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Patrick Sturm, Leben mit dem Tod in den Reichsstädten Esslingen, Nördlingen und Schwäbisch Hall, Epidemien und deren Auswirkungen vom frühen 15. bis zum frühen 17. Jahrhundert (Esslinger Studien, Schriftenreihe 23), Ostfildern: Thorbecke 2014. 502 S. ISBN 978-3-7995-0538-3. € 29,90

This work focuses on the low temperature fabrication process of InN thin films via microwave plasma-assisted reactive high power impulse magnetron sputtering (MAR-HiPIMS). The influence of microwave plasma on the HiPIMS discharge process at various nitrogen flows and microwave powers was monitored and characterised through in situ diagnostics, including following HiPIMS I(V,t) curves, optical emission spectroscopy (OES), as well as performing time-resolved Langmuir probe and time-of-flight mass spectroscopy (ToF-MS) measurements. This was followed by the deposition of InN films via standard reactive HiPIMS (reference sample) and MAR-HiPIMS and their characterisation via X-ray diffraction (XRD), reflectometry (XRR), as well as scanning and transmission electron microscopy (SEM, TEM). It was found that the microwave plasma facilitates the dissoci-ation/activation of nitrogen species and supplies seed electrons to the magnetron discharge plasma. Furthermore, the energy of the incoming ions was determined via ToF-MS, and it was possible to identify their plasma origin and temporal behaviour. The produced R-HiPIMS sample was highly metallic, with no nitride phase detected. The MAR-HiPMS film, however, was stoichiometric and exhibited (0002) direction texturing, with an optical bandgap of approx. 1.5 eV, electron concentration of 2.72 x 1020 cm -3 and electron mobility of 7.16 cm2V- 1s- 1 (in the range for polycrystalline InN).

Within the project SealWasteSafe, we advance construction materials and monitoring concepts of sealing structures applied for underground disposal of nuclear or toxic waste. As these engineered barriers have high demands concerning integrity, an innovative alkali-activated material (AAM) is improved and tested on various laboratory scales. This AAM has low reaction kinetics related to a preferential slow release of the heat of reaction in comparison to alternative salt concretes based on Portland cement or magnesium oxychloride cements. Hence, crack formation due to thermally induced strain is reduced. After successful laboratory scale analysis (Sturm et al., 2021), the AAM is characterised on a larger scale by manufacturing test specimens (100–300 L). Conventional salt concrete (DBE, 2004) and the newly developed AAM are compared using two specimen geometries, i.e. cylindrical and cuboid. A comprehensive multisensor monitoring scheme is developed to compare the setting process of AAM and salt concrete for these manufactured specimens. The analysed parameters include temperature and humidity of the material, acoustic emissions, and strain variations. Passive sensor systems based on radiofrequency identification technology (RFID) embedded in the concrete, enable wireless access to temperature and humidity measurements and are compared to conventional cabled systems. Additionally, fibre-optic sensors (FOS) are embedded to record strain, but also have potential to record temperature and moisture conditions. Part of this project aims at demonstrating the high reliability of sensors and also their resistance to highly alkaline environments and to water intrusion along cables or at sensor locations. Further technical improvements were implemented so that first results clearly show the scalability of the setting process from previous small-scale AAM experiments and particularly the high potential of the newly developed approaches. Furthermore, ultrasonic methods are used for quality assurance to detect obstacles, potential cracks and delamination. On the one hand, both active and passive ultrasonic measurements complement the results obtained from the multisensor monitoring scheme for the produced specimens. On the other hand, the unique large aperture ultrasonic system (LAUS) provides great depth penetration (up to nearly 10 m) and can thus be applied at in situ sealing structures built as a test site in Morsleben by the Federal Company for Radioactive Waste Disposal (Bundesgesellschaft für Endlagerung, BGE) as shown by Effner et al. (2021). An optimised field lay-out identified from forward modelling studies and advanced imaging techniques applied to the measured data will further improve the obtained results. To characterise the inside of the test engineered barrier and achieve a proof-of-concept, an ultrasonic borehole probe is developed to enable phased arrays that can further improve the detection of potential cracks. Modelling results and first analysis of semispherical specimens confirmed the reliability of the directional response caused by the phased arrays of the newly constructed ultrasonic borehole probe. Overall, the project SealWasteSafe improves the construction material, multisensor monitoring concepts and ultrasonics for quality assurance. This will help to develop safe sealing structures for nuclear waste disposal. The outcomes are particularly valuable for salt as a host rock but partly also transferrable to alternative conditions.

