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The largest uncertainty in projections of future sea-level change results from the potentially changing dynamical ice discharge from Antarctica. Basal ice-shelf melting induced by a warming ocean has been identified as a major cause for additional ice flow across the grounding line. Here we attempt to estimate the uncertainty range of future ice discharge from Antarctica by combining uncertainty in the climatic forcing, the oceanic response and the ice-sheet model response. The uncertainty in the global mean temperature increase is obtained from historically constrained emulations with the MAGICC-6.0 (Model for the Assessment of Greenhouse gas Induced Climate Change) model. The oceanic forcing is derived from scaling of the subsurface with the atmospheric warming from 19 comprehensive climate models of the Coupled Model Intercomparison Project (CMIP-5) and two ocean models from the EU-project Ice2Sea. The dynamic ice-sheet response is derived from linear response functions for basal ice-shelf melting for four different Antarctic drainage regions using experiments from the Sea-level Response to Ice Sheet Evolution (SeaRISE) intercomparison project with five different Antarctic ice-sheet models. The resulting uncertainty range for the historic Antarctic contribution to global sea-level rise from 1992 to 2011 agrees with the observed contribution for this period if we use the three ice-sheet models with an explicit representation of ice-shelf dynamics and account for the time-delayed warming of the oceanic subsurface compared to the surface air temperature. The median of the additional ice loss for the 21st century is computed to 0.07 m (66% range: 0.02-0.14 m; 90% range: 0.0-0.23 m) of global sea-level equivalent for the low-emission RCP-2.6 (Representative Concentration Pathway) scenario and 0.09 m (66% range: 0.04-0.21 m; 90% range: 0.01-0.37 m) for the strongest RCP-8.5. Assuming no time delay between the atmospheric warming and the oceanic subsurface, these values increase to 0.09 m (66% range: 0.04-0.17 m; 90% range: 0.02-0.25 m) for RCP-2.6 and 0.15 m (66% range: 0.07-0.28 m; 90% range: 0.04-0.43 m) for RCP-8.5. All probability distributions are highly skewed towards high values. The applied ice-sheet models are coarse resolution with limitations in the representation of grounding-line motion. Within the constraints of the applied methods, the uncertainty induced from different ice-sheet models is smaller than that induced by the external forcing to the ice sheets.
We present a dynamic equilibrium simulation of the ice sheet-shelf system on Antarctica with the Potsdam Parallel Ice Sheet Model (PISM-PIK). The simulation is initialized with present-day conditions for bed topography and ice thickness and then run to steady state with constant present-day surface mass balance. Surface temperature and sub-shelf basal melt distribution are parameterized. Grounding lines and calving fronts are free to evolve, and their modeled equilibrium state is compared to observational data. A physically-motivated calving law based on horizontal spreading rates allows for realistic calving fronts for various types of shelves. Steady-state dynamics including surface velocity and ice flux are analyzed for whole Antarctica and the Ronne-Filchner and Ross ice shelf areas in particular. The results show that the different flow regimes in sheet and shelves, and the transition zone between them, are captured reasonably well, supporting the approach of superposition of SIA and SSA for the representation of fast motion of grounded ice. This approach also leads to a natural emergence of sliding-dominated flow in stream-like features in this new 3-D marine ice sheet model.
The potential of ecological models for supporting environmental decision making is increasingly acknowledged. However, it often remains unclear whether a model is realistic and reliable enough. Good practice for developing and testing ecological models has not yet been established. Therefore, TRACE, a general framework for documenting a model's rationale, design, and testing was recently suggested. Originally TRACE was aimed at documenting good modelling practice. However, the word 'documentation' does not convey TRACE's urgency. Therefore, we re-define TRACE as a tool for planning, performing, and documenting good modelling practice. TRACE documents should provide convincing evidence that a model was thoughtfully designed, correctly implemented, thoroughly tested, well understood, and appropriately used for its intended purpose. TRACE documents link the science underlying a model to its application, thereby also linking modellers and model users, for example stakeholders, decision makers, and developers of policies. We report on first experiences in producing TRACE documents. We found that the original idea underlying TRACE was valid, but to make its use more coherent and efficient, an update of its structure and more specific guidance for its use are needed. The updated TRACE format follows the recently developed framework of model 'evaludation': the entire process of establishing model quality and credibility throughout all stages of model development, analysis, and application. TRACE thus becomes a tool for planning, documenting, and assessing model evaludation, which includes understanding the rationale behind a model and its envisaged use. We introduce the new structure and revised terminology of TRACE and provide examples. (C) 2014 Elsevier B.V. All rights reserved.
