Sanitär- und Kommunaltechnik; Umwelttechnik
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Compared to the designated European upper reference level of 300 Bq m-3 for indoor radon concentrations, the contribution of building materials appears to be low. Taking into account the recommended limit of 100 Bq m-3 by WHO as well as the increased dose conversion factor, the contribution of building products is quite relevant, especially at low air change rates. Therefore in Germany a maximum contribution of building materials to the indoor radon concentration of 20 Bq m-3 is discussed.
Because measurements of low concentrations are associated with high uncertainties, radon exhalation rates are often determined in chambers without air exchange and indoor conditions are extrapolated.
This study investigated the suitability of direct low level radon measurement under simulated indoor conditions with commercially available instruments, based on the preliminary EU standard for the determination of the emission of volatile organic compounds (VOC) from building materials in test chambers.
Measurements are possible with a relative uncertainty ranging from 7 to 18 %. Four major problems were identified:
1. Detector sensitivity: Two of four instruments were identified to determine low radon concentrations in a sufficiently short measuring time.
2. Thoron discrimination: Thoron was discriminated by aging the sampled air in a hose before the detector.
3. Sampling setup: An external chamber measurement was feasible as long as all main system parts were under slight overpressure.
4. Blank value: For VOC-emission testing ambient air, conditioned by filtration and sorption, is used to generate an air exchange. Regarding radon, this treatment is non-effective. If all instrument background levels have been characterized, the blank value must be measured with a second detector in parallel.
Sewage sludge ashes (SSA) contain up to 13% P and are thus promising raw materials for fertilizer production. However, SSAs also contain heavy metals and the main P-bearing mineral phases whitlockite and aluminium phosphate are poorly bioavailable. We developed and patented a process that produces fertilizers from SSA addressing the above mentioned challenges. SSA is thermo-chemically treated at ~950°C under reducing conditions (reductive: dry sewage sludge) in a rotary kiln together with an alkali compound such as sodium or potassium sulfate, hydroxide or carbonate. Some undesired trace elements such as As, Hg, Pb and Cd are evaporated and separated via off gas treatment system. The poorly soluble phosphates are transformed into calcium alkali phosphates (CaNaPO4 or CaKPO4) that are not water soluble but completely soluble in neutral ammonium citrate solution (NAC). Pot experiments showed that the fertilizer performance of the treated SSA containing calcium alkali phosphates as the single P-bearing mineral phase was comparable to the performance of triple superphosphate. The PNAC-solubility of fertilizer products correlated very well with the resulting contents of calcium alkali phosphates and the P-uptake of plants in pot experiments. The effect of the ratio alkali/P on the PNAC-solubility was investigated by crucible experiments and trial series with a medium scale rotary kiln using different SSAs and alkali phosphates. The effects of operational parameters such as the temperature and the retention time were investigated as well as concurring side reactions of the alkali compounds e.g. with SiO2 present in SSA. The alkali/P ratio must be roughly adjusted at 2 to achieve 100% PNAC-solubility for a common type of SSA. A demonstration trial with an output of 2 t recycling fertilizer was carried out in an industrial rotary kiln (product output 30 kg/h). The PNAC-solubility of the product varied between 60% and 80% during the 4 days campaign showing that the transformation of the mineral P-phases to calcium alkali phosphates was not complete. This was observed although the amount of Na2SO4 additive was dosed according to the results of the pre-investigations. Structure analysis by XRD showed that besides the target compound CaNaSO4 also some Ca3(PO4)2 remained in the SSA as well as some unreacted Na2SO4 additive. Obviously, the conditions in the industrial rotary kiln were not optimal for the process showing that some process aspects have to be reconsidered for the scale-up.