The 87Sr/86Sr isotope ratio can, in principle, be used for provenancing of cement. However, while commercial cements consist of multiple components, no detailed investigation into their individual 87Sr/86Sr isotope ratios or their influence on the integral 87Sr/86Sr isotope ratio of the resulting cement was conducted previously. Therefore, the present study aimed at determining and comparing the conventional 87Sr/86Sr isotope ratios of a diverse set of Portland cements and their corresponding Portland clinkers, the major component of these cements. Two approaches to remove the additives from the cements, i.e. to measure the conventional 87Sr/86Sr isotopic fingerprint of the clinker only, were tested, namely, treatment with a potassium hydroxide/sucrose solution and sieving on a 11-µm sieve. Dissolution in concentrated hydrochloric acid/nitric acid and in diluted nitric acid was employed to determine the 87Sr/86Sr isotope ratios of the cements and the individual clinkers. The aim was to find the most appropriate sample preparation procedure for cement provenancing, and the selection was realised by comparing the 87Sr/86Sr isotope ratios of differently treated cements with those of the corresponding clinkers. None of the methods to separate the clinkers from the cements proved to be satisfactory. However, it was found that the 87Sr/86Sr isotope ratios of clinker and cement generally corresponded, meaning that the latter can be used as a proxy for the clinker 87Sr/86Sr isotope ratio. Finally, the concentrated hydrochloric acid/nitric acid dissolution method was found to be the most suitable sample preparation method for the cements; it is thus recommended for 87Sr/86Sr isotope analyses for cement provenancing. Graphical abstract

Ulrike Leuschner, Briefe der Liebe. Henriette von der Malsburg und Georg Ernst von und zu Gilsa 1765 bis 1767 (Veröffentlichungen der Historischen Kommission für Hessen, Bd. 46, Kleine Schriften, Bd. 15), Marburg: 2018. 272 S. ISBN 978-3-942225-41-0. Ln. € 28,–

Additive manufacturing of alkali-activated materials currently attracts a lot of attention, because of the possibility to produce customized high-performance elements for a range of applications, potentially being more resource-efficient than conventionally produced parts. Here, we describe a new additive manufacturing process for alkali-activated materials that is based on selective laser-heating of lithium aluminate/microsilica slurries. The new process-material combination allows to manufacture elements with complex geometries at high building rates and high accuracy. The process is versatile and transferrable to structures of sizes differing by orders of magnitude. The mechanical strength of the obtained materials was in the range of values reported for conventional metakaolin-based geopolymers, and superior to what has been hitherto reported for alkali-activated materials produced by additive manufacturing. This mechanical performance was obtained despite the fact that the degree of reaction of the lithium aluminate and the microsilica was low, suggesting that significant reactions took place only at the surface of the microsilica particles.

Due to environmental concerns regarding the use of Portland cement as the principal binder material in concrete and mortar it is imperative to identify alternative materials that could reduce the carbon footprint of the construction industry. One alternative to address these issues is the use of alkali activated materials, in particular, when based on waste streams that currently have no or only limited industrial application. This paper reports a preliminary study into the synthesis of geopolymer mortar utilizing Brown Coal Fly Ash. The ash had a CaO content of ~39%, indicating that synthesis at ambient or low temperature may be feasible. The paper reports initial trials on the effect of curing temperature, ambient to 120 °C, on the mechanical properties of the mortars produced. The results showed that ambient cured mortar achieved a compressive strength of 6.5 MPa at 3 days. A curing temperature of 60 °C gave the optimum results with a compressive strength of almost 20 MPa and a flexural strength of 3.5 MPa obtained.

The influence of starting materials and synthesis route on the properties and the structure of cementitious sodium aluminosilicate gels is not fully understood, partly due their amorphous nature and the fact that they often contain residual reactants, which can make the results of single-pulse NMR spectroscopy applied to these materials difficult to interpret or ambiguous. To overcome some of these limitations, 29Si{27Al} TRAPDOR NMR as well as 27Al{29Si} and 27Al{1H} REDOR NMR spectroscopy were applied to materials synthesized by the one-part alkali-activation route from three different amorphous silica starting materials, including rice husk ash. The latter led to formation of a fully amorphous sodium aluminosilicate gel (geopolymer), while the materials produced from the other silicas contained amorphous phase and crystalline zeolites. Application of the double-resonance NMR methods allowed to identify hydrous alumina gel domains in the rice husk ash-based material as well as significantly differing amounts of residual silica in the three cured materials. Four-coordinated Al existed not only in the aluminosilicate gel framework but also in a water-rich chemical environment with only a small amount of Si in proximity, likely in the alumina gel or possibly present as extra-framework Al in the aluminosilicate gel. The results demonstrate how the employment of different silica starting materials determines the phase assemblage of one-part alkali-activated materials, which in turn influences their engineering properties such as the resistance against chemically/biologically aggressive media.

