Mercury speciation in contaminated soils by thermal release analysis

Thermal release analysis of mercury species in contaminated soils was performed by temperature controlled continuous heating of the samples in a furnace coupled to an Atomic Absorption Spectrophotometer (AAS). It was shown that this method allows the identification of different redox states of Hg-species through their characteristic releasing temperature ranges. The method was applied to Hg-contaminated samples from an inactive chlor-alkali production plant in former East Germany (GER), and from a gold mining area in Poconé, Mato Grosso, Brazil (BRA), as well as synthetic soil samples obtained by spiking pre-heated soil matrices (GER and BRA) with the following mercury species: Hg⁰, Hg₂Cl₂, HgCl₂, HgO and HgS. The samples GER, in general, frequently showed the presence of Hg²⁺ probably bound to humic substances, in the case of samples with higher total carbon content. Only in highly contaminated samples (>3000 ppm of mercury) was Hg⁰ the predominant species. The samples BRA more frequently showed the presence of mercury species in the lower oxidation states, i.e. Hg¹⁺ in combination with Hg⁰. The method allows observing changes in Hg-speciation in the samples with time, mainly changes among the oxidation states Hg⁰, Hg¹⁺ and Hg²⁺. The treated GER matrix showed a stronger tendency to oxidise Hf-species than the BRA treated matrix, in which only added Hg⁰ is partially oxidised to Hg²⁺ and Hg¹⁺. In contrast, the BRA matrix showed a pronounced tendency to reduce spiked Hg²⁺ to Hg¹⁺. This may be the reason for the presence of Hg¹⁺ in the majority of original BRA samples. The method appears to be very useful to study speciation of mercury and its dynamics. It can be used as a tool for monitoring mercury oxidation states and/or reactions of mercury in soils.     

Genetic structure and history of Swiss maize (<Emphasis Type="Italic">Zea mays</Emphasis> L. ssp. <Emphasis Type="Italic">mays</Emphasis>) landraces

Between 1930 and 2003 with emphasis on the 1940s maize landraces (Zea mays L. ssp. mays) from all over Switzerland were collected for maintenance and further use in a new Swiss breeding program. The genetic relationship and diversity among these accessions stored in the Swiss gene bank is largely unknown. Our hypothesis was that due to the unique geographic, climatic, and cultural diversity in Switzerland a diverse population of maize landraces had developed over the past three centuries. The aims were to characterize the genetic diversity of the Swiss landraces and their genetic relationship with accessions from neighbouring regions as well as reviewing their history, collection, and maintenance. The characterization and grouping was based on analyses with ten microsatellite markers. Geographic, cultural, and climatic conditions explained a division in two distinct groups of accessions. One group consisted of landraces collected in the southern parts of Switzerland. This group was related to the Italian Orange Flints. The other group contained accessions from northern Switzerland which were related to Northern European Flints in particular German Flints. Historic evidence was found for a frequent exchange of landraces within the country resulting in a lack of region-specific or landrace-specific genetic groups. The relatively large separation between the accessions, indicated by high F _ST (0.42), might be explained partly by a bottleneck during the collection and maintenance phase as well as by geographical and cultural separation of north and south of the country. Due to the high genetic diversity, the accessions here are a potential resource for broadening the European flint pool.     

Thermal and oxidation protection of carbon fiber by continuous liquid phase pre-ceramic coatings for high temperature application

Thermal and oxidation resistant coating is necessary for carbon fiber (CF) in CF reinforced concrete (CFRC) composite application in order to fulfil a high level of safety standard in case of fire. Pre-ceramic coatings such as Polysilazane, Polysiloxane, and Methyl silicone resin have been deposited on CF filament yarn by means of wet chemical continuous dip coating method. The surface analyses e.g. scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) results showed the changes of surface morphology by the coatings. Thermo gravimetric analysis (TGA) revealed that the high temperature (up to 800 °C) oxidation stability of CF was significantly improved with coatings. Thermo-mechanical properties also significantly enhanced up to 600 °C. CF yarn retains its original strength and elasticity modulus/stiffness at 700 °C due to thermal and oxidation resistant coatings.     

Mercury and methylmercury in sediments and suspended particles from the river Elbe,North Germany

Total Hg and McHg concentrations have been determined in sediments and suspended particulate matter from one of the most Hg-polluted rivers of the world, the Elbe river in Northern Germany. Results of total Hg and McHg are presented. Total Hg concentrations in suspended particulate matter (SPM) are 30 mg kg^?1 in the average and up to 150 mg kg^?1 as the maximum value. Total Hg-fluxes ^?1 calculated from measurements of an automatically operating station upstream Hamburg as about 17 ta?1 in suspended particles. A new McHg determination by HPLC chromatography and photometric detection was developed and verified. Methylmercury concentrations were up to 10% of the total Hg, i. e. 2.7 mg kg^?1 (dw).     

Surface functionalisation of UHMW polyethylene textile with atmospheric pressure plasma

Ultrahigh molecular weight polyethylene (UHMW PE) has high chemical resistance, good flexibility and remarkable strength along with low density, which makes it a good choice for lightweight textile reinforced composites. One drawback is the low melting point, limiting the possible applications at high temperatures. However its chemical structure leads to almost no chemical interactions of the interface. One way to enhance these interactions is the application of atmospheric pressure plasma. Polyethylene (PE) as yarn and in woven form was plasma treated in atmospheric air plasma generated by means of dielectric barrier discharge technique and the resulting effects on wettability, chemical composition and surface structure were studied. It was found that oxygen containing functional groups are introduced into the outer layer of the PE, thus increasing wettability and dyeability significantly. It could be shown that the changes last for at least 3 months in air without the necessity of any precautions. A degradation of the textile fibre during air plasma treatment was also observed, leading to a decrease of tensile strength and maximum elongation after more than five minutes of air plasma treatment.     