Pot experiments are often performed to analyze the plant-availability of phosphorus (P) in P-fertilizers. However, these experiments do not determine the P compounds present in the soil which are responsible for the yield increase. In order to better understand the results of pot experiments we analyzed the soils by P K-edge X-ray absorption near-edge structure (XANES) spectroscopy to determine the P species and unravel transformation processes. We carried out pot experiments with maize testing different waste water derived recycling P-fertilizers on an acidic and a neutral soil. Soils samples before sowing and after harvest were collected and prepared for analysis. A combination of macro- and µ-XANES spectroscopy was used to determine the chemical state of the overall soil P and to identify P compounds in P-rich spots localized by micro-X-ray fluorescence (µ-XRF). P K-edge macro-XANES spectroscopy detected organic P and/or P sorbed onto organic matter or other substrates in the unfertilized and fertilized soils. In addition, µ-XRF mapping in combination with P K-edge µ-XANES spectroscopy evidenced that some P phases present in recycling P-fertilizers (magnesium phosphate and calcium sodium phosphate) react with co-fertilized ammonium nitrate and form highly plant-available ammonium phosphates in the soil. In opposite, apatites were not affected by the presence of ammonium. Thus, for a boost of the plant-availability of P in recycling P-fertilizers these fertilizers should be directly co-fertilized with nitrogen (N) sources that contain a high amount of ammonium instead of nitrate. Possibly, a specific preparation of NP-fertilizers by granulation of recycling P-fertilizers with ammonium compounds and a nitrification inhibitor could enhance the plant-availability of the produced fertilizer whereby they become more competitive to commercially available NP-fertilizers based on phosphate rock.
Sub-aerial biofilms (SAB) are ubiquitous, self-sufficient microbial ecosystems found on mineral surfaces at all altitudes and latitudes. SABs, which are the principal causes of weathering on exposed terrestrial surfaces, are characterized by patchy growth dominated by associations of algae, cyanobacteria, fungi and heterotrophic bacteria. A recently developed in vitro system to study colonization of rocks exposed to air included two key SAB participants - the rock-inhabiting ascomycete Knufia petricola (CBS 123872) and the phototrophic cyanobacterium Nostoc punctiforme ATCC29133. Both partners are genetically tractable and we used them here to study weathering of granite, K-feldspar and plagioclase. Small fragments of the various rocks or minerals (1–6 mm) were packed into flow-through columns and incubated with 0.1% glucose and 10 μM thiamine-hydrochloride (90 μL min−1) to compare weathering with and without biofilms. Dissolution of the minerals was followed by: (i) analysing the degradation products in the effluent from the columns via Inductively Coupled Plasma Spectroscopy and (ii) by studying polished sections of the incubated mineral fragments/grains using scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analyses. K. petricola/N. punctiforme stimulated release of Ca, Na, Mg and Mn. Analyses of the polished sections confirmed depletion of Ca, Na and K near the surface of the fragments. The abrupt decrease in Ca concentration observed in peripheral areas of plagioclase fragments favored a dissolution-reprecipitation mechanism. Percolation columns in combination with a model biofilm can thus be used to study weathering in closed systems. Columns can easily be filled with different minerals and biofilms, the effluent as well as grains can be collected after long-term exposure under axenic conditions and easily analyzed.
The worldwide produced plastic amount was about 314 m tones in 2013. A content of about 5-12 m tones of plastic products is estimated to attain to the environment. There, they are exposed to environmental aging conditions like UV light, abrasion, water, oxidation etc. and degrade to small particles. If the particles reach a dimension < 5 mm they are called microplastic. Today microplastic is almost ubiquitary and was found in the aquatic as well as in the terrestrial environment. The main representatives are polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyethylene terephthalat (PET).
Analyzing microplastics in environmental samples turned out to be very challenging, due to the fact that there are only a few synthetic particles beside a huge number of natural. Furthermore, the different polymers particles vary in their shape, their density and their chemical characteristics. Until now, there is no standard procedure for sampling, concentration and analyzing. We developed a thermal decomposition method for analyzing micro plastics in environmental samples. The method is a combination of a thermal extraction on solid-phase adsorption agents with a subsequent analysis of the decomposition products by thermal desorption gas chromatography mass spectrometry. In contrast to more established methods, such as IR or Ramen spectroscopy, our method enables measurements within few hours and gives an integration result of polymer specific decomposition products. Therefore, it is possible to identify and to quantify polymers in environmental matrices.