Geopolymer-zeolite composites were synthesized using a silica-rich industrial byproduct from chlorosilane production and sodium aluminate. Pastes were cured at 80 °C and 80% RH, and subsequently dried in two different climates: at 23 °C and 50% RH, and under vacuum. 1H MAS, 23Na MAS and 29Si MAS NMR and XRD measurements were performed after the drying procedures as well as after subsequent aging. Zeolite Na-A was found beside traces of faujasite-type zeolite and zeolite EMT as major crystalline phases in the cured composites; the fraction of geopolymeric gel in the reaction products was determined to be ~18% on a molar basis. Various water species could be distinguished using 1H MAS and 1H-29Si CP MAS NMR, applying rotor-synchronized echo experiments. The largest fraction of the pore water resides in the α-cages of the zeolite Na-A and in the geopolymeric gel; in addition, water exists in the β-cages of the zeolites and adsorbed at sodium ions. The water species in α-cages and in the pores of the geopolymeric gel exhibit slightly different chemical shifts of 4.7 ppm and 4.9 ppm, respectively, in the 1H MAS NMR spectra. Changes of the water content in the geopolymer pores of differently dried samples were observed and led to slightly varied chemical shifts in the 29Si MAS NMR spectra too. Measurements after more than 500 days revealed no significant aging effects of the composites, which confirm their chemical stability.

Two brick clays (rich in 2:1 clay minerals) and a low-grade kaolinitic clay were studied regarding their transformations during calcination and their performance in blended cement mortars. The mortars with calcined clays exhibited decreased workability (slump flow), but this effect could be mitigated by employment of a conventional superplasticizer; however, compressive strength of the hardened mortar was lowered in some cases. While the kaolinitic clay generally yielded the highest strength, the performance of a brick clay could be increased by grinding to higher fineness and by mixing it with the kaolinitic clay.

The use of calcined clays as supplementary cementitious materials (SCMs) has been identified as a viable option to decrease the CO2 emissions related to cement production. However, while extensive data is available about kaolinitic clays in this context, other clays such as illitic clays appear to be under-studied. Therefore, in the present study, two illitic clays were compared to two low-grade kaolinitic clays in terms of transformations in the calcination temperature range 650–900 °C, and performance of the calcined clays in blended cement pastes as measured by strength evolution, heat release, hydrated phase formation and portlandite consumption. The illitic clays required a higher calcination temperature for complete dehydroxylation of their illite than what is necessary for dehydroxylation of kaolinite. These higher calcination temperatures also led to particle sintering, significantly decreasing the specific surface area of the illitic clays, particularly for the clay with the higher Fe2O3 content. Nevertheless, while the kaolinitic clays generally exhibited the best performance as SCM, the illitic clay with lower Fe2O3 content performed similar to the kaolinitic clays when calcined at optimum temperature and applied at a moderate substitution rate. These findings demonstrate that several different clays have the potential to be used as SCM and indicate possible routes to identify suitable deposits for this purpose.

Concrete structures for sealing of tunnels in the host rock are an essential part of systems for nuclear waste storage. However, concretes based on blended cements or magnesium oxychloride cements, which are commonly considered for this application, can deteriorate severely due to a significant heat of hydration and associated deformation and cracking. Alkali-activated materials (AAMs) offer a potential solution to this problem because of their low heat release during hardening. To explore their suitability for the construction of sealing structures in evaporite rock, various AAMs with salt aggregate were studied regarding fresh properties, heat release, mechanical properties and microstructure. The heat of reaction of the AAMs was up to 55% lower than that of a blended cement designed for sealing structures, indicating significant benefits for the intended application. Other relevant properties such as mechanical strength and permeability depended strongly on the mix-design of the AAMs and curing conditions.

While calcined clays in general have been credited with a great potential to mitigate CO2 emissions related to cement production and consumption, calcined brick clays are currently understudied in this regard. In the present work, two brick clays, a low-grade kaolinitic clay, and a mixed clay composed of 50% brick clay and 50% low-grade kaolinitic clay were studied regarding transformations on calcination, and strength and durability performance as well as pore structure of mortars made with the blended cements. All calcined clays exhibited pozzolanic reactivity, with the performance of the brick clays inferior to the low-grade kaolinitic clay. However, the mixed clay performed very similar to the low-grade kaolinitic clay, which points to a viable option for optimal use of brick clays in cementitious systems. The carbonation resistance of the blended cement mortars was generally worse than that of the plain Portland cement mortar, as expected, but the former exhibited a significantly improved chloride penetration resistance. The latter improvement was due to pore structure refinement in the blended cement mortars, compared to the Portland cement mortar.

One-part geopolymers were synthesized from two different silica materials (a silica-rich residue from chlorosilane production and a commercial microsilica) and sodium aluminate at three different SiO2/Al2O3 ratios and a nominal water/solids ratio of 0.5. The degree of reaction of the silica in the cured geopolymers (i.e. the fraction of silica dissolved to form aluminosilicates and minor products) was determined using two different methods: chemical attack with HCl to dissolve the reaction products and evaluation of peak areas of 29Si MAS NMR spectra. It was found that the degree of reaction of the silica decreases with increasing the silica content of the starting mix, and that it is almost constant after 1 day of curing and almost independent from the kind of starting silica. From the results of the NMR-based method, the mean SiO2/Al2O3 ratio of the reaction products (aluminosilicates and minor products) can be estimated to be ca. 2.0, nearly independent of the starting composition of the geopolymers. The dissolution method is biased, but of sufficient precision to be useful for following changes of the degree of reaction. Major crystalline phases in the cured geopolymers are zeolite A and/or hydrosodalite. Depending on the starting composition, the relative amounts of these zeolites vary; additionally, sodalite (only for the residue from chlorosilane production with >1 wt% Cl-), faujasite, and zeolite EMT can appear in the geopolymers. The 29Si and 27Al MAS NMR results indicate mainly Si(4Al) and Al(4Si) sites, in line with the presence of zeolite A, hydrosodalite, sodalite, and geopolymeric gel of comparatively low SiO2/Al2O3 ratio.

