Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe2O3 and Fe2O3-based solid superacids were studied. The reaction with alpha-Fe2O3 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the inital breakdown step was performed using alpha-Fe2O3, alpha-Fe2O3 preconverted to FeF3, and sulfate-promoted alpha-Fe2O3 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined

Analysing the temporal dynamics of model performance for hydrological models

The temporal dynamics of hydrological model performance gives insights into errors that cannot be obtained from global performance measures assigning a single number to the fit of a simulated time series to an observed reference series. These errors can include errors in data, model parameters, or model structure. Dealing with a set of performance measures evaluated at a high temporal resolution implies analyzing and interpreting a high dimensional data set. This paper presents a method for such a hydrological model performance assessment with a high temporal resolution and illustrates its application for two very different rainfall-runoff modeling case studies. The first is the Wilde Weisseritz case study, a headwater catchment in the eastern Ore Mountains, simulated with the conceptual model WaSiM-ETH. The second is the Malalcahuello case study, a headwater catchment in the Chilean Andes, simulated with the physics-based model Catflow. The proposed time-resolved performance assessment starts with the computation of a large set of classically used performance measures for a moving window. The key of the developed approach is a data-reduction method based on self-organizing maps (SOMs) and cluster analysis to classify the high-dimensional performance matrix. Synthetic peak errors are used to interpret the resulting error classes. The final outcome of the proposed method is a time series of the occurrence of dominant error types. For the two case studies analyzed here, 6 such error types have been identified. They show clear temporal patterns, which can lead to the identification of model structural errors

Invigorating hydrological research through journal publications

Over the past five years, the editors of a number of journals in the discipline of hydrology have met informally to discuss challenges and concerns in relation to the rapidly changing publishing landscape. Two of the previous meetings, in Götenborg in July 2013 and in Prague in June 2015, were followed by joint editorials (Blöschl et al. 2014; Koutsoyiannis et al. 2016) published in all participating journals. A meeting was convened in Vienna in April 2017 [during the General Assembly of the European Geosciences Union (EGU)] that was attended by 21 editors representing 14 journals. Even though the journals are published in very different settings, the editors found common cause in a vision of the editor’s role beyond just that of gatekeeper ensuring high-quality publications, to also being critical facilitators of scientific advances. In that enabling spirit, we as editors acknowledge the need to anticipate and adapt to the changing publishing landscape. This editorial communicates our views on the implications for authors, readers, reviewers, institutional assessors, and the community of editors, as discussed during the meeting and subsequently

Advancing catchment hydrology to deal with predictions under change

Throughout its historical development, hydrology as an earth science, but especially as a problem-centred engineering discipline has largely relied (quite successfully) on the assumption of stationarity. This includes assuming time invariance of boundary conditions such as climate, system configurations such as land use, topography and morphology, and dynamics such as flow regimes and flood recurrence at different spatio-temporal aggregation scales. The justification for this assumption was often that when compared with the temporal, spatial, or topical extent of the questions posed to hydrology, such conditions could indeed be considered stationary, and therefore the neglect of certain long-term non-stationarities or feedback effects (even if they were known) would not introduce a large error. However, over time two closely related phenomena emerged that have increasingly reduced the general applicability of the stationarity concept: the first is the rapid and extensive global changes in many parts of the hydrological cycle, changing formerly stationary systems to transient ones. The second is that the questions posed to hydrology have become increasingly more complex, requiring the joint consideration of increasingly more (sub-) systems and their interactions across more and longer timescales, which limits the applicability of stationarity assumptions. Therefore, the applicability of hydrological concepts based on stationarity has diminished at the same rate as the complexity of the hydrological problems we are confronted with and the transient nature of the hydrological systems we are dealing with has increased. The aim of this paper is to present and discuss potentially helpful paradigms and theories that should be considered as we seek to better understand complex hydrological systems under change. For the sake of brevity we focus on catchment hydrology. We begin with a discussion of the general nature of explanation in hydrology and briefly review the history of catchment hydrology. We then propose and discuss several perspectives on catchments: as complex dynamical systems, self-organizing systems, co-evolving systems and open dissipative thermodynamic systems. We discuss the benefits of comparative hydrology and of taking an information-theoretic view of catchments, including the flow of information from data to models to predictions. In summary, we suggest that these perspectives deserve closer attention and that their synergistic combination can advance catchment hydrology to address questions of change