The use of the method is demonstrated for various polymers (PE, PP, PS, PET) in spiked and first time also in real environmental samples.
Small grain sizes of municipal solid waste incineration (MSWI) bottom ash (BA) contain elemental and chemically bonded metals in appreciable amounts, especially copper. As different copper species have in general a higher density compared to the prevalent minerals, processes for density separation seemed to be favorable for the recovery of copper. Investigations with a centrifugal classifier were therefore carried out with BA from MWSI which have been used for a few years as the covering material for a landfill. The results show an appreciable enrichment of the precious copper. The concentrates contained up to 60 mg/kg copper in the dry weight (DW) (in general about 30 – 40 mg/kg DW) with enrichment factors of around 20 and a copper recovery of up to 50 % (in general around 20 %). A test series in order to evaluate the potential benefit for sequential processing illustrate the low efficiency for a further processing of the tailings.
The widespread use of antibiotics in livestock farming leads to trace residues in food products and wastewater, potentially entailing antimicrobial resistance in food-borne pathogens. The determination of antibiotics in aqueous environments and foodstuff is thus of major concern.
Analytical assays based on molecularly imprinted polymers (MIPs) have emerged as a valuable tool in this field due to the low production costs, stability, format adaptability and the possibility to imprint and thus their ability to recognize a wide variety of target analytes. With regard to optical sensing technologies, however, MIPs have only been used in considerably few applications, especially in fluorescence sensors. This limitation is basically due to the fact that the incorporation of a fluorescently responding moiety into a polymer matrix is challenging. One way to overcome this limitation is to use tailor-made fluorescent indicator monomers for direct transfer of the binding event into an optical signal. If such a monomer is integrated into a thin MIP-shell on microspheres such core/shell particles can be readily used in advanced multiplexing sensory fiber-optic microarrays.
Here, we propose such a fiber-optic microarray based on fluorescent MIP microspheres for antibiotics. The binding behavior and the selectivity of a microarray using these MIP were examined and compared with a non-imprinted polymer (NIP) control, employing the target molecules and other structurally closely related antibiotics.
Reactive geomembranes and geotextiles are an innovative approach to control the migration of contaminants in geotechnical applications. Within a joint research project in cooperation with a medium-sized enterprise, the preparation and characterization of “reactive” geomembranes and geotextiles modified by the addition of zero-valent metal nanoparticles was performed. Zero-valent iron (ZVI) nanoparticles were added to polyethylene or to the fillings of geo-containers or geosynthetic clay liners. These geosynthetic products consist of mixtures of sand with clay or bentonite, typically embedded in geotextile nonwovens or geomats. The permeability of these geo-containers can be adjusted by the ratio of clay or bentonite to sand. ZVI nanoparticles were also added as reactive material to geomembranes made of polyethylene with additives like the antioxidant Irganox 1010 or glycerin. These additives prohibit oxidation of the nanoparticle and act as hydrogen donor in the dechlorination of chlorinated hydrocarbons. Contaminates such as chlorinated hydrocarbons and toxic heavy metal compounds are either decomposed or converted to less toxic species (e.g. Cr-(VI) reduction to Cr-(III)). The paper reports the first experimental results from manufacturing of the reactive geomembrane model materials and characterization of the products with microscopic techniques. First breakthrough measurements of the ZVI modified geomembrane compared to a reference sample are presented.
Advanced oxidation processes have become an important part of research due to their capacity to degrade many environmental pollutants during water treatment. Especially the heterogeneous photocatalysis is a promising method because it often results in a full mineralization of many hazardous compounds. Incomplete degradation reactions can result in transformation products due to oxidative conditions. The transformation products may have a higher toxicity than the precursor substances and are often only partly removed during water treatment. Since a lot of these compounds are still unknown, transformation products are not detected by target analysis used in sewage treatment plants and are often released into the aquatic ecosystems. Therefore, extensive and effective non-target analytical methods are necessary for the monitoring and identification of the transformation products which can be generated during waste water treatment.