Above- and belowground processes in plants are tightly coupled via carbon and water fluxes through the soil-plant-atmosphere system. The oxygen isotopic composition of atmospheric CO₂ and water vapour (H₂Ov) provides a valuable tool for investigating the transport and cycling of carbon and water within this system. However, detailed studies on the coupling between ecosystem components and environmental drivers are sparse. Therefore, we conducted a H2 (18)O-labelling experiment to investigate the effect of drought on the speed of the link between below- and aboveground processes and its subsequent effect on C(18)OO released by leaves and soils. A custom-made chamber system, separating shoot from soil compartments, allowed separate measurements of shoot- and soil-related processes under controlled conditions. Gas exchange of oxygen stable isotopes in CO₂ and H₂Ov served as the main tool of investigation and was monitored in real time on Fagus sylvatica saplings using laser spectroscopy. H₂(18)O-labelling showed that drought caused a slower transport of water molecules from soil to shoot, which was indicated by its direct derivation from independently measured concentrations and (18)O/(16)O ratios of CO₂ and H₂Ov, respectively. Furthermore, drought reduced the (18)O equilibrium between H₂O and CO₂ at the shoot level, resulting in less-enriched C(18)OO fluxes from leaf to atmosphere compared with control plants. Compared with the shoot, (18)O equilibrium was not instantaneous in the soil and no drought effect was apparent.

Journal of Experimental Botany, 65 (6), ISSN:1460-2431, ISSN:0022-0957

Field measurements of photosynthetic carbon isotope discrimination ((13)Δ) of Fagus sylvatica, conducted with branch bags and laser spectrometry, revealed a high variability of (13)Δ, both on diurnal and day-to-day timescales. We tested the prediction capability of three versions of a commonly used model for (13)Δ [called here comprehensive ((13)(Δcomp)), simplified ((13) Δsimple) and revised ((13)(Δrevised)) versions]. A Bayesian approach was used to calibrate major model parameters. Constrained estimates were found for the fractionation during CO(2) fixation in (13)(Δcomp), but not in (13)(Δsimple), and partially for the mesophyll conductance for CO(2)(gi). No constrained estimates were found for fractionations during mitochondrial and photorespiration, and for a diurnally variable apparent fractionation between current assimilates and mitochondrial respiration, specific to (13)(Δrevised). A quantification of parameter estimation uncertainties and interdependencies further helped explore model structure and behaviour. We found that (13)(Δcomp) usually outperformed (13)(Δsimple) because of the explicit consideration of gi and the photorespiratory fractionation in (13)(Δcomp) that enabled a better description of the large observed diurnal variation (≈9‰) of (13)Δ. Flux-weighted daily means of (13)Δ were also better predicted with (13)(Δcomp) than with (13)(Δsimple).

One-part geopolymers offer advantages over conventional geopolymers with regard to handling and storage of feedstocks. However, they often suffer from a low degree of reaction, a high amount of crystalline byproducts, and consequently low strength. In this study, one-part geopolymers were produced from rice husk ash (RHA) and sodium aluminate, and investigated by XRD, ATR-FTIR, SEM and compressive strength testing. The compressive strength of the material was ∼30 MPa, i.e. significantly higher than for comparable one-part geopolymers. This is attributed to an almost complete reaction of the RHA and the absence of crystalline byproducts (zeolites) in the hardened geopolymer.

This contribution presents the results of structural and compressive strength investigations on cured and high-temperature treated silica-based one-part geopolymer-zeolite composites. The specimens were synthesized from two different silica sources, sodium aluminate and water. The phase content as well as the compressive strength of the cured composites varied depending on the starting mix-design and the silica feedstock. Besides geopolymeric gel, A-type zeolites and hydrosodalites were the major reaction products. One of the silica feedstocks yielded significantly higher compressive strength (19 MPa), while the other one appears to cause less variation in phase content. Strength testing indicated an improvement on heating up to 200–400 °C (28 MPa) followed by a moderate decrease up to 700 °C. Above 700 °C the systems underwent new phase formation and shrinkage (volume decrease) deformations. After exposure at 1000 °C the different mixes consisted of a mix of several stuffed silica phases, almost pure hexagonal nepheline or amorphous phase. Depending on the mix-design, the onset temperature of the high temperature phase transformations varied.