Improving the photochemical properties of molecular photoswitches is crucial for the development of light-responsive systems in materials and life sciences. ortho-Fluoroazobenzenes are a new class of rationally designed photochromic azo compounds with optimized properties, such as the ability to isomerize with visible light only, high photoconversions, and unprecedented robust bistable character. Introducing sigma-electron-withdrawing F atoms ortho to the N=N unit leads to both an effective separation of the n -> pi* bands of the E and Z isomers, thus offering the possibility of using these two transitions for selectively inducing E/Z iso-merizations, and greatly enhanced thermal stability of the Z isomers. Additional para-electron-withdrawing groups (EWGs) work in concert with ortho-F atoms, giving rise to enhanced separation of the n -> pi* transitions. A comprehensive study of the effect of substitution on the key photochemical properties of ortho-fluoroazobenzenes is reported herein. In particular, the position, number, and nature of the EWGs have been varied, and the visible light photoconversions, quantum yields of isomerization, and thermal stabilities have been measured and rationalized by DFT calculations.
Towards an understanding of climate proxy formation in the Chew Bahir basin, southern Ethiopian Rift
(2018)
Deciphering paleoclimate from lake sediments is a challenge due to the complex relationship between climate parameters and sediment composition. Here we show the links between potassium (K) concentrations in the sediments of the Chew Bahir basin in the Southern Ethiopian Rift and fluctuations in the catchment precipitation/evaporation balance. Our micro-X-ray fluorescence and X-ray diffraction results suggest that the most likely process linking climate with potassium concentrations is the authigenic illitization of smectites during episodes of higher alkalinity and salinity in the closed -basin lake, due to a drier climate. Whole-rock and clay size fraction analyses suggest that illitization of the Chew Bahir clay minerals with increasing evaporation is enhanced by octahedral Al-to-Mg substitution in the clay minerals, with the resulting layer charge increase facilitating potassium-fixation. Linking mineralogy with geochemistry shows the links between hydroclimatic control, process and formation of the Chew Bahir K patterns, in the context of well-known and widely documented eastern African climate fluctuations over the last 45,000 years. These results indicate characteristic mineral alteration patterns associated with orbitally controlled wet-dry cycles such as the African Humid Period (similar to 15-5 ka) or high-latitude controlled climate events such as the Younger Dryas (similar to 12.8-11.6 ka) chronozone. Determining the impact of authigenic mineral alteration on the Chew Bahir records enables the interpretation of the previously established pXRF-derived aridity proxy K and provides a better paleohydrological understanding of complex climate proxy formation.
Ventilator-induced lung injury is aggravated by antibiotic mediated microbiota depletion in mice
(2018)
BackgroundAntibiotic exposure alters the microbiota, which can impact the inflammatory immune responses. Critically ill patients frequently receive antibiotic treatment and are often subjected to mechanical ventilation, which may induce local and systemic inflammatory responses and development of ventilator-induced lung injury (VILI). The aim of this study was to investigate whether disruption of the microbiota by antibiotic therapy prior to mechanical ventilation affects pulmonary inflammatory responses and thereby the development of VILI.MethodsMice underwent 6-8weeks of enteral antibiotic combination treatment until absence of cultivable bacteria in fecal samples was confirmed. Control mice were housed equally throughout this period. VILI was induced 3 days after completing the antibiotic treatment protocol, by high tidal volume (HTV) ventilation (34ml/kg; positive end-expiratory pressure=2 cmH(2)O) for 4h. Differences in lung function, oxygenation index, pulmonary vascular leakage, macroscopic assessment of lung injury, and leukocyte and lymphocyte differentiation were assessed. Control groups of mice ventilated with low tidal volume and non-ventilated mice were analyzed accordingly.ResultsAntibiotic-induced microbiota depletion prior to HTV ventilation led to aggravation of VILI, as shown by increased pulmonary permeability, increased oxygenation index, decreased pulmonary compliance, enhanced macroscopic lung injury, and increased cytokine/chemokine levels in lung homogenates.ConclusionsDepletion of the microbiota by broad-spectrum antibiotics prior to HTV ventilation renders mice more susceptible to developing VILI, which could be clinically relevant for critically ill patients frequently receiving broad-spectrum antibiotics.
