content.