Stable isotope measurements of the biosphere–atmosphere CO2 exchange can be used to constrain carbon budget estimates on different spatial and temporal scales. Eddy covariance (EC) measurements can provide a direct measure of the isotope flux ratio of CO2 and thus indicate the ecosystem fingerprint on the isotope budget of the atmosphere. For the first time we report on EC flux measurements of stable CO2 isotopologues over a forest canopy. We used a quantum cascade laser absorption spectrometer (QCLAS, Aerodyne Research Inc.) for the simultaneous measurement of 12CO2, 13CO2 and CO18O isotopologue fluxes with a sampling rate of 10 Hz over the Lageren mixed forest site in Switzerland during an intensive field campaign in 2008. The total CO2 flux measured with the closed-path QCLAS matches well the half-hourly fluxes measured with a conventional open-path infrared gas analyzer (R2 = 0.988). The 18O isotope discrimination is strongly reduced after precipitation events, reflecting 18O isotope exchange of CO2 with water in various water pools of the ecosystem. The 13CO2/12CO2 flux ratio is surprisingly constant on a diurnal timescale, but the substantial random noise in the half-hourly EC flux ratio puts a limit on resolving diurnal variations of only a few permil. Hence, we explore which component in our EC set-up is limiting the precision of the measured flux ratios. On the one hand we use data simulations to estimate the error contribution from the QCLAS instrument. On the other hand different EC data processing procedures are examined to quantify the uncertainty inherently associated with turbulent flux measurements and calculations. We show that the random error associated with EC data processing is of the same order of magnitude as the flux ratio uncertainty from the instrument precision. Therefore, a direct determination of ecosystem discrimination on hourly or diurnal time scales with the EC technique remains a challenge.

When conducting (13)CO(2) plant-soil pulse labelling experiments, tracer material might cause unwanted side effects which potentially affect δ(13)C measurements of soil respiration (δ(13)C(SR)) and the subsequent data interpretation. First, when the soil matrix is not isolated from the atmosphere, contamination of the soil matrix with tracer material occurs leading to a physical back-diffusion from soil pores. Second, when using canopy chambers continuously, (13)CO(2) is permanently re-introduced into the atmosphere due to leaf respiration which then aids re-assimilation of tracer material by the canopy. Accordingly, two climate chamber experiments on European beech saplings (Fagus sylvatica L.) were conducted to evaluate the influence of soil matrix (13)CO(2) contamination and canopy recycling on soil (13)CO(2) efflux during (13)CO(2) plant-soil pulse labelling experiments. For this purpose, a combined soil/canopy chamber system was developed which separates soil and canopy compartments in order to (a) prevent diffusion of (13)C tracer into the soil chamber during a (13)CO(2) canopy pulse labelling and (b) study stable isotope processes in soil and canopy individually and independently. In combination with laser spectrometry measuring CO(2) isotopologue mixing ratios at a rate of 1 Hz, we were able to measure δ(13)C in canopy and soil at very high temporal resolution. For the soil matrix contamination experiment, (13)CO(2) was applied to bare soil, canopy only or, simultaneously, to soil and canopy of the beech trees. The obtained δ(13)C(SR) fluxes from the different treatments were then compared with respect to label re-appearance, first peak time and magnitude. By determining the δ(13)C(SR) decay of physical (13)CO(2) back-diffusion from bare soils (contamination), it was possible to separate biological and physical components in δ(13)C(SR) of a combined flux of both. A second pulse labelling experiment, with chambers permanently enclosing the canopy, revealed that (13)CO(2) recycling at canopy level had no effect on δ(13)C(SR) dynamics.

Recent (13) CO(2) canopy pulse chase labeling studies revealed that photosynthesis influences the carbon isotopic composition of soil respired CO(2) (δ(13) C(SR)) even on a diel timescale. However, the driving mechanisms underlying these short-term responses remain unclear, in particular under drought conditions. The gas exchange of CO(2) isotopes of canopy and soil was monitored in drought/nondrought-stressed beech (Fagus sylvatica) saplings after (13) CO(2) canopy pulse labeling. A combined canopy/soil chamber system with gas-tight separated soil and canopy compartments was coupled to a laser spectrometer measuring mixing ratios and isotopic composition of CO(2) in air at high temporal resolution. The measured δ(13) C(SR) signal was then explained and substantiated by a mechanistic carbon allocation model. Leaf metabolism had a strong imprint on diel cycles in control plants, as a result of an alternating substrate supply switching between sugar and transient starch. By contrast, diel cycles in drought-stressed plants were determined by the relative contributions of autotrophic and heterotrophic respiration throughout the day. Drought reduced the speed of the link between photosynthesis and soil respiration by a factor of c. 2.5, depending on the photosynthetic rate. Drought slows the coupling between photosynthesis and soil respiration and alters the underlying mechanism causing diel variations of δ(13) C(SR).

