Sanitär- und Kommunaltechnik; Umwelttechnik
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Flame retardants are increasingly used in consumer products as e.g. electronics and furniture as well as in construction. Along with the increased usage, concerns about negative effects of flame retardants on human health and the environment have been raised. Concerning construction products one application for flame retardants is the furnishing of steel structures with reactive flameproof coatings. These coatings consist of a complex mixture of different chemicals, additives and solvents. For the evaluation of the risk possibly posed by their application to the environment, this whole mixture should be tested.
Two different leaching tests were applied according to DIN/TS 16637-2 (sample permantly submerged in water) and DIN EN 16105 (immersion and drying cycles), respectively, which can be used for plate-like products. Eluates were divided into subsamples for the measurement of different parameters: pH-value, conductivity, total organic carbon (TOC), cation and anion concentration. For screening of organic compounds, aqueous samples were liquid/liquid extracted using three solvents with different polarity (toluene, hexane and ethylacetate). GC-MS chromatograms were recorded in the SCAN mode and mass spectra of the peaks were compared with spectras stored in the NIST library.
Eluates of leaching test accroding to DIN CEN TS 16637-2 showed low electrical conductivity (20 to 150 µS/cm) and low release of cation and anions often near the LOQ. Diffferences could be observed for plates treated with the reactive coating at both sides and plates coated only at one side, while the other side is only furnished by the corrosive protection layer. Release of TOC and Zn was approx twice or 10 fold higher in the case of plates coated on one side. Furthermore, the comparison of the results for both types of plates showed that a large portion of the released compounds originate rather from the corrosion protection layer than from the reactive coating itself. Leaching tests according to DIN EN 16105 have not been finished yet, but first results show that the conductivity is much lower (1-4 µS/cm) than for the tests according to DIN/TS 16637-2 leading to the assumption that the release of compounds is lower.
By comparison of the mass spectra with library data, mainly organic solvents as xylene, 1-methoxy-2-propanol acetate and n-btuyl carbamate have been tentatively identified so far in the first test fraction done by DIN CEN TS 16637-2.
To understand the metabolic fate of food relevant mycotoxins in vitro systems were mainly used as the method of choice, so far. Yet, in recent years coupling of electrochemistry mass spectrometry (EC-MS) gained increasing importance as promising technique for fast simulation of metabolic processes and was successfully applied in particular for drug metabolism [1].
The aim of our work was to investigate the potential of EC-MS to predict phase I metabolites of priority mycotoxins and to compare the results with in vitro experiments. Hence, the EU-regulated Fusarium mycotoxins zearalenone (ZEN) and patulin as well as dihydroergocristine (DHEC) as model compound of ergot alkaloids were electrochemically oxidized and analyzed by EC MS for the first time.
Electrochemical conditions were set-up individually for each of the three mycotoxins. By using a coulometric flow through cell with a diamond working electrode oxidation of the chosen mycotoxins was observed after applying potentials between 1.7 and 2.0 V vs. Pd/H2. The electrochemically generated reaction products were analyzed online by mass-spectrometric detection.
All of the three chosen mycotoxins were electrochemically converted to mono- and/or dihydroxylated products confirming the results of ZEN related metabolism studies [2, 3] and in case of DHEC own results from in vitro assays. Due to a lack of metabolism studies concerning the oxidative fate of patulin, interpretation of EC-MS data and performing microsomal studies is of particular relevance.
Beside the identified products from electrochemical oxidation of ZEN, patulin and DHEC there is still a number of yet unknown compounds. Additional structural characterization of detected compounds by NMR and X-ray analysis will be facilitated by their large-scale production using preparative EC cells.