Titanium dioxide (TiO2) is the most frequently used photocatalyst because of its inexpensiveness, non-toxicity, chemical stability and its high photocatalytic activity. If TiO2 is irradiated electron-hole pairs are generated on the surface of the TiO2, resulting in the formation of active oxidized species such as hydroxyl radicals which can react with environmental pollutants.
A model system has been developed to simulate photocatalytic reactions in a laboratory scale. The commonly used pharmaceuticals metformin and gabapentin were selected as model substances because of their high input in waste water and the little information about their fate during water treatment. Metformin is the drug of choice for treating type 2 diabetes. More than half of the total amount of pharmaceuticals in the environment are the antidiabetic agent metformin and its major transformation product guanylurea. Gabapentin is used as antiepileptic drug and for the treatment of neuropathic pain. It is found in waste water influent in the high ng/L range.
First results of the optimization of the photocatalyst and its application are shown.
The recent experience of Italian seismic events provided wide observational information about typical behaviour, damage patterns and intrinsic vulnerability of monumental buildings. Evidence indicates that historical constructions are by far the most vulnerable from the seismic point of view. As a consequence, they demand for the definition of urgent strategies for the protection of cultural heritage from seismic hazard. The main goal of an in-depth knowledge of the structure should help to avoid inadequate, unsuitable or dangerous rehabilitation operations, as well as to select non-invasive and reversible techniques for the best exploitation of material and technology features. The definition of reliable models and methods for seismic risk assessment of historical constructions is today a very important topic. Typical problems of masonry structures concern aspects like inherent structural lacks, material degradation, geotechnical problems, buckling behaviour of slender elements and dynamic loading vulnerability. Modelling the mechanical behaviour of masonry may play an important role, due to both inherent material complexity and great scatter in mechanical properties. Effective procedures for the identification of the structural parameters from static and dynamic testing are thus required. In particular, dynamic measurements may be very useful for the identification of mechanical properties and soil restraints and, consequently, for the calibration of advanced numerical finite element models. The paper addresses two case studies of structural monitoring and seismic assessment of medieval masonry towers in Italy: the bell tower of Aversa and the bell tower of Capua. These monuments, placed in the Campania region, were monitored by means of full-scale environmental vibration testing. Measured responses are then used for modal identification with a typical finite element model updating technique based on vibration test results. Parameters optimization is carried out on the basis of a criterion which minimises a weighted error on modal properties. A satisfactory improvement in the determination of modal parameters is thus obtained, resulting in a close agreement between the modal properties observed in dynamic tests and those calculated from numerical model. Seismic assessment is finally performed based on nonlinear static analysis of the tower under multimodal distributions of lateral loads. Results from nonlinear analysis indicate the potential collapse mechanisms and evidence dangerous structural weakness which may play a role in the seismic vulnerability of the towers.
In the beginning of the 1980s earth building has undergone a renaissance, which nowadays leads to an increasing use of load-bearing earth constructions and in particular, earth block masonry. At present there are no common structural standards according to the semi-probabilistic calculation concept, which is the state-of-the-art in European standards. A solid database is needed for the determination of the materials partial safety factor. Therefore, compressive strength tests were carried out with two types of earth blocks and two types of prefabricated earth mortar. The evaluation showed that the variation of the compressive strength was remarkably less than expected, which seems to indicate high quality standards of the components earth block and mortar with regard to industrial production. On the basis of these results and together with the reliability method, a partial safety factor for earth block masonry subjected to compression was determined. The main aim of the research was the development of a first valid database for material parameters of earth block masonry with particular regard to statistical characteristics. The results showed that a common calculation method for earth block masonry based on partial safety factors following the valid masonry construction standard is feasible.