Atmospheric O2 and CO2 flask measurements from the high altitude research station Jungfraujoch, Switzerland, and from the observatory at Puy de Dôme, France, are presented. Additionally, the Jungfraujoch δ13C record of CO2 is discussed. The observations on flask samples collected at the Jungfraujoch station show, since 2003, an enhancement of the oxygen trend which amounts to about 45 per meg/year with a corresponding CO2 increase of around 2.4 ppm/year. This enhancement is comparable with that observed at the Puy de Dôme station where oxygen, since mid 2002, has decreased with a rate of about 50 per meg/year whilst the CO2 increase was of around 1.7 ppm/year but exhibiting a higher variability. Several processes influence δO2/N2. However, these processes are marked with different oxidation ratios (O2:CO2) that can be used to distinguish them. The apparent slopes calculated from correlation plots between de-trended CO2 and δO2/N2 records as well as between corresponding trends are significantly larger than the observed terrestrial exchange and fossil fuel emission slopes indicating a strong oceanic influence. Since ocean–atmosphere exchange can have very variable O2:CO2 ratios depending on processes within the ocean, it is to our understanding the only possibility to explain our observations. The stability of the δO2/N2 scale is critical in this regard, therefore, it is addressed here and we found no significant scale drift which would influence our trend calculations. In our view more important are criterions on the data selection before trend analysis.

The biophysical properties of native cardiac erg1 and recombinant HERG1 channels have been shown to be influenced by the extracellular K(+) concentration ([K(+)](o)). The erg1 conductance, for example, increases dramatically with a rise in [K(+)](o). In the brain, where local [K(+)](o) can change considerably with the extent of physiological and pathophysiological neuronal activity, all three erg channel subunits are expressed. We have now investigated and compared the effects of an increase in [K(+)](o) from 2 to 10 mm on the three rat erg channels heterologously expressed in CHO cells. Upon increasing [K(+)](o), the voltage dependence of activation was shifted to more negative potentials for erg1 (DeltaV(0.5) = -4.0 +/- 1.1 mV, n = 28) and erg3 (DeltaV(0.5) = -8.4 +/- 1.2 mV, n = 25), and was almost unchanged for erg2 (DeltaV(0.5) = -2.0 +/- 1.3 mV, n = 6). For all three erg channels, activation kinetics were independent of [K(+)](o), but the slowing of inactivation by increased [K(+)](o) was even more pronounced for erg2 and erg3 than for erg1. In addition, with increased [K(+)](o), all three erg channels exhibited significantly slower time courses of recovery from inactivation and of deactivation. Whole-cell erg-mediated conductance was determined at the end of 4 s depolarizing pulses as well as with 1 s voltage ramps starting from the fully activated state. The rise in [K(+)](o) resulted in increased conductance values for all three erg channels which were more pronounced for erg2 (factor 3-4) than for erg1 (factor 2.5-3) and erg3 (factor 2-2.5). The data demonstrate that most [K(+)](o)-dependent changes in the biophysical properties are well conserved within the erg K(+) channel family, despite gradual differences in the magnitude of the effects.

Above- and belowground processes in plants are tightly coupled via carbon and water fluxes through the soil-plant-atmosphere system. The oxygen isotopic composition of atmospheric CO₂ and water vapour (H₂Ov) provides a valuable tool for investigating the transport and cycling of carbon and water within this system. However, detailed studies on the coupling between ecosystem components and environmental drivers are sparse. Therefore, we conducted a H2 (18)O-labelling experiment to investigate the effect of drought on the speed of the link between below- and aboveground processes and its subsequent effect on C(18)OO released by leaves and soils. A custom-made chamber system, separating shoot from soil compartments, allowed separate measurements of shoot- and soil-related processes under controlled conditions. Gas exchange of oxygen stable isotopes in CO₂ and H₂Ov served as the main tool of investigation and was monitored in real time on Fagus sylvatica saplings using laser spectroscopy. H₂(18)O-labelling showed that drought caused a slower transport of water molecules from soil to shoot, which was indicated by its direct derivation from independently measured concentrations and (18)O/(16)O ratios of CO₂ and H₂Ov, respectively. Furthermore, drought reduced the (18)O equilibrium between H₂O and CO₂ at the shoot level, resulting in less-enriched C(18)OO fluxes from leaf to atmosphere compared with control plants. Compared with the shoot, (18)O equilibrium was not instantaneous in the soil and no drought effect was apparent.