The organophosphate nerve agents Tabun (GA), Sarin (GB) and Soman (GD) are among the most toxic chemical warfare agents (CWA) known, and exert their biological effects by irreversibly inhibiting acetylcholinesterase enzymes of the human nerve system. The use of these agents in the past century has killed millions of civilians around the world during World Wars I and II, and after that, approximately 40.000 tons of chemical ammunition were dumped into the Baltic Sea, containing ca. 13.000 tons of chemical warfare agents. Since their production, almost all the nations of the world have been strictly avoiding the development and use of CWA, participating in active destruction of CWA stockpiles, especially since the Chemical Weapon Convention (CWC) of 1993. However, CWA have been used in offensive ways against civilian population by terrorists, as for instance in the fatal Tokyo subway terror incident of 1995 or, most recently, against antigovernment demonstrators in Syria in 2013. Due to their higher toxicity and continuous use, it is therefore very important to develop simple and fast detection methods relying on new nerve agent sensing modalities for use in control and inspection.
A practically useful fluorescent probe must possess a rapid response and high sensitivity, and shall be implementable into easy-to-use devices for real time detection by untrained personnel. Taking into account this fact, in this work we have synthesized several mesoporous silica materials containing boron–dipyrromethene (BODIPY) moieties for the detection of nerve agents GA, GB and GD in the gas phase. Development of our system indicated that the most potent materials are able to respond to the presence of nerve agent simulants diethyl cyanophosphonate, diethyl chlorophosphate and diisopropyl fluorophosphate, which have to be used in a laboratory setting, yet also for the real nerve agents Sarin, Soman and Tabun, producing a strong quenching of the fluorescence. Furthermore, a portable device for the detection of GA, GB and GD in the gas phase has been prepared for in situ sensing and rapid screening applications, consisting of strips that are able to indicate the targets down to below 1 mgm-3 which is below the LD50 values.
Influence of the of dealumination and porosity on the acid sites of natural zeolite clinoptilolite
(2016)
Heavy feedstock from crude and bio oil is a widely available and renewable resource for production of fuel and starting materials for other organic valuables by cracking or hydrocracking. Catalytic processing of heavy feedstock can meet the increased demand of energy up to a great extent. It requires the application of acidic catalysts like zeolites. However, the used synthetic catalysts are difficult to recover and reuse and are mostly spent.
The use of natural zeolite as spent catalysts may open new perspectives in the chemical use of heavy feed feedstock by chemical conversion. Natural zeolites are not expensive, widely available and environment friendly. Clinoptilolite is the most abundant natural zeolite. Clinoptilolite has a crystalline structure with a defined micropore system of medium size showing unique ion exchange and sorption properties. However, it is catalytically active only in the H-form. Also certain porosity is required for improvement of the accessibility of active sites.
This paper deals with the tuning of acid properties and of the mesoporosity of the clinoptilolite by variation of the Si/Al framework ratio, extra-framework aluminum and modification of the porosity by specific acid and water vapor treatment. The preparation of hierarchical pore structures containing interconnected micro-meso-macropores is an important factor influencing the catalytic performance.
The obtained materials have been characterized by XRD, TEM, FTIR, Raman, TG/DSC. The chemical composition has been determined by ICP-AES. The porosity have been investigated by nitrogen adsorption desorption measurements. The acidity has been measured by Ammonia-TPD. The extent of dealumination, stability of the clinoptilolite against acid treatment and the change in the nature of acid sites and their local structure has been studied by solid state 29Si and 27Al MAS NMR spectroscopy in detail. The catalytic activity has been investigated in the acetalization of benzaldehyde with 1,3-butanediol. The impact of the porosity, change of the Si/Al ratio as well as present Al species on catalytic properties will be discussed.
Tapping mode AFM (TM-AFM) is a standard technique to image biomolecules and cells avoiding damage to susceptible samples.
For preparing AFM samples we fixed (untreated and radiated) plasmids chemically on ultra-smooth mica silanized with APTES.
The recorded AFM images were examined concerning the contour length, the conformation and the writhing number of the plasmids.
We found that the measured contour length is in accordance with the number of base pairs. Apart from that, we indicate different structures of plasmids from our AFM images, which were assigned to our plasmid data from agarose gel-electrophoresis.