The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (T-H) of similar to 232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below T-H using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b(1)' and 1b(1)" peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important. (C) 2015 AIP Publishing LLC.
Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.
We report on oxygen K-edge soft x-ray emission spectroscopy from a liquid water jet at the Linac Coherent Light Source. We observe significant changes in the spectral content when tuning over a wide range of incident x-ray fluences. In addition the total emission yield decreases at high fluences. These modifications result from reabsorption of x-ray emission by valence-excited molecules generated by the Auger cascade. Our observations have major implications for future x-ray emission studies at intense x-ray sources. We highlight the importance of the x-ray pulse length with respect to the core-hole lifetime.
A cationic surfactant containing a spiropyrane unit is prepared exhibiting a dual-responsive adjustability of its surface-active characteristics. The switching mechanism of the system relies on the reversible conversion of the non-ionic spiropyrane (SP) to a zwitterionic merocyanine (MC) and can be controlled by adjusting the pH value and via light, resulting in a pH-dependent photoactivity: While the compound possesses a pronounced difference in surface activity between both forms under acidic conditions, this behavior is suppressed at a neutral pH level. The underlying switching processes are investigated in detail, and a thermodynamic explanation based on a combination of theoretical and experimental results is provided. This complex stimuli-responsive behavior enables remote-control of colloidal systems. To demonstrate its applicability, the surfactant is utilized for the pH-dependent manipulation of oil-in-water emulsions.
The water vapor-induced swelling, as well as subsequent phase-transition kinetics, of thin films of a diblock copolymer (DBC) loaded with different amounts of the salt NaBr, is investigated in situ. In dilute aqueous solution, the DBC features an orthogonally thermoresponsive behavior. It consists of a zwitterionic poly(sulfobetaine) block, namely, poly(4-(N-(3'-methacrylamidopropyl)-N, N-dimethylammonio) butane-1-sulfonate) (PSBP), showing an upper critical solution temperature, and a nonionic block, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), exhibiting a lower critical solution temperature. The swelling kinetics in D2O vapor at 15 degrees C and the phase transition kinetics upon heating the swollen film to 60 degrees C and cooling back to 15 degrees C are followed with simultaneous time-of-flight neutron reflectometry and spectral reflectance measurements. These are complemented by Fourier transform infrared spectroscopy. The collapse temperature of PNIPMAM and the swelling temperature of PSBP are found at lower temperatures than in aqueous solution, which is attributed to the high polymer concentration in the thin-film geometry. Upon inclusion of sub-stoichiometric amounts (relative to the monomer units) of NaBr in the films, the water incorporation is significantly increased. This increase is mainly attributed to a salting-in effect on the zwitterionic PSBP block. Whereas the addition of NaBr notably shifts the swelling temperature of PSBP to lower temperatures, the collapse temperature of PNIPMAM remains unaffected by the presence of salt in the films.
Ventral striatum and amygdala activity as convergence sites for early adversity and conduct disorder
(2017)
Childhood family adversity (CFA) increases the risk for conduct disorder (CD) and has been associated with alterations in regions of affective processing like ventral striatum (VS) and amygdala. However, no study so far has demonstrated neural converging effects of CFA and CD in the same sample. At age 25 years, functional MRI data during two affective tasks, i.e. a reward (N = 171) and a face-matching paradigm (N = 181) and anatomical scans (N = 181) were acquired in right-handed currently healthy participants of an epidemiological study followed since birth. CFA during childhood was determined using a standardized parent interview. Disruptive behaviors and CD diagnoses during childhood and adolescence were obtained by diagnostic interview (2–19 years), temperamental reward dependence was assessed by questionnaire (15 and 19 years).
CFA predicted increased CD and amygdala volume. Both exposure to CFA and CD were associated with a decreased VS response during reward anticipation and blunted amygdala activity during face-matching. CD mediated the effect of CFA on brain activity. Temperamental reward dependence was negatively correlated with CFA and CD and positively with VS activity. These findings underline the detrimental effects of CFA on the offspring's affective processing and support the importance of early postnatal intervention programs aiming to reduce childhood adversity factors.
