Michael Plötze

Microbial Fuel Cell Biosensor for In situ Assessment of Microbial Activity

Microbial fuel cell (MFC)-based sensing was explored to provide useful information for the development of an approach to in situ monitoring of substrate concentration and microbial respiration rate. The ability of a MFC to provide meaningful information about in situ microbial respiration and analyte concentration was examined in column systems, where Geobacter sulfurreducens used an external electron acceptor (an electrode) to metabolize acetate. Column systems inoculated with G. sulfurreducens were operated with influent media at varying concentrations of acetate and monitored for current generation. Current generation was mirrored by bulk phase acetate concentration, and a correlation (R(2)=0.92) was developed between current values (0-0.30 mA) and acetate concentrations (0-2.3 mM). The MFC-system was also exposed to shock loading (pulses of oxygen), after which electricity production resumed immediately after media flow recommenced, underlining the resilience of the system and allowing for additional sensing capacity. Thus, the electrical signal produced by the MFC-system provided real-time data for electron donor availability and biological activity. These results have practical implications for development of a biosensor for inexpensive real-time monitoring of in situ bioremediation processes, where MFC technology provides information on the rate and nature of biodegradation processes.

Weathering-associated bacteria from the Damma glacier forefield: physiological capabilities and impact on granite dissolution.

ABSTRACT Several bacterial strains isolated from granitic rock material in front of the Damma glacier (Central Swiss Alps) were shown (i) to grow in the presence of granite powder and a glucose-NH4Cl minimal medium without additional macro- or micronutrients and (ii) to produce weathering-associated agents. In particular, four bacterial isolates (one isolate each of Arthrobacter sp., Janthinobacterium sp., Leifsonia sp., and Polaromonas sp.) were weathering associated. In comparison to what was observed in abiotic experiments, the presence of these strains caused a significant increase of granite dissolution (as measured by the release of Fe, Ca, K, Mg, and Mn). These most promising weathering-associated bacterial species exhibited four main features rendering them more efficient in mineral dissolution than the other investigated isolates: (i) a major part of their bacterial cells was attached to the granite surfaces and not suspended in solution, (ii) they secreted the largest amounts of oxalic acid, (iii) they lowered the pH of the solution, and (iv) they formed significant amounts of HCN. As far as we know, this is the first report showing that the combined action of oxalic acid and HCN appears to be associated with enhanced elemental release from granite, in particular of Fe. This suggests that extensive microbial colonization of the granite surfaces could play a crucial role in the initial soil formation in previously glaciated mountain areas.

Structure and luminescence characteristics of quartz from pegmatites

Abstract Samples of pegmatite quartz from several localities in Norway and Namibia were investigated by cathodoluminescence (CL) microscopy and spectroscopy, electron paramagnetic resonance (EPR) measurements, and trace-element analysis (ICP-MS) to obtain information about their structure and luminescence characteristics. The defect structure and trace-element composition of the pegmatite quartz samples that were studied differ from those of quartz of other origin (hydrothermal, igneous and metamorphic quartz). EPR measurements reveal an almost complete lack of intrinsic lattice defects associated with O or Si vacancies (e.g., E’ center, O23- center), whereas some trace elements (Al, Ti, Ge, Li) are apparently enriched and form paramagnetic centers. The results indicate that there possibly is a redistribution of alkali ions during electron irradiation. The diamagnetic [AlO4/M+]0 center transforms into the paramagnetic [AlO4]0 center, while the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO4]0 and [TiO4]0 to form paramagnetic centers ([TiO4/Li+]0, [GeO4/Li+]0). These defects result in a specific luminescence behavior, which is very similar for all samples. In general, quartz from pegmatites shows homogeneous CL without growth zoning or internal structures suggesting constant physicochemical conditions during crystal growth. The CL emission is dominated by a transient bluish-green CL, which disappears after 60.100 s of electron irradiation. The two main emission bands centered at 505 nm (2.45 eV) and 390 nm (3.18 eV) are probably related to alkali-compensated, trace-element centers in the quartz structure. Other CL emission bands, which are characteristic features of igneous, metamorphic, or hydrothermal quartz (e.g., at 450 nm = 2.75 eV, 580 nm = 2.14 eV, 650 nm = 1.91 eV) are almost completely lacking. This fact indicates that the defects responsible for these CL emissions are absent in pegmatite quartz.