One-part-geopolymers, produced by addition of water to a mixture of solid silica and sodium alumi-nate, are a less exhaustively studied approach to form geopolymeric binders. Depending on the silica source, the reaction products show significant amounts of zeolite Na-A besides amorphous compounds. Previously, 29Si MAS NMR has been used to analyze the chemical structure of such one-part geopolymers, having crystalline structures and amorphous phases (Q2, Q3, Q4).
In this work, pure zeolites and three different one-part-geopolymers cured for 1 day were investigated by 29Si-27Al TRAPDOR NMR. It was used to identify aluminum phases in overlapping silicon sites. Zeolites Na-X (Si/Al=1.4) and Na-Y (Si/Al=2.7) served as model systems to measure the TRAPDOR effect of the structural units Q4(mAl). Both materials show several Q4(mAl) signals, which are all separated by their chemical shifts. The more aluminum surrounds the silicon tetrahedron the higher are the normalized TRAPDOR difference signals (S0/∆S). The intensity ratios between Q4(mAl) to Q4({m-1}Al) of these signals is fixed but vary slightly between both zeolites. These results are transferred to the complex geopolymer structure.
Many microorganisms possess circular molecules of plasmid DNA. Their conformation may vary from more compact to relaxed forms. Structural changes have important consequences for the physiological role of plasmids and will influence plasmid transcription, replication and their susceptibility to environmental stresses. Radiation is a common form of stress and can cause structural damage to DNA such as single (SSB) and double strand breaks (DSB). Recently, it has been indicated that secondary low-energy electrons play an important role in biological damage under vacuum condition. Therefore, our studies focus on irradiating the plasmid pUC19 with low-energy electrons for the first time under physiological conditions.
N4-acetyl-SMX is the most important cross-reacting compound for the SMX-ELISA with concentrations of 1064 - 2488 ng/L in influent wastewater and 40 - 160 ng/L in effluent wastewater.
The ELISAgrams for estrone show less interfering signals than for SMX.
ELISAgrams of SMX and estrone display in effluent wastewater more interfering signals than in influent wastewater.
Pyrotechnic smoke generators fall under the Directive 2013/29/EU in Europe and could potentially belong to all categories except consumer fireworks. These types are especially present in the field of “Other Pyrotechnic Articles” of the categories P1 and P2, e.g. as simulation devices for paintball or airsoft gaming. The specific users of these products are aware of the corresponding smoke liberation during use and usually wear protective equipment to minimize exposure to potentially harmful aerosols. However, such products are often misused against the labelling requirements in locations where these articles are not supposed to be used, like football stadiums and demonstrations. In contrast to the intended use, uninvolved third parties are likely exposed to these reaction products without proper protective equipment. This study aims at identifying the transient particle size range of the aerosols emitted during the functioning of such common smoke generators for simulation purposes. In total four different types of articles were investigated, with five colors per type (white, blue, green, red, orange). Results show that the majority of the particles were emitted in a range between 40 nm and 350 nm, with some variation depending on the smoke color. Particles with diameters of less than 100 nm are generally of specific concern, as they can penetrate the alveolar system of the human lungs and therefore present a specific hazard.
In 2011, the German Association of Engineers (VDI) started working on a set of guidelines towards increased resource efficiency. These guidelines represent a framework that defines resource efficiency and outlines considerations for the producing industry. A special guideline for SMEs is included as well as guidelines on methodologies for evaluating resource use indicators, such as the cumulative raw material demand of products and production systems. Resource efficiency, defined here as the ratio of specific quantifiable use to natural resource consumption, can be evaluated by defining a function which expresses the specific use and quantifies the resource requirements through a set of indicators (use of raw materials, energy, water, land and ecosystem services including sinks). The results from this also depend on the system boundary parameters and the allocation rules for by-products and waste treatment options. Optimising resource use is possible at all stages of a product’s or production system’s life cycle chain (raw material extraction, production and manufacturing, use and consumption, and the end-of-life stage). VDI guidelines are widely accepted across Germany’s industrial sector and therefore represent an important means of mainstreaming resource efficiency in this target area. As well as providing a methodological framework, the guidelines describe strategies and measures towards increasing resource efficiency, and they enable industrial producers and service providers to identify potential areas of improvement. The full article presents an overview of the methodology and contents of these guidelines and discusses their impact in achieving absolute reductions in the industrial use of natural resources.