Normally in paleoseismology, the study of the tectonic slip-rate is performed in trenches on the fault scarp, or by the estimation of fault movements from the geomorphic features. In this work, we have carried out a paleoseismic analysis of the Benis Fault, located in southeast Spain, combined with a geothermal analysis inside a deep cave related to the fault (-350 m). Thus, we have estimated the last earthquake magnitude and time of occurrence from evidence of ceiling collapse and displaced carbonate blocks inside a cave, which is developed across the fault. The magnitude was obtained from the application of the empirical relationship of the fault parameters and coseismic vertical displacement, yielding a value ranging between M 5.9 and M 6.5. Moreover, we dated this paleoearthquake by the paleontological record of a "Lynx pardinus spelaea", with an age of 65 +/- 18 ka BP. Additionally, we have measured the thermal profile of the Benis Cave (-350 m of depth), from single rock point temperature measurements during 2 years. The temperature profile shows three different parts inside the cave, the shallow heterogeneous thermal zone till 50 m depth; the homogeneous thermal zone 150 m till with constant temperature and the hetero-thermal deep zone, deeper than 150 m and till the deepest zone (350 m). Furthermore, we have estimated the Vertical Geothermal Gradient, 1.85 degrees C/100 m for the deepest zone (-150; -290 m). The temperature increases with depth, showing a reverse thermal profile in comparison with normal gradients in deep caves. Finally, we have calculated the heat flux of 0.46 mWm(2). (C) 2016 Elsevier Ltd and INQUA. All rights reserved.
The hyperthermal events of the Cenozoic, including the Paleocene-Eocene Thermal Maximum, provide an opportunity to investigate the potential effects of climate warming on marine ecosystems. Here, we examine the shallow benthic marine communities preserved in the late Cretaceous to Eocene strata on the Gulf Coastal Plain (United States). In stark contrast to the ecological shifts following the end-Cretaceous mass extinction, our data show that the early Cenozoic hyperthermals did not have a long-term impact on the generic diversity nor composition of the Gulf Coastal Plain molluscan communities. We propose that these communities were resilient to climate change because molluscs are better adapted to high temperatures than other taxa, as demonstrated by their physiology and evolutionary history. In terms of resilience, these communities differ from other shallow-water carbonate ecosystems, such as reef communities, which record significant changes during the early Cenozoic hyperthermals. These data highlight the strikingly different responses of community types, i.e., the almost imperceptible response of molluscs versus the marked turnover of foraminifera and reef faunas. The impact on molluscan communities may have been low because detrimental conditions did not devastate the entire Gulf Coastal Plain, allowing molluscs to rapidly recolonise vacated areas once harsh environmental conditions ameliorated.
The hyperthermal events of the Cenozoic, including the Paleocene-Eocene Thermal Maximum, provide an opportunity to investigate the potential effects of climate warming on marine ecosystems. Here, we examine the shallow benthic marine communities preserved in the late Cretaceous to Eocene strata on the Gulf Coastal Plain (United States). In stark contrast to the ecological shifts following the end-Cretaceous mass extinction, our data show that the early Cenozoic hyperthermals did not have a long-term impact on the generic diversity nor composition of the Gulf Coastal Plain molluscan communities. We propose that these communities were resilient to climate change because molluscs are better adapted to high temperatures than other taxa, as demonstrated by their physiology and evolutionary history. In terms of resilience, these communities differ from other shallow-water carbonate ecosystems, such as reef communities, which record significant changes during the early Cenozoic hyperthermals. These data highlight the strikingly different responses of community types, i.e., the almost imperceptible response of molluscs versus the marked turnover of foraminifera and reef faunas. The impact on molluscan communities may have been low because detrimental conditions did not devastate the entire Gulf Coastal Plain, allowing molluscs to rapidly recolonise vacated areas once harsh environmental conditions ameliorated.
From the surface exudates of Senecio roseiflorus fourteen known methylated flavonoids and one phenol were isolated and characterized. The structures of these compounds were determined on the basis of their spectroscopic analysis. The surface exudate and the flavonoids isolated showed moderate to good antiplasmodial activity with 5,4'-dihydroxy-7-dimethoxyflavanone having the highest activity against chloroquine-sensitive (D6) and resistant (W2) strains of Plasmodium falciparum, with IC50 values of 3.2 +/- 0.8 and 4.4 +/- 0.01 mu g/mL respectively.