Pulse labelling experiments provide a common tool to study short-term processes in the plant-soil system and investigate below-ground carbon allocation as well as the coupling of soil CO(2) efflux to photosynthesis. During the first hours after pulse labelling, the measured isotopic signal of soil CO(2) efflux is a combination of both physical tracer diffusion into and out of the soil as well as biological tracer release via root and microbial respiration. Neglecting physical back-diffusion can lead to misinterpretation regarding time lags between photosynthesis and soil CO(2) efflux in grassland or any ecosystem type where the above-ground plant parts cannot be labelled in gas-tight chambers separated from the soil. We studied the effects of physical (13)CO(2) tracer back-diffusion in pulse labelling experiments in grassland, focusing on the isotopic signature of soil CO(2) efflux. Having accounted for back-diffusion, the estimated time lag for first tracer appearance in soil CO(2) efflux changed from 0 to 1.81±0.56 h (mean±SD) and the time lag for maximum tracer appearance from 2.67±0.39 to 9.63±3.32 h (mean±SD). Thus, time lags were considerably longer when physical tracer diffusion was considered. Using these time lags after accounting for physical back-diffusion, high nocturnal soil CO(2) efflux rates could be related to daytime rates of gross primary productivity (R(2)=0.84). Moreover, pronounced diurnal patterns in the δ(13)C of soil CO(2) efflux were found during the decline of the tracer over 3 weeks. Possible mechanisms include diurnal changes in the relative contributions of autotrophic and heterotrophic soil respiration as well as their respective δ(13)C values. Thus, after accounting for physical back-diffusion, we were able to quantify biological time lags in the coupling of photosynthesis and soil CO(2) efflux in grassland at the diurnal time scale.

Along with predicted climate change, increased risks for summer drought are projected for Central Europe. However, large knowledge gaps exist in terms of how drought events influence the short-term ecosystem carbon cycle. Here, we present results from 13CO2 pulse labeling experiments at an intensively managed lowland grassland in Switzerland. We investigated the effect of extreme summer drought on the short-term coupling of freshly assimilated photosynthates in shoots to roots as well as to soil CO2 efflux. Summer drought was simulated using rainout shelters during two field seasons (2010 and 2011). Soil CO2 efflux and its isotopic composition were measured with custom-built chambers coupled to a quantum cascade laser spectrometer (QCLAS-ISO, Aerodyne Research Inc., MA, USA). During the 90 min pulse labeling experiments, we added 99.9 atom % 13CO2 to the grass sward. In addition to the isotopic analysis of soil CO2 efflux, this label was traced over 31 days into bulk shoots, roots and soil. Drought reduced the incorporation of recently fixed carbon into the shoots, but increased the relative allocation of fresh assimilates below ground compared to the control grasslands. Contrary to our hypothesis, we did not find a change of allocation speed in response to drought. Although drought clearly reduced soil CO2 efflux rates, about 75% of total tracer uptake in control plots was lost via soil CO2 efflux during 19 days after pulse labeling, compared to only about 60% under drought conditions. Thus, the short-term coupling of above- and below-ground processes was reduced in response to summer drought. The occurrence of a natural spring drought in 2011 lead to comparable albeit weaker drought responses increasing the confidence in the generalizability of our findings.

We present the continuous data record of atmospheric CO2 isotopes measured by laser absorption spectroscopy for an almost four year period at the High Altitude Research Station Jungfraujoch (3580 m a.s.l.), Switzerland. The mean annual cycles derived from data of December 2008 to September 2012 exhibit peak-to-peak amplitudes of 11.0 μmol mol−1 for CO2, 0.60‰ for δ13C and 0.81‰ for δ18O. The high temporal resolution of the measurements also allow to capture variations on hourly and diurnal time scales. For CO2 the mean diurnal peak-to-peak amplitude is about 1 μmol mol−1 in spring, autumn and winter and about 2 μmol mol−1 in summer. The mean diurnal variability in the isotope ratios is largest during the summer months too, with an amplitude of about 0.1‰ both in the δ13C and δ18O, and a smaller or no discernible diurnal cycle during the other seasons. The day-to-day variability, however, is much larger and depends on the origin of the air masses arriving at Jungfraujoch. Backward Lagrangian particle dispersion model simulations revealed a close link between air composition and prevailing transport regimes and could be used to explain part of the observed variability in terms of transport history and influence region. A footprint clustering showed significantly different wintertime CO2, δ13C and δ18O values depending on the origin and surface residence times of the air masses. Based on the experiences gained from our measurements, several major updates on the instrument and the calibration procedures were performed in order to further improve the data quality. We describe the new measurement and calibration setup in detail and demonstrate the enhanced performance of the analyser. A precision of about 0.02‰ for both isotope ratios has been obtained for an averaging time of 10 min.

Recent advances in mid-IR laser and detector technologies increasingly allow for both ultra-compact and robust, field deployable analyzer developments. Highlights for unique real-world applications and novel instrumental developments are presented.