In the last several decades, the rural exodus has led to an increasing number of inhabitants in the urban areas. The increased building and infrastructural construction caused the transformation of the landscape and to an increased land sealing in these areas. Consequently, the increased land sealing influences the air temperatures in the cities, since houses, streets and squares heat up continuously. As a result, the city and metropolitan areas became significantly warmer than their surroundings - the effect is known as Urban Heat Island (UHI). These changes have a negative impact for the quality of life. To deal with the negative effects of UHI, a high level of technical and financial effort is necessary. The costs caused by the UHI effects are in the range of several billion US dollars worldwide per year. The recent studies on UHI showed that the established methods like parks and green spaces or bright coatings for roof areas will soon not be able to effectively cope with the UHI effect in urban areas. Therefore there is a need for additional methods to mitigate UHI effect in the cities. The streets, sidewalks and squares represent approximately 30% to 40% of the inner cities areas. If these areas are designed functionally, they can have a significant impact on the UHI. This contribution focuses on development of a concrete paving stone with self-cooling properties. For the cooling effect the evaporative cooling is used. The paving stone is able to store large quantities of water and deliver during appropriate environmental conditions. This paper deals with the results of the long-term experiments on the test-fields under different climatic conditions. To interpret the test-field-results, laboratory tests were carried out as well. The paper presents and discuss the obtained results, and points out the difficulties occurred.
In 2011, the German Association of Engineers (VDI) started working on a set of guidelines dealing with the improvement of resource efficiency. These guidelines represent a framework that defines resource efficiency and outlines proposals for the producing industry. A special guideline for small and medium-sized enterprises (SMEs) is included as well as guidelines on methodologies for evaluating resource use indicators, such as the cumulative raw material demand of products and production systems. The work on resource use indicators is still in progress. The evaluation of raw materials expenditure will include water, soil and land use. The model will include the availability of raw materials (criticality). Improving resource efficiency at the end-of-life stage is illustrated in this paper by the example of materials recovery from waste, here from residues out of municipal solid waste incineration (MSWI). With mechanical treatment valuable materials like ferrous and non-ferrous metals and secondary construction material can be extracted from MSWI bottom ash. The potential contribution on the resource efficiency is discussed.
The reliable characterization of subsurface contamination of spatially extended contaminated sites is a challenging task, especially with an unknown history of land use. Conventional technologies often fail due to temporal and financial constraints and thus hinder the redevelopment of abandoned areas in particular. Here we compare two site screening techniques that can be applied quickly at relatively low cost, namely Direct Push (DP)-based groundwater sampling and tree core sampling. The effectiveness of both methods is compared for a rural megasite contaminated with chlorinated hydrocarbons. Unexpected pollution hot spots could be identified using both of these methods, while tree coring even enabled the delineation of the contaminant plume flowing into an adjacent wetland inaccessible for DP units. Both methods showed a good agreement in revealing the spatial pattern of the contamination. The correlation between groundwater concentrations and equivalent concentrations in wood was linear and highly significant for trichloroethene. Correlation was less obvious for its metabolite cis-dichloroethene, but still significant. As outcome of our study we recommend tree coring and for initial screening in combination with a DP sampling to retrieve quantitative data on groundwater pollutants in order to assess the contamination situation of a non- or only partly investigated site. The subsequent placement of monitoring wells for long-term monitoring of contamination levels is recommended. A combination of methods would achieve more relevant information at comparable or possibly even lower efforts in comparison to a conventional site investigation.