Thermochemistry and Photochemistry in Cooler Hydrogen Dominated Extrasolar Planets: The Case of GJ436b

We introduce a new thermochemical kinetics and photochemical model. We use high-temperature bidirectional reaction rates for important H, C, O and N reactions (most importantly for CH$_4$ to CO interconversion), allowing us to attain thermochemical equilibrium, deep in an atmosphere, purely kinetically. This allows ab initio chemical modeling of an entire atmosphere, from deep-atmosphere thermochemical equilibrium to the photochemically dominated regime. We use our model to explore the atmospheric chemistry of cooler ($T_{eff} < 10^3$ K) extrasolar giant planets. In particular, we choose to model the nearby hot Neptune GJ436b, the only planet in this temperature regime for which spectroscopic measurements and estimates of chemical abundances now exist. Recent {\it Spitzer} measurements with retrieval have shown that methane is driven strongly out of equilibrium and is deeply depleted on the dayside of GJ 436b, whereas quenched carbon monoxide is abundant. This is surprising because GJ 436b is cooler than many of the heavily irradiated hot Jovians and thermally favorable for CH$_4$, and thus requires an efficient mechanism for destroying it. We include realistic estimates of ultraviolet flux from the parent dM star GJ 436, to bound the direct photolysis and photosensitized depletion of CH$_4$. While our models indicate fairly rich disequilibrium conditions are likely in cooler exoplanets over a range of planetary metallicities, we are unable to generate the conditions for substantial CH$_4$ destruction. One possibility is an anomalous source of abundant H atoms between 0.01-1 bars (which attack CH$_4$), but we cannot as yet identify an efficient means to produce these hot atoms

Inefficient induction of circulating TAA-specific CD8+ T-cell responses in hepatocellular carcinoma

Background & Aims: In hepatocellular carcinoma (HCC), CD8+ T-cell responses targeting tumor-associated antigens (TAA) are considered to be beneficial. However, the molecular profile of TAA-specific CD8+ T cells in HCC is not well defined due to their low frequency. Results: In this study, we demonstrate that TAA-specific CD8+ T-cell responses are not efficiently induced in the peripheral blood of HCC patients as supported by the following observations: First, in HCC patients, frequencies of TAA-specific CD8+ T cells were not increased compared to healthy donors (HD) or patients with liver cirrhosis. Second, a remarkable proportion of TAA-specific CD8+ T cells were naïve despite the presence of antigen within the tumor tissue. Third, antigen-experienced TAA-specific CD8+ T cells lack the characteristic transcriptional regulation of exhausted CD8+ T cells, namely EomeshiTbetdim, and express inhibitory receptors only on a minor proportion of cells. This suggests restricted antigen recognition and further supports the hypothesis of inefficient induction and activation. Methods: By applying peptide/MHCI tetramer-based enrichment, a method of high sensitivity, we now could define the heterogeneity of circulating TAA-specific CD8+ T cells targeting glypican-3, NY-ESO-1, MAGE-A1 and MAGE-A3. We focused on therapy-naïve HCC patients of which the majority underwent transarterial chemoembolization (TACE). Conclusion: Our analysis reveals that circulating TAA-specific CD8+ T cells targeting 4 different immunodominant epitopes are not properly induced in therapy-naïve HCC patients thereby unravelling new and unexpected insights into TAA-specific CD8+ T-cell biology in HCC. This clearly highlights severe limitations of these potentially anti-tumoral T cells that may hamper their biological and clinical relevance in HCC

Joint editorial: Invigorating hydrological research through journal publications

Editors of several journals in the field of hydrology met during the General Assembly of the European Geosciences Union – EGU in Vienna in April 2017. This event was a follow-up of similar meetings held in 2013 and 2015. These meetings enable the group of editors to review the current status of the journals and the publication process, and to share thoughts on future strategies. Journals were represented at the 2017 meeting by their editors, as shown in the list of authors. The main points on invigorating hydrological research through journal publications are communicated in this joint editorial published in the journals listed here