It has long been appreciated that material chemistry and topology profoundly affect cell adhesion and migration. Here, aqueous poly(N- isopropyl acrylamide) nanogels are designed, synthesized and printed in form of colloidal arrays on glass substrates using wrinkled polydimethylsiloxane templates. Using low-temperature plasma treatment, nanogels are chemically grafted onto glass supports thus leading to highly stable nanogel layers in cell culture media. Liquid cell atomic force microscopy investigations show that surface-grafted nanogels retain their swelling behavior in aqueous media and that extracellular matrix protein coating do not alter their stability and topography. It is demonstrated that surface-grafted nanogels could serve as novel substrates for the analysis of cell adhesion and migration. Nanogels influence size, speed, and dynamics of focal adhesions and cell motility forcing cells to move along highly directional trajectories. Moreover, modulation of nanogel state or spacing serves as an effective tool for regulation of cell motility. It is suggested that nanogel arrays deposited on solid surfaces could be used to provide a precise and tunable system to understand and control cell migration. Additionally, such nanogel arrays will contribute to the development of implantable systems aimed at supporting and enhancing cell migration during, for instance, wound healing and tissue regeneration.
Vertical flow filters and vertical flow constructed wetlands are established wastewater treatment systems and have also been proposed for the treatment of contaminated groundwater. This study investigates the removal processes of volatile organic compounds in a pilot-scale vertical flow filter. The filter is intermittently irrigated with contaminated groundwater containing benzene, MTBE and ammonium as the main contaminants. The system is characterized by unsaturated conditions and high contaminant removal efficiency. The aim of the present study is to evaluate the contribution of biodegradation and volatilization to the overall removal of benzene and MTBE. Tracer tests and flow rate measurements showed a highly transient flow and heterogeneous transport regime. Radon-222, naturally occurring in the treated groundwater, was used as a gas tracer and indicated a high volatilization potential. Radon-222 behavior was reproduced by numerical simulations and extrapolated for benzene and MTBE, and indicated these compounds also have a high volatilization potential. In contrast, passive sampler measurements on top of the filter detected only low benzene and MTBE concentrations. Biodegradation potential was evaluated by the analysis of catabolic genes involved in organic compound degradation and a quantitative estimation of biodegradation was derived from stable isotope fractionation analysis. Results suggest that despite the high volatilization potential, biodegradation is the predominant mass removal process in the filter system, which indicates that the volatilized fraction of the contaminants is still subject to subsequent biodegradation. In particular, the upper filter layer located between the injection tubes and the surface of the system might also contribute to biodegradation, and might play a crucial role in avoiding the emission of volatilized contaminants into the atmosphere.
Reliable age models are fundamental for any palaeoclimate reconstruction. Available interpolation procedures between age control points are often inadequately reported, and very few translate age uncertainties to proxy uncertainties. Most available modeling algorithms do not allow incorporation of layer counted intervals to improve the confidence limits of the age model in question.
We present a framework that allows detection and interactive handling of age reversals and hiatuses, depth-age modeling, and proxy-record reconstruction. Monte Carlo simulation and a translation procedure are used to assign a precise time scale to climate proxies and to translate dating uncertainties to uncertainties in the proxy values. The presented framework allows integration of incremental relative dating information to improve the final age model. The free software package COPRA1.0 facilitates easy interactive usage.
Deciphering chemical mediators regulating specialized metabolism in a symbiotic cyanobacterium
(2022)
Genomes of cyanobacteria feature a variety of cryptic biosynthetic pathways for complex natural products, but the peculiarities limiting the discovery and exploitation of the metabolic dark matter are not well understood. Here we describe the discovery of two cell density-dependent chemical mediators, nostoclide and nostovalerolactone, in the symbiotic model strain Nostoc punctiforme, and demonstrate their pronounced impact on the regulation of specialized metabolism. Through transcriptional, bioinformatic and labeling studies we assigned two adjacent biosynthetic gene clusters to the biosynthesis of the two polyketide mediators. Our findings provide insight into the orchestration of specialized metabolite production and give lessons for the genomic mining and high-titer production of cyanobacterial bioactive compounds.