Wild bee monitoring in six agriculturally dominated landscapes of Saxony-Anhalt (Germany) in 2014

Wild bee species abundance based on combined flight traps (yellow funnels with perspex windows) placed at ecotones between semi-natural habitats and agricultural fields. Design: six agricultural dominated landscapes of 4x4 km with one trap per square km in Saxony-Anhalt (Germany), activity of traps in late spring-early summer (three sampling rounds) and late summer (three sampling rounds).

TERENO (Terrestrial Environmental Observatories) wild bee monitoring in six agriculturally dominated landscapes of Saxony-Anhalt (Germany)

In 2001 we started as part of the EU FP5 project Greenveins monitoring of insect communities in the normal landscape of Saxony-Anhalt (Germany), which is dominated by agricultural use. We selected four landscape sites of 4x4 km and recorded insects using combined flight traps, combining the ideas of window and yellow pan traps (see Duelli et al., 1999). Traps consist of a yellow funnel (25 cm diameter) filled with water (preserving agent added) and two perspex windows mounted in a way that they are crossed in the center. Within each square km of a site one trap was placed at ecotones between semi-natural habitats and agricultural fields (16 traps per site). Traps were operated in late spring-early summer (three sampling rounds) and late summer (three sampling rounds). Follow-up sampling started in 2010 as long-term monitoring within the TERENO project (www.tereno.net), contributing to the LTER network (Long-Term Ecosystem Research) in Germany (www.lter-d.de) and internationally as well (www.lter-europe.net). Metadata about the sites and related activities and data sets can be found in the DEIMS Repository for Research Sites and Datasets (https://data.lter-europe.net/deims/). In 2010 another two landscapes were added and yearly sampled in the same way. Due to long processing time of trapped insects data of follow-up years will be available about 18 months after trapping.

Wild bee monitoring in six agriculturally dominated landscapes of Saxony-Anhalt (Germany) in 2012

Wild bee species abundance based on combined flight traps (yellow funnels with perspex windows) placed at ecotones between semi-natural habitats and agricultural fields. Design: six agricultural dominated landscapes of 4x4 km with one trap per square km in Saxony-Anhalt (Germany), activity of traps in late spring-early summer (three sampling rounds) and late summer (three sampling rounds).

Wild bee monitoring in six agriculturally dominated landscapes of Saxony-Anhalt (Germany) in 2013

Wild bee species abundance based on combined flight traps (yellow funnels with perspex windows) placed at ecotones between semi-natural habitats and agricultural fields. Design: six agricultural dominated landscapes of 4x4 km with one trap per square km in Saxony-Anhalt (Germany), activity of traps in late spring-early summer (three sampling rounds) and late summer (three sampling rounds).

Splitting monoidal stable model categories

If C is a stable model category with a monoidal product then the set of homotopy classes of self-maps of the unit forms a commutative ring, [S,S]C. An idempotent e of this ring will split the homotopy category: [X,Y]C≅e[X,Y]C⊕(1−e)[X,Y]C. We prove that provided the localised model structures exist, this splitting of the homotopy category comes from a splitting of the model category, that is, C is Quillen equivalent to LeSC×L(1−e)SC and [X,Y]LeSC≅e[X,Y]C. This Quillen equivalence is strong monoidal and is symmetric when the monoidal product of C is.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Bumps and rings in a two-dimensional neural field: splitting and rotational instabilities

In this paper we consider instabilities of localised solutions in planar neural field firing rate models of Wilson-Cowan or Amari type. Importantly we show that angular perturbations can destabilise spatially localised solutions. For a scalar model with Heaviside firing rate function we calculate symmetric one-bump and ring solutions explicitly and use an Evans function approach to predict the point of instability and the shapes of the dominant growing modes. Our predictions are shown to be in excellent agreement with direct numerical simulations. Moreover, beyond the instability our simulations demonstrate the emergence of multi-bump and labyrinthine patterns. With the addition of spike-frequency adaptation, numerical simulations of the resulting vector model show that it is possible for structures without rotational symmetry, and in particular multi-bumps, to undergo an instability to a rotating wave. We use a general argument, valid for smooth firing rate functions, to establish the conditions necessary to generate such a rotational instability. Numerical continuation of the rotating wave is used to quantify the emergent angular velocity as a bifurcation parameter is varied. Wave stability is found via the numerical evaluation of an associated eigenvalue problem.

Research Update: Photoelectrochemical water splitting and photocatalytic hydrogen production using ferrites (MFe2O4) under visible light irradiation

The utilization of solar light for the photoelectrochemical and photocatalytic production of molecular hydrogen from water is a scientific and technical challenge. Semiconductors with suitable properties to promote solar-driven water splitting are a desideratum. A hitherto rarely investigated group of semiconductors are ferrites with the empirical formula MFe2O4 and related compounds. This contribution summarizes the published results of the experimental investigations on the photoelectrochemical and photocatalytic properties of these compounds. It will be shown that the potential of this group of compounds in regard to the production of solar hydrogen has not been fully explored yet.