This report supports the implementation of European regulations on biocidal products for the product types 7, 9 and 10. Emission of active substances from material preservatives into environmental compartments can occur due precipitation. Risk characterisations have to be based on estimations of environmental concentrations of target substances leached from material preservatives. Harmonised test procedures are required to predict environmental impact due to leaching. Seventeen treated articles, mainly paints, but also a textile, sealing tapes and sealing masses were investigated by intermittent contact to water to prove suitability of the proposed laboratory test procedure. Parameters that affect leaching of active substances were examined.
Further development of a semi-analytical model to describe laboratory leaching data revealed that the model can be improved if changes of the leachability of substances during the test are supposed and integrated. Six paints and a textile were exposed to weathering to compare results from laboratory and field experiments. Similarities between leaching processes in both test approaches were observed. Generally, emissions of active substances are considerably higher in laboratory tests than from vertically installed test specimens exposed to weathering. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. In addition, the influence of meteorological parameters on leaching processes was investigated. Factors besides the amount of driving rain were identified that effect leaching processes by complex interaction. Relations between laboratory and field data were analysed, and the applicability of the semi-analytical model was tested for field data. Guidance documents for leaching tests under laboratory and field conditions were drafted and discussed with experts on EU Level workshop 3./4. July 2014, BAM, Berlin), and are included in this Report.
Improving resource efficiency at the end-of-life stage is illustrated in this paper by the example of materials recovery from waste, here from residues out of municipal solid waste incineration (MSWI). With mechanical treatment valuable materials like ferrous and non-ferrous metals and secondary construction material can be extracted from MSWI bottom ash. The potential contribution on the resource efficiency will be discussed.
In order to estimating the amount and kind of emissions from polymeric sporting tracks a laboratory test was developed in BAM that combines artificial weathering and subsequent batch and column tests [1, 2, 3]. The goal consisted in nvestigating a possible change of emissions into soil and groundwater of a new sporting ground as a function of ageing and egradation of the system. At various stages of the weathering, the samples were removed and subjected to especially designed column extraction tests for the solid samples. Both these extracts and the accumulated rainwater run-off of the weathering device were subjected to analytical tests of their ingredients. The overall aim of the test consisted in developing ontrollable, reproducible, and standardisable conditions and methods of investigation that would allow an estimation of the emissions in the course of outdoor application of about five years.
Determining a pore structure’s mechanical and chemical data on lime rendering exposed
outdoors and including masonry in the laboratory, with regard to their behaviour on moisture
transport and weathering was the objective. In search of clues for a dose-response relation -
i.e. upon a connection between the emission rate of SO2 and NOx on one hand and the degree
of damage to mainly plaster having a lime component on the other - it has been of interest to
what extent their structural characteristics including pore space are modified and so
consequently also physico-technical properties and chemical composition. For determining
corresponding criteria, a widely diversified spectrum of test methods such as to obtain data
concerning porosity and moisture transport, mechanical behaviour, and chemistry as well is
available. A description of the manufacture of plate-shaped rendering specimens with lime
putty, industrially hydrated lime and dolomitic hydrate (the last two also having a cement
admixture) and also hydraulic lime as binding agents is included. First deposition velocity and
absorption rate for SO2 were determined in laboratory tests on these materials in dry and
moist states. After their exposure on outdoor racks at six locations in the Berlin region with
differing SO2 atmospheric contents over at least 5 years, the samples of course show timedependent
modifications of chemical and physical qualities which are especially reflected in
the form of profiles of structure, strength and concentration, e.g. for sulphate. Local climatic
differences, however, partly exert a greater influence on material than emissions. Similar
investigations were performed on samples of comparable composition exposed 4 and 17
years. But the real surprise is furnished by the renderings’ behaviour depending upon
orientation and upon height at a building. Since weathering behaviour and moisture transport
(absorption, storage, release) are directly interdependent, further criteria are necessary for a
critical assessment of a plasters’ pore structure. Starting from sands, plasters were
characterized. The structural parameters were lastly influenced by the respective contents of
sand, binder and mixing water. These results and those gained from bricks naturally find their
expression in masonry sections manufactured there from, and above all in their capillary and
evaporative behaviours, and also when applying different test liquids. Summary and cited
literature is given at the end of this report.