The surface chemistry / functionalization of nanomaterials and microparticles largely controls the stability of these materials as well as their solubility and subsequent biofunctionalization and their interactions with biological systems. Moreover, in the case of some nanomaterials like semiconductor quantum dots or lanthanide-based upconversion nanocrystals, the ligand shell strongly affects their optical properties, e.g., via passivation of surface states and traps that favor luminescence quenching or the protection of surface atoms from quenching water molecules. This renders analytical methods for the quantification of surface groups like functionalities very important. Targets of broad interest are here amino, carboxyl, alkine and maleimide groups used for common bioconjugation reactions and typical ligands like thiols and polyethylene glycol (PEG) molecules of varying length, used for the tuning of material hydrophilicity and biocompatibility, minimization of unspecific interactions, prevention of biofouling, and enhancement of blood circulation times as well as surface-bound biomolecules like streptavidin or other biomolecules relevant e.g., for diagnostic assays. Here, we focus on simple optical methods relying on standard laboratory instrumentation, validated by method comparison and/or mass balances and present examples for their use for the characterization of different types of nanomaterials and microparticles.
Luminescence-based detection methods, ranging from fluorescence spectroscopy for photophysical and mechanistic studies over sensing applications, chromatographic separation techniques and the microarray technology with fluorescence detection to fluorescence microscopy, flow cytometry, single molecule spectroscopy, and molecular imaging to integrating sphere spectroscopy, are among the most widely used methods in the life and material sciences. This is due to e.g., their unique sensitivity enabling the detection of single molecules, potential for multiplexing, ease of combination with spatial resolution, and suitability for remote sensing. Many of these advantages are closely linked to the choice of suitable molecular and nanoscale fluorescent reporters, typically required for signal generation. This includes organic dyes without and with sensor function, fluorophore-encoded polymeric and silica nanoparticles as well as nanocrystalline systems like semiconductor quantum dots and upconversion phosphors, emitting in the visible (vis), near-infrared (NIR), and IR (infrared). Current challenges present the environment sensitivity of most fluorophores, rendering fluorescence spectra, measured intensities/fluorescence quantum yields, and fluorescence decay kinetics matrix-dependent, and instrument-specific distortions of measured fluorescence signals that need to be considered for quantification and comparability of data, particularly fluorescence spectra.
Here, current applications of luminescence-based methods and different types of reporters will be presented. In this context, suitable spectroscopic tools for the characteri-zation of the optical properties of fluorescent reporters and fluorophore-encoded microparticles, analytical tools for the determination of the surface chemistry of different types of particles, and different multiplexing strategies will be discussed.
We have studied the influence of gamma rays on physical properties of different commercially available silica optical fibers stepwise irradiated up to a total dose of 100 kGy. The detection of radiation-induced changes in silica glass offers the possibility of using selected optical fibers as distributed radiation sensors. The measurements performed by us were based on optical backscatter reflectometry and Brillouin distributed sensing. The measurement methods enable an analysis of radiation-induced modification of the group refractive index and density of the optical fibers. The most distinct physical effect observed by us concerns the increase of the optical attenuation with rising total radiation doses. Quantitative measurement results indicate a crucial impact of fiber dopants on radiation-induced physical and sensory characteristics of silica optical fibers affected by differences in fiber fabrication techniques. Based on the obtained results, the suitability of distributed Brillouin sensing for dosimetry applications seems to be improved by modifying the refractive index profile of the fiber core.
This study presents diagnostic techniques to assess the structural vulnerability of earthen buildings. Medieval structures at Ambel (near Zaragoza, Spain), once a preceptory or monastic house belonging to the Military Orders, provide a useful case study. After more than a thousand years of construction, failure and repair from the 10th century to the present day, Ambel preceptory today is characterised by marked inhomogeneities: construction materials and structural typologies are juxtaposed, with structural discontinuities at the interfaces between construction phases. This paper argues that, while static analysis is an essential prerequisite before a suitable maintenance program can be defined, no evaluation of the structural behaviour of any historic building can ignore an understanding of the building’s history.