When conducting (13)CO(2) plant-soil pulse labelling experiments, tracer material might cause unwanted side effects which potentially affect δ(13)C measurements of soil respiration (δ(13)C(SR)) and the subsequent data interpretation. First, when the soil matrix is not isolated from the atmosphere, contamination of the soil matrix with tracer material occurs leading to a physical back-diffusion from soil pores. Second, when using canopy chambers continuously, (13)CO(2) is permanently re-introduced into the atmosphere due to leaf respiration which then aids re-assimilation of tracer material by the canopy. Accordingly, two climate chamber experiments on European beech saplings (Fagus sylvatica L.) were conducted to evaluate the influence of soil matrix (13)CO(2) contamination and canopy recycling on soil (13)CO(2) efflux during (13)CO(2) plant-soil pulse labelling experiments. For this purpose, a combined soil/canopy chamber system was developed which separates soil and canopy compartments in order to (a) prevent diffusion of (13)C tracer into the soil chamber during a (13)CO(2) canopy pulse labelling and (b) study stable isotope processes in soil and canopy individually and independently. In combination with laser spectrometry measuring CO(2) isotopologue mixing ratios at a rate of 1 Hz, we were able to measure δ(13)C in canopy and soil at very high temporal resolution. For the soil matrix contamination experiment, (13)CO(2) was applied to bare soil, canopy only or, simultaneously, to soil and canopy of the beech trees. The obtained δ(13)C(SR) fluxes from the different treatments were then compared with respect to label re-appearance, first peak time and magnitude. By determining the δ(13)C(SR) decay of physical (13)CO(2) back-diffusion from bare soils (contamination), it was possible to separate biological and physical components in δ(13)C(SR) of a combined flux of both. A second pulse labelling experiment, with chambers permanently enclosing the canopy, revealed that (13)CO(2) recycling at canopy level had no effect on δ(13)C(SR) dynamics.

In this study we present a combined soil/canopy chamber system that allows the investigation of carbon flow through the atmosphere-plant-soil system via a 13CO2 canopy labelling approach – especially when using short vegetation such as tree saplings. The developed chamber system clearly separates soil and canopy compartment in order to (a) prevent physical diffusion of 13C tracer into the soil chamber during a 13CO2 canopy pulse labelling (b) study stable isotope processes in soil and canopy individually and independently. In combination with novel laser spectrometry, measuring CO2 (Aerodyne Research Inc.) and H2O (Los Gatos Research Inc.) isotopologue mixing ratios at a rate of 1 Hz, we were able to trace the label transport from leaves to roots in small beech saplings (Fagus sylvatica L.) without interference due to contamination of the soil matrix and/or canopy re-labelling via tracer returning from soil respiration. A very tight coupling between above- (photosynthesis) and belowground (soil respiration) processes was found, where newly assimilated carbon fixed from the 13CO2 atmosphere re-appeared in soil respiration 2 h after it has been photosynthetically fixed. We were able to demonstrate that leaf metabolism acts on substrate for soil respiration on a diurnal timescale, with input of fresh photosynthates during daytime and starch re-mobilisation during nighttime. Long-term fluctuations in the δ13C of soil respiration, as observed under reduced water availability, could not be described by any biological or instrumental mechanism, as they did occur in an atypical ca. 15 hourly rhythm – potential mechanisms driving these fluctuations are hypothesized.

The successful 2d segmentation method CSC has recently been generalized to 3d. We shortly introduce the concept of both 2D- and 3D-CSC and present two use cases (classification of MR brain data and CT bone data) which demonstrate that analysis of segments generated by the CSC allows high quality classification of 3d data by relatively easy means.

The biophysical properties of native cardiac erg1 and recombinant HERG1 channels have been shown to be influenced by the extracellular K(+) concentration ([K(+)](o)). The erg1 conductance, for example, increases dramatically with a rise in [K(+)](o). In the brain, where local [K(+)](o) can change considerably with the extent of physiological and pathophysiological neuronal activity, all three erg channel subunits are expressed. We have now investigated and compared the effects of an increase in [K(+)](o) from 2 to 10 mm on the three rat erg channels heterologously expressed in CHO cells. Upon increasing [K(+)](o), the voltage dependence of activation was shifted to more negative potentials for erg1 (DeltaV(0.5) = -4.0 +/- 1.1 mV, n = 28) and erg3 (DeltaV(0.5) = -8.4 +/- 1.2 mV, n = 25), and was almost unchanged for erg2 (DeltaV(0.5) = -2.0 +/- 1.3 mV, n = 6). For all three erg channels, activation kinetics were independent of [K(+)](o), but the slowing of inactivation by increased [K(+)](o) was even more pronounced for erg2 and erg3 than for erg1. In addition, with increased [K(+)](o), all three erg channels exhibited significantly slower time courses of recovery from inactivation and of deactivation. Whole-cell erg-mediated conductance was determined at the end of 4 s depolarizing pulses as well as with 1 s voltage ramps starting from the fully activated state. The rise in [K(+)](o) resulted in increased conductance values for all three erg channels which were more pronounced for erg2 (factor 3-4) than for erg1 (factor 2.5-3) and erg3 (factor 2-2.5). The data demonstrate that most [K(+)](o)-dependent changes in the biophysical properties are well conserved within the erg K(+) channel family, despite gradual differences in the magnitude of the effects.

The Color Structure Code (CSC) [RE98] is a very efficient segmentation method for color images. It operates with a hierarchical region growing method. Originally, the CSC was constructed to work on two dimensional images. The generalization of the CSC for 3d images, is not a trivial task. Some important modifications of the original (2d) algorithm have to be done as the under lying 2-dimensional hierarchical hexagon topology cannot be generalized in all aspects to three dimensions.