Impacts of high-nitrate freshwater inputs on macrotidal ecosystems. I. Seasonal evolution of nutrient limitation for the diatom-dominated phytoplankton of the Bay of Brest (France)

The chemical factors (inorganic nitrogen, phosphate, silicic acid) that potentially or actually control primary production were determined for the Bay of Brest, France, a macrotidal ecosystem submitted to high-nitrate-loaded freshwater inputs (winter nitrate freshwater concentrations >700 mu M, Si:N molar ratio as low as 0.2, i.e. among the lowest ever published). Intensive data collection and observations were carried out from February 1993 to March 1994 to determine the variations of physical [salinity, temperature, photosynthetically active radiation (PAR), freshwater discharges] and chemical (oxygen and nutrients) parameters and their impacts on the phytoplankton cycle (fluorescence, pigments, primary production). With insufficient PAR the winter stocks of nutrients were almost nonutilized and the nitrate excess was exported to the adjacent ocean, due to rapid tidal exchange. By early April, a diatom-dominated spring bloom developed (chlorophyll a maximum = 7.7 mu g l(-1); primary production maximum = 2.34 g C m(-2) d(-1)) under high initial nutrient concentrations. Silicic acid was rapidly exhausted over the whole water column; it is inferred to be the primary limiting factor responsible for the collapse of the spring bloom by mid-May. Successive phytoplankton developments characterized the period of secondary blooms during summer and fall (successive surface chlorophyll a maxima = 3.5, 1.6, 1.8 and 1.0 mu g l(-1); primary production = 1.24, 1.18 and 0.35 g C m(-2) d(-1)). Those secondary blooms developed under lower nutrient concentrations, mostly originating from nutrient recycling. Until August, Si and P most likely limited primary production, whereas the last stage of the productive period in September seemed to be N limited instead, this being a period of total nitrate depletion in almost the whole water column. Si limitation of spring blooms has become a common feature in coastal ecosystems that receive freshwater inputs with Si:N molar ratios <1. The peculiarity of Si Limitation in the Bay of Brest is its extension through the summer period.

Splitting of a prevalent Mycobacterium bovis spoligotype by variable-number tandem-repeat typing reveals high heterogeneity in an evolving clonal group

Mycobacterium bovis populations in countries with persistent bovine tuberculosis usually show a prevalent spoligotype with a wide geographical distribution. This study applied mycobacterial interspersed repetitive-unit-variable-number tandem-repeat (MIRU-VNTR) typing to a random panel of 115 M. bovis isolates that are representative of the most frequent spoligotype in the Iberian Peninsula, SB0121. VNTR typing targeted nine loci: ETR-A (alias VNTR2165), ETR-B (VNTR2461), ETR-D (MIRU4, VNTR580), ETR-E (MIRU31, VNTR3192), MIRU26 (VNTR2996), QUB11a (VNTR2163a), QUB11b (VNTR2163b), QUB26 (VNTR4052), and QUB3232 (VNTR3232). We found a high degree of diversity among the studied isolates (discriminatory index [D] = 0.9856), which were split into 65 different MIRU-VNTR types. An alternative short-format MIRU-VNTR typing targeting only the four loci with the highest variability values was found to offer an equivalent discriminatory index. Minimum spanning trees using the MIRU-VNTR data showed the hypothetical evolution of an apparent clonal group. MIRU-VNTR analysis was also applied to the isolates of 176 animals from 15 farms infected by M. bovis SB0121; in 10 farms, the analysis revealed the coexistence of two to five different MIRU types differing in one to six loci, which highlights the frequency of undetected heterogeneity.

Design principles for maximizing photovoltage in metal-oxide-protected water-splitting photoanodes

Metal oxide protection layers for photoanodes may enable the development of large-scale solar fuel and solar chemical synthesis, but the poor photovoltages often reported so far will severely limit their performance. Here we report a novel observation of photovoltage loss associated with a charge extraction barrier imposed by the protection layer, and, by eliminating it, achieve photovoltages as high as 630mV, the maximum reported so far for water-splitting silicon photoanodes. The loss mechanism is systematically probed in metal-insulator-semiconductor Schottky junction cells compared to buried junction p(+) n cells, revealing the need to maintain a characteristic hole density at the semiconductor/insulator interface. A leaky-capacitor model related to the dielectric properties of the protective oxide explains this loss, achieving excellent agreement with the data. From these findings, we formulate design principles for simultaneous optimization of built-in field, interface quality, and hole extraction to maximize the photovoltage of oxide-protected water-splitting anodes.

Engineering interfacial silicon dioxide for improved metal-insulator-semiconductor silicon photoanode water splitting performance

Silicon photoanodes protected by atomic layer deposited (ALD) TiO2 show promise as components of water splitting devices that may enable the large-scale production of solar fuels and chemicals. Minimizing the resistance of the oxide corrosion protection layer is essential for fabricating efficient devices with good fill factor. Recent literature reports have shown that the interfacial SiO2 layer, interposed between the protective ALD-TiO2 and the Si anode, acts as a tunnel oxide that limits hole conduction from the photoabsorbing substrate to the surface oxygen evolution catalyst. Herein, we report a significant reduction of bilayer resistance, achieved by forming stable, ultrathin (<1.3 nm) SiO2 layers, allowing fabrication of water splitting photoanodes with hole conductances near the maximum achievable with the given catalyst and Si substrate. Three methods for controlling the SiO2 interlayer thickness on the Si(100) surface for ALD-TiO2 protected anodes were employed: (1) TiO2 deposition directly on an HF-etched Si(100) surface, (2) TiO2 deposition after SiO2 atomic layer deposition on an HF-etched Si(100) surface, and (3) oxygen scavenging, post-TiO2 deposition to decompose the SiO2 layer using a Ti overlayer. Each of these methods provides a progressively superior means of reliably thinning the interfacial SiO2 layer, enabling the fabrication of efficient and stable water oxidation silicon anodes.