Fungal secondary metabolites such as phomopsin A (PHO-A) produced by the fungus Diaporthe toxica are referred to as “emerging” mycotoxins. Recently, we developed a biosynthetic approach to gain access to 15N-isotopically labelled PHO-A as internal standard (IS) for PHO-A matrix independent quantification of PHO-A in various commodities. Aim of the present work was to elucidate the applicability of the new IS for accurate quantification and to investigate the phomopsin formation on various legume seeds as well as plant material. In summary, the applicability of the SIDA-HPLC-MS/MS method could be proven and the potential of D. toxica to produce high amounts of phomopsins under unfavorable conditions on lupins and other legume seeds could be shown. Moreover, a novel toxic methylated PHO-A derivative was unveiled in natural samples infested with D. toxica.
The goal of the present study is to assess the feasibility to develop a first reliable database of materials parameters for Earth Block Masonry (EBM). The database is crucial when defining the materials safety factors. In the first part an experimental campaign of compressive tests were carried out on two types of earth block and two types of earth mortar. The results showed that the mean variation of the compressive strength was remarkably less than expected. This low variation is related to a production with high quality standards of the materials employed. In the second part a partial safety factor for EBM under uniaxial compression was determined through the reliability method. The results proved the reliability of a common calculation method for EBM based on partial safety factors following the current standards.
UHPC-AAC/CLC composite panels with self-cleaning properties. Materials and production technology
(2016)
The aim of this study is to show the development of a façade composite panel combining either an autoclaved aerated concrete or a cellular lightweight concrete insulation layer with a box-type external ultra-high performance concrete (UHPC) supporting layer. The paper presents the materials characteristics of the different components and the production technology of the panel. The efficiency of surface modifications of the materials forming the external shell of the panel is reported. The activation of self-cleaning properties is described. The test results showed that the most efficient way to use the water-repellent agent is its application on the substrate before the concrete cast.
Concerning the production technology, the preliminary studies showed more advantages of a two-step manufacturing procedure of the UHPC boxes than a one-step procedure.
In order to provide nutrition for a growing world population pesticides are a necessary tool. Crop protection agents may be considered safe, if handled correctly. Nevertheless, they are subject to transformation processes and metabolization in the environment and technical installations. Transformation products (TP) and metabolites may be more harmful than the mother substance and thereby pose a threat to environmental and human health.
With 19 % market share in 2014, triazole pesticides are the class of organic fungicides which are most commonly used in Germany. However, only little data is available concerning their TP and metabolites. In this study the fate of the triazole fungicides propiconazole and difenoconazole in soil and water using model reaction systems mimicking their pathway in the environment and the industrial water treatment is investigated.
During application the substances may directly contaminate soil as well as surface waters. In these compartments, transformation by global irradiation needs to be considered. Due to their moderate mobility both pesticides may also end up in ground water from which drinking water is produced. Owing to the vigorous conditions during drinking water production the formation of a variety of technical TP can be expected. Additionally, for all compartments the degradation by bacteria is a factor which needs to be taken into account. For this survey, the potential for metabolization by model organisms is investigated.
In this work degradation and transformation of the fungicides is monitored using quantitative target analysis. Major components in the reaction mixtures are identified by non-target analysis. GC-EI-MS-spectra, HR-MS-measurements, or the comparison with native standards are utilised for structural elucidation. For identification, products will be isolated and characterized by NMR. Toxicity assessment of these TP is essential to define threshold values in the environment.
The model reaction systems will be presented and possible TP will be shown.
Here, we present an overview of the research activities of division Biophotonics concerning the design and (bio)analytical application of molecular and nanoscale functional chromophores for e.g., biomarker analysis including methods for the reliable determination of their application relevant properties. This includes the absolute determination of their brightness and photoluminescemce quantum yield, determining the signal size from the material side, as well as the development of fluorescence standards for such measurements and instrument calibration strategies, thereby providing important prerequisites for the comparison of material performance, the mechanistic understanding of nonradiative decay channels, and the rational design of new optical reporters. Moreover, for particle-based systems, ranging from nm-sized semiconductor quantum dots to m-sized polymeric and silica beads, simple optical methods and assays for the assessment of their surface chemistry are presented, which enable the quantification of the number of total and derivatizable surface functionalities, ligands per particle and particle-bound biomolecules. In addition, validation concepts for such methods are introduced utilizing method comparisons, multimodal and cleavable probes.