Wet-chemical silvering of inert polyethylene terephthalate yarn in a spool dyeing apparatus

Inert polyethylene terephthalate (PET) yarns, which were spooled crosswise onto a cylindrical dyeing bobbin, were silvered successfully with a wet-chemical method by using a newly developed one-bath method on a laboratory scale. In order to characterize the silver coating such as design, homogeneity, and crack formation, the surface morphology (SM) was analyzed using scanning electron microscopy (SEM). The chemical compositions of the surface (percentage of carbon, oxygen, nitrogen, silicium, and silver) were investigated with energy-dispersive x-ray spectroscopy (EDX). Furthermore, the testing of textile-chemical and textile-physical properties such as the washing-fastness, tensile strength, and electrical conductivity was carried out.     

Improvement of thermo-mechanical properties of basalt fiber using heat resistant polymeric coatings

Heat resistant coatings of textile materials are required so that they can fulfill the high security demand in the case of resistance to fire and improve thermo-mechanical properties. These coatings also enhance the interface properties of textiles in the composites. Liquid phase coatings, based on polysilazane and polysiloxane polymers were deposited onto the basalt fiber (BF) yarn using impregnation coating method. Tensile testing under thermal stress was conducted to examine the thermo-mechanical properties of both coated and uncoated yarns. The thermo-mechanical study indicated that the heat resistant coatings enhanced 40–70 % tensile strength and 25–40 % stiffness of original BF yarns up to 400 °C. BF yarn retained 65–90 % of its tensile strength at 500 °C due to coatings, whereas the uncoated BF yarn lost 85 % strength at this temperature. Thermo gravimetric analysis (TGA) showed that the coatings have good thermal stability. In addition, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, optical microscopy and fourier transform infrared (FTIR) spectroscopy analyses were executed in order to evaluate the surface microstructure as well as surface chemical compositions of the BF yarns.     

Differenzierte Erfassung der Bioaktivität von Pilzen und Bakterien zweier Böden unter Fichte

Differential determination of fungal- and bacterial bioactivity in two spruce forest ecosystems To determine the general bioactivity and the contribution of actinomycetes and fungi in organic and mineral horizons of two spruce forests (Luvic Cambisol and Dystric Podzoluvisol) different physiological methods were utilized and compared. According to microbial measurements (ATP-quantity, heat output) the activity in Ebersberger Forst surpassed that of Höglwald in each horizon. The measurements of ergosterol and chitin delivered contradictory results. A similarity between the amount of glucosamine and that of fluorescein diacetate hydrolysis was observed. In the activity of lignin degrading fungi and ethylene production both soils differed entirely.     

The role of humic substances in the aqueous mobilization of mercury from contaminated floodplain soils

The water-mobilizability of mercury from contaminated floodplain soils of the river Elbe in Northern Germany was evaluated by batch extraction experiments. It was shown that only a small amount of the total mercury present (about 1% per extraction) can be mobilized by water. This mercury is transported entirely in the form of a complex bound to humic acids (HA); particulates and fulvic acids (FA) did not seem to contribute to the process. It could not be removed from the HA even at pH 1, indicating an extremely strong complexation e.g. by sulfur-containing ligands. Furthermore, the influence of pH on the mobilization was investigated. It was found that in the range of natural pH-values, there was no observable effect of pH on the mobilization of either mercury or dissolved organic carbon (DOC). This surprising finding is explained by an unexpectedly high buffering capacity of the humics, both in the acidic and in the alkaline region. Only at extreme pH-values there was deviation from this behaviour. In contrast to other heavy metals, the amount of mobilized mercury decreases at pH < 3; and at pH > 12, an increased mobilization of mercury was observed because the humics are mobilized completely, accompanied by the total amount of mercury bound to them.     

Estimating Gaseous Mercury Emissions from Contaminated Floodplain Soils to the Atmosphere with Simple Field Measurement Techniques

The atmospheric emission of mercury (Hg) from a contaminatedwetlands system was studied in the floodplains along the riverElbe (Northern Germany). Results suggest that wetlands can beimportant transformation and phase transfer regions, linking theterrestrial, aquatic and atmospheric compartments of regionalbiogeochemical Hg cycles. Fluxes determined by flux chambermeasurements averaged 43 ± 5 ng m^-2 h^-1. Additionally,soil gas probe sampling was introduced to determine mercuryconcentrations in soil air. This technique shows some promise fordetecting and confining mercury contamination in soils. We alsopropose that measurements of total gaseous mercury (TGM) in soilair and the near-surface atmosphere, in combination with simplesoil physical parameters, may be suitable for calculatingsemiquantitative estimates of Hg evaporation from contaminatedsoils, based on laminar diffusion considerations. The results arecompared to other Hg flux measurements, and the advantages anddisadvantages of different approaches to quantify Hg emissionsfrom soils are discussed, especially with regard to possiblesystematic bias.