Climatic cycles during a Neoproterozoic “snowball” glacial epoch

The profound glaciations of the Neoproterozoic Cryogenian period (ca. 850–544 Ma) represent an extreme climatic mode when, it is claimed, Earth was fully or almost completely covered with ice for millions of years. We show that the geochemistry and mineralogy of fine-grained Neoproterozoic sedimentary rocks in Oman are best explained by climatic oscillations that drove variations in the intensity of chemical weathering on contemporary land surfaces. The cold climate modes of the Cryogenian were therefore cyclical, punctuated with well-defined warm-humid interglacial periods. The hydrological cycle and the routing of sediment were active throughout the glacial epoch, which requires substantial open ocean water. This reconstruction represents a significantly different target for numerical climate models at this critical time in the evolution of Earths biosphere.

Alteration of clay minerals-gamma-irradiation effects on physicochemical properties

Abstract In the present work, the influence of gamma-irradiation (1.1 MGy, 60 Co) on physicochemical parameters (“crystallinity”, specific surface, cation exchange capacity, main layer charge) of various clay minerals (montmorillonite, illite and samples of the serpentine–kaolin group) were investigated. The influence of gamma-irradiation on the physicochemical properties is generally weak. A reduction of lattice iron during irradiation could be measured, which causes decreasing values of cation exchange capacity (CEC) and main layer charge of the smectites. A weak loss of “crystallinity” of kaolinite could be observed. The results show that the structure of clay minerals is stable even at high gamma-irradiation doses.

Pioneering fungi from the Damma glacier forefield in the Swiss Alps can promote granite weathering.

Fungi were isolated from fine granitic sediments, which were collected at 15 sampling points within a 20 m × 40 m area in front of the Damma glacier in the central Swiss Alps. From the 45 fungal isolates grown on nutrient-rich agar media at 4 °C, 24 isolates were selected for partial sequencing and identification based on the small subunit ribosomal DNA. Sequencing data revealed that the isolated fungi represented three fungal phyla and 15 species. The weathering potential of 10 of the 15 fungal species was tested with dissolution experiments using powdered granite material (<63 μm). The results showed that the zygomyceteous species Mucor hiemalis, Umbelopsis isabellina and Mortierella alpina dissolved the granite powder most efficiently due to the release of a variety of organic acids, mainly citrate, malate and oxalate. In particular, the high concentrations of Ca, Fe, Mg and Mn in the solutions clustered well with the high amounts of exuded citrate. This is the first report on fungi that were isolated from a non-vegetated glacier forefield in which the fungis capabilities to dissolve granite minerals were examined.

Thallium speciation and extractability in a thallium- and arsenic-rich soil developed from mineralized carbonate rock

We investigated the speciation and extractability of Tl in soil developed from mineralized carbonate rock. Total Tl concentrations in topsoil (0-20 cm) of 100-1000 mg/kg are observed in the most affected area, subsoil concentrations of up to 6000 mg/kg Tl in soil horizons containing weathered ore fragments. Using synchrotron-based microfocused X-ray fluorescence spectrometry (μ-XRF) and X-ray absorption spectroscopy (μ-XAS) at the Tl L3-edge, partly Tl(I)-substituted jarosite and avicennite (Tl2O3) were identified as Tl-bearing secondary minerals formed by the weathering of a Tl-As-Fe-sulfide mineralization hosted in the carbonate rock from which the soil developed. Further evidence was found for the sequestration of Tl(III) into Mn-oxides and the uptake of Tl(I) by illite. Quantification of the fractions of Tl(III), Tl(I)-jarosite and Tl(I)-illite in bulk samples based on XAS indicated that Tl(I) uptake by illite was the dominant retention mechanism in topsoil materials. Oxidative Tl(III)uptake into Mn-oxides was less relevant, probably because the Tl loadings of the soil exceeded the capacity of this uptake mechanism. The concentrations of Tl in 10 mM CaCl2-extracts increased with increasing soil Tl contents and decreasing soil pH, but did not exhibit drastic variations as a function of Tl speciation. With respect to Tl in contaminated soils, this study provides first direct spectroscopic evidence for Tl(I) uptake by illite and indicates the need for further studies on the sorption of Tl to clay minerals and Mn-oxides and its impact on Tl solubility in soils.

Adsorption of arsenic on polyaluminum granulate.

The kinetics and efficiencies of arsenite and arsenate removal from water were evaluated using polyaluminum granulates (PAG) with high content of aluminum nanoclusters. PAG was characterized to be meso- and macroporous, with a specific surface area of 35 ± 1 m(2) g(-1). Adsorption experiments were conducted at pH 7.5 in deionized water and synthetic water with composition of As-contaminated groundwater in the Pannonian Basin. As(III) and As(V) sorption was best described by the Freundlich and Langmuir isotherm, respectively, with a maximum As(V) uptake capacity of ~200 μmol g(-1) in synthetic water. While As(III) removal reached equilibrium within 40 h, As(V) was removed almost entirely within 20 h. Micro X-ray fluorescence and electron microscopy revealed that As(III) was distributed uniformly within the grain, whereas As(V) diffused up to 81 μm into PAG. The results imply that As(V) is adsorbed 3 times faster while being transported 10(5) times slower than As(III) in Al hydroxide materials.

Effect of slope aspect on transformation of clay minerals in Alpine soils

Abstract Two soil profile sequences on paragneiss debris in the Val di Rabbi (Northern Italy) along an altitude gradient ranging from 1200 to 2400 m a.s.l. were studied to evaluate the effect of aspect on the weathering of clay minerals. All the soils had a coarse structure, a sandy texture and a low pH. Greater weathering intensities of clay-sized phyllosilicates (greater content of smectites) were observed in soils on the north-facing slope. On the south-facing slope, smectite was found only in the surface horizon of the soil profile at the highest altitude. Hot citrate treatment of north-facing soils revealed the presence of low-charged 2:1 clay minerals, the expansion of which was hindered in the untreated state by interlayered polymers. However, the hot citrate treatment encountered some problems with the samples of the south-facing soils: as confirmed by Fourier transform infrared spectroscopy, the hot citrate treatment was unable to remove all interlayer Al polymers. The 2:1 phyllosilicates were not expanded by ethylene glycol solvation in several samples, although thermogravimetric analyses indicated the presence of clay minerals with interlayer H2O. At the same time, the collapse of clay minerals to 1.0 nm following K-saturation was evident. Theoretically, this should indicate that 2:1 phyllosilicates had no evident substitution of trioctahedral cations (Mg2+, Fe2+) by dioctahedral cations (Al3+ and Fe3+). X-ray diffraction analysis of the J060 region and determination of the layer charge of clay minerals by the long-chain (C18) alkylammonium ion, however, did not confirm this. A transformation from trioctahedral to dioctahedral species was observed and low-charge clay minerals (ξ ~ 0.30) were identified in the surface horizons of the southfacing sites. In the south-facing soils, the podzolization process was less pronounced because of a lower water flux through the soil and probably less complexing organic molecules that would remove the interlayer polymers. Besides the eluviation process, clay minerals underwent a process of ionic substitutions in the octahedral sheet that led to the reduction of the layer charge. This process was more obvious in the north-facing sites.

Effect of Soil Conditioners on the Pressure and Rate-Dependent Shear Strength of Different Clays

Tunneling using the earth pressure balance machines method in clayey soils requires the addition of conditioning chemicals to reduce the torque moment of the machine and to guarantee a safe and economical excavation process. Injection of foams and polymers at the cutter head of the tunnel boring machine with subsequent remolding in the pressure chamber transforms the excavated material into a deformable soil paste with preferably low strength and adhesion. The soil becomes more compressible and can develop viscous properties, such that the pressure and rate dependency of the shear strength of the mixtures are of major importance for the proper design and analysis of the tunneling processes. In this paper, the results of vane shear strength measurements on various conditioned clays and clay-sand mixtures at various shearing velocities and applied pressures are presented and analyzed. The results clearly show the effects of the chemicals used and also point out the differences in their efficiency depending on the clay mineralogy. This allows for an improved understanding of the working mechanisms